TWI531678B - Chemical conversion treatment plated steel plate and manufacturing method thereof - Google Patents
Chemical conversion treatment plated steel plate and manufacturing method thereof Download PDFInfo
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- TWI531678B TWI531678B TW101133526A TW101133526A TWI531678B TW I531678 B TWI531678 B TW I531678B TW 101133526 A TW101133526 A TW 101133526A TW 101133526 A TW101133526 A TW 101133526A TW I531678 B TWI531678 B TW I531678B
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- chemical conversion
- conversion treatment
- mass
- steel sheet
- film
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AQIRUZAFJNDMIS-UHFFFAOYSA-N carbonic acid ethene Chemical compound C=C.C=C.C=C.C=C.C(O)(O)=O AQIRUZAFJNDMIS-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KPSZWAJWFMFMFF-UHFFFAOYSA-N delta-Hexylen-alpha-carbonsaeure Natural products CC=CCCCC(O)=O KPSZWAJWFMFMFF-UHFFFAOYSA-N 0.000 description 1
- KPSZWAJWFMFMFF-NSCUHMNNSA-N delta-heptenoic acid Chemical compound C\C=C\CCCC(O)=O KPSZWAJWFMFMFF-NSCUHMNNSA-N 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- CHWMPPNDIBLYMB-UHFFFAOYSA-N n',n'-bis(prop-2-enyl)ethane-1,2-diamine Chemical compound NCCN(CC=C)CC=C CHWMPPNDIBLYMB-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate 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
- 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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Description
本發明是有關於一種耐候性、耐水性、皮膜密接性及加工性優異的化學轉化處理鍍Al系鋼板及其製造方法。 The present invention relates to a chemical conversion-treated Al-based steel sheet excellent in weather resistance, water resistance, film adhesion, and workability, and a method for producing the same.
鍍鋼板為了防止成形加工時的咬合而在其表面形成包含有機樹脂的化學轉化處理皮膜(例如參照專利文獻1、專利文獻2)。專利文獻1、專利文獻2中記載：在鋅系鍍鋼板的表面形成包含胺基甲酸酯樹脂等有機樹脂的化學轉化處理皮膜。如此藉由利用包含有機樹脂的化學轉化處理皮膜被覆鍍鋼板的表面，而不僅可提高耐咬合性，而且亦可提高耐蝕性或耐變色性等。 The plated steel sheet is formed with a chemical conversion treatment film containing an organic resin on the surface thereof in order to prevent seizure during molding (see, for example, Patent Document 1 and Patent Document 2). Patent Document 1 and Patent Document 2 describe that a chemical conversion treatment film containing an organic resin such as a urethane resin is formed on the surface of a zinc-based plated steel sheet. By coating the surface of the plated steel sheet with a chemical conversion treatment film containing an organic resin, the seizure resistance can be improved, and corrosion resistance, discoloration resistance, and the like can be improved.
另一方面，為了提高化學轉化處理鍍鋼板的耐候性，而使用耐候性優異的氟樹脂作為構成化學轉化處理皮膜的有機樹脂。如此為了提高耐候性而使用氟樹脂時，大多使用有機溶劑系氟樹脂組成物。但是，此種有機溶劑系氟樹脂組成物存在火災的危險性或有害性、大氣污染等的問題。 On the other hand, in order to improve the weather resistance of the chemical conversion-treated steel sheet, a fluororesin having excellent weather resistance is used as the organic resin constituting the chemical conversion treatment film. When a fluororesin is used in order to improve weather resistance, an organic solvent-based fluororesin composition is often used. However, such an organic solvent-based fluororesin composition has problems such as fire risk, harmfulness, and air pollution.
另外，亦提出各種水系氟樹脂組成物(例如參照專利文獻3)。但是此種水系氟樹脂組成物均必需高溫的燒接(例如180℃~230℃、參照專利文獻3)。此種高溫的燒接實際上無法實現現場的塗裝(通常使用風乾樹脂)，在加熱乾燥為主流的工廠生產線中亦不利。 Further, various water-based fluororesin compositions have also been proposed (for example, refer to Patent Document 3). However, such a water-based fluororesin composition is required to be sintered at a high temperature (for example, 180 ° C to 230 ° C, see Patent Document 3). Such high-temperature burning is practically impossible to achieve on-site coating (usually using air-dried resin), which is also disadvantageous in a factory line where heating and drying are mainstream.
而且，為了消除水系氟樹脂組成物的問題點，亦提出導入硬化性部位(有機官能基)而在低溫下亦可造膜的水 系氟樹脂組成物(例如參照專利文獻4)。但是，使有機官能基反應並硬化而得的皮膜，會導致優先自該硬化部發生耐候劣化，因此皮膜變成多孔質狀，而導致耐水性降低。另外，為了改善密接性而實施利用環氧系樹脂或胺基甲酸酯樹脂等的基底處理時，亦會導致有機樹脂優先發生耐候劣化，而導致皮膜密接性急遽降低。 Further, in order to eliminate the problem of the aqueous fluororesin composition, it is also proposed to introduce a curable portion (organic functional group) and to form a film at a low temperature. A fluororesin composition (for example, refer to Patent Document 4). However, the film obtained by reacting and hardening the organic functional group causes weathering deterioration to occur preferentially from the hardened portion, so that the film becomes porous and the water resistance is lowered. In addition, when the substrate is treated with an epoxy resin or a urethane resin in order to improve the adhesion, the organic resin is preferentially deteriorated in weather resistance, and the film adhesion is rapidly lowered.
專利文獻1：日本專利特開2005-15834號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2005-15834
專利文獻2：日本專利特開2005-206764號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2005-206764
專利文獻3：日本專利特開昭57-38845號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. SHO 57-38845
專利文獻4：日本專利特開平5-202260號公報 Patent Document 4: Japanese Patent Laid-Open No. Hei 5-202260
如上所述，藉由在鍍鋼板的表面形成包含有機樹脂的化學轉化處理皮膜，而可提高耐咬合性或耐蝕性、形成於其上的皮膜(塗膜)的密接性等。然而，形成包含有機樹脂的化學轉化處理皮膜的先前的化學轉化處理鍍鋼板，用作外包裝建材時，有耐候性不充分的情況。即，胺基甲酸酯樹脂等多數有機樹脂因紫外線而導致劣化，因此使用先前的化學轉化處理鍍鋼板作為外包裝建材時，有導致被覆鍍鋼板的表面的化學轉化處理皮膜隨著時間經過而消失的擔憂。若如此導致化學轉化處理皮膜消失，則有產生變色或鏽等而損及美觀的擔憂，因而作為外包裝建材欠佳。 As described above, by forming a chemical conversion treatment film containing an organic resin on the surface of the plated steel sheet, the seizure resistance or the corrosion resistance, the adhesion of the film (coating film) formed thereon, and the like can be improved. However, in the case of forming a chemical conversion treated plated steel sheet containing a chemical conversion treatment film of an organic resin, when it is used as an outer packaging building material, the weather resistance is insufficient. In other words, many organic resins such as urethane resins are deteriorated by ultraviolet rays. Therefore, when the chemical conversion-treated steel sheet is used as the outer packaging building material, the chemical conversion treatment film on the surface of the coated steel sheet may pass over time. Disappearing fears. If the chemical conversion treatment film disappears as described above, there is a concern that discoloration, rust, or the like may occur and the appearance is deteriorated, so that the outer packaging material is unsatisfactory.
提高此種化學轉化處理鍍鋼板的耐候性的方法認為有：使用耐候性優異的氟樹脂作為構成化學轉化處理皮膜 的有機樹脂。因此，本發明者進行了預備實驗：使用操作容易的水系氟樹脂的乳液在鍍鋼板的表面形成化學轉化處理皮膜。其結果是，藉由使用水系氟樹脂的乳液，而可提高耐紫外線性，但另一方面，導致造膜性、耐水性及皮膜密接性降低。本發明者的進一步研究的結果推測，這些品質的降低的原因是，製造水系氟樹脂的乳液時所使用的乳化劑(例如全氟辛酸銨鹽)殘存於化學轉化處理皮膜中(參照後述的參考實驗)。 A method for improving the weather resistance of such a chemical conversion-treated steel sheet is considered to be: using a fluororesin excellent in weather resistance as a chemical conversion treatment film Organic resin. Therefore, the inventors conducted preliminary experiments to form a chemical conversion treatment film on the surface of a plated steel sheet using an emulsion of an aqueous fluororesin which is easy to handle. As a result, the ultraviolet ray resistance can be improved by using the emulsion of the aqueous fluororesin, but on the other hand, the film forming property, the water resistance, and the film adhesion are lowered. As a result of further research by the present inventors, it is estimated that the reason for the decrease in the quality is that an emulsifier (for example, ammonium perfluorooctanoate) used in the production of an emulsion of a water-based fluororesin remains in the chemical conversion treatment film (refer to a reference experiment described later). .
如以上所述，形成包含有機樹脂的化學轉化處理皮膜的先前的化學轉化處理鍍鋼板，有耐候性不充分的情況。 另外，藉由使用水系氟樹脂作為有機樹脂，而可提高化學轉化處理鍍鋼板的耐候性(耐紫外線性)，但另一方面，會導致造膜性、耐水性及皮膜密接性降低，因此無法同時具有耐候性、耐水性及皮膜密接性。 As described above, the prior chemical conversion-treated plated steel sheet containing the chemical conversion treatment film containing the organic resin may have insufficient weather resistance. In addition, by using a water-based fluororesin as the organic resin, the weather resistance (UV resistance) of the chemical conversion-treated steel sheet can be improved, but on the other hand, the film forming property, the water resistance, and the film adhesion are lowered, so that it is impossible to At the same time, it has weather resistance, water resistance and film adhesion.
本發明的目的是提供具有包含有機樹脂的化學轉化處理皮膜，且耐候性、耐水性、皮膜密接性及加工性均優異的化學轉化處理鍍Al系鋼板。 An object of the present invention is to provide a chemical conversion-treated Al-based steel sheet having a chemical conversion treatment film containing an organic resin and excellent in weather resistance, water resistance, film adhesion, and workability.
本發明者發現，藉由使用導入了親水性官能基的高分子量的含氟樹脂作為有機樹脂，且利用4A族金屬化合物將這些含氟樹脂交聯，而可提高化學轉化處理皮膜的耐候性、耐水性及皮膜密接性，並進一步進行研究，從而完成了本發明。 The present inventors have found that by using a high molecular weight fluorine-containing resin having a hydrophilic functional group as an organic resin and crosslinking the fluorine-containing resin with a Group 4A metal compound, the weather resistance of the chemical conversion treatment film can be improved. The water resistance and the film adhesion were further studied, and the present invention was completed.
即，本發明的第一發明是關於以下的化學轉化處理鍍 Al系鋼板。 That is, the first invention of the present invention relates to the following chemical conversion treatment plating Al-based steel sheet.
[1]一種化學轉化處理鍍Al系鋼板，其包括：Al系合金鍍鋼板，其具有包含85質量%~99質量%的Al的Al系合金鍍敷層；化學轉化處理皮膜，其形成於上述Al系合金鍍鋼板的表面，並且膜厚為0.5 μm~10 μm，上述化學轉化處理皮膜包含：含氟樹脂，其含有選自由羧基、磺酸基及這些的鹽所組成群中的親水性官能基0.05質量%~5質量%及F原子7質量%~20質量%；4A族金屬化合物，其相對於上述含氟樹脂而以金屬換算計為0.1質量%~5質量%；以及平均粒徑為0.1 μm~10 μm的樹脂粒子，上述化學轉化處理皮膜的表面的上述樹脂粒子的面積佔有率為0.1面積%以上。 [1] A chemical conversion-treated Al-based steel sheet comprising: an Al-based alloy-plated steel sheet having an Al-based alloy plating layer containing 85% by mass to 99% by mass of Al; and a chemical conversion treatment film formed on the above The surface of the Al-based alloy plated steel sheet having a film thickness of 0.5 μm to 10 μm, the chemical conversion treatment film comprising: a fluorine-containing resin containing a hydrophilic functional group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a salt thereof 0.05% by mass to 5% by mass and 6% by mass to 20% by mass of the F atom; the Group 4A metal compound is 0.1% by mass to 5% by mass in terms of metal in terms of the fluorine-containing resin; and the average particle diameter is In the resin particles of 0.1 μm to 10 μm, the area ratio of the resin particles on the surface of the chemical conversion treatment film is 0.1% by area or more.
[2]如[1]所述之化學轉化處理鍍Al系鋼板，其中上述含氟樹脂所具有的羧基(carboxyl)與磺酸基(sulfo acid)的比率，以羧基/磺酸基的莫耳比計為5~60的範圍內。 [2] The chemical conversion-treated Al-based steel sheet according to [1], wherein a ratio of a carboxyl group to a sulfo acid of the fluorine-containing resin is a carboxyl group/sulfonic acid group molar The ratio is in the range of 5 to 60.
[3]如[1]或[2]所述之化學轉化處理鍍Al系鋼板，其中上述樹脂粒子是在聚乙烯樹脂粒子的表面結合有氟樹脂微粒子的聚乙烯-氟樹脂粒子。 [3] The chemical conversion-treated Al-based steel sheet according to [1] or [2], wherein the resin particles are polyethylene-fluororesin particles in which fluororesin fine particles are bonded to the surface of the polyethylene resin particles.
[4]如[3]所述之化學轉化處理鍍Al系鋼板，其中上述化學轉化處理皮膜進一步含有聚乙烯樹脂；上述聚乙烯-氟樹脂粒子在上述化學轉化處理皮膜的表面的一部分中，自上述化學轉化處理皮膜的表面突起；上述聚乙烯樹脂被覆上述化學轉化處理皮膜的表面的其餘部分的全部或一部分。 [4] The chemical conversion-treated Al-based steel sheet according to [3], wherein the chemical conversion treatment film further contains a polyethylene resin; and the polyethylene-fluororesin particles are in a part of a surface of the chemical conversion treatment film, The surface of the chemical conversion treatment film is protruded; and the polyethylene resin covers all or a part of the remaining portion of the surface of the chemical conversion treatment film.
[5]如[1]至[4]中任一項所述之化學轉化處理鍍Al系鋼板，其中上述化學轉化處理皮膜進一步含有磷酸鹽；相對於上述含氟樹脂，上述磷酸鹽的量以P換算計為0.05質量%~3質量%的範圍內。 [5] The chemical conversion-treated Al-based steel sheet according to any one of [1] to [4] wherein the chemical conversion treatment film further contains a phosphate; the amount of the phosphate is relative to the fluorine-containing resin The P conversion is in the range of 0.05% by mass to 3% by mass.
[6]如[1]至[5]中任一項所述之化學轉化處理鍍Al系鋼板，其中上述化學轉化處理皮膜進一步含有矽烷偶合劑(silane coupling agent)；相對於上述含氟樹脂，上述矽烷偶合劑的量為0.5質量%~5質量%的範圍內。 [6] The chemical conversion-treated Al-based steel sheet according to any one of [1] to [5] wherein the chemical conversion treatment film further contains a silane coupling agent; and the fluorine-containing resin, The amount of the above decane coupling agent is in the range of 0.5% by mass to 5% by mass.
[7]如[1]至[6]中任一項所述之化學轉化處理鍍Al系鋼板，其中上述4A族金屬選自由Ti、Zr、Hf及這些的組合所組成的群。 [7] The chemical conversion-treated Al-based steel sheet according to any one of [1] to [6] wherein the Group 4A metal is selected from the group consisting of Ti, Zr, Hf, and a combination thereof.
[8]如[1]至[7]中任一項所述之化學轉化處理鍍Al系鋼板，其中進一步具有基底化學轉化處理皮膜，其形成於上述Al系合金鍍鋼板、與上述化學轉化處理皮膜之間，且含有閥金屬(valve metal)的氧化物或氫氧化物、及閥金屬的氟化物。 [8] The chemical conversion-treated Al-based steel sheet according to any one of [1] to [7] further comprising a base chemical conversion treatment film formed on the Al-based alloy plated steel sheet and the chemical conversion treatment described above Between the membranes, it contains oxides or hydroxides of valve metals and fluorides of valve metals.
本發明的第二發明是關於以下的化學轉化處理鍍Al系鋼板的製造方法。 A second invention of the present invention relates to a method for producing a chemical conversion-treated Al-based steel sheet.
[9]一種化學轉化處理鍍Al系鋼板的製造方法，其包括：準備具有包含85質量%~99質量%的Al的Al系合金鍍敷層的Al系合金鍍鋼板的步驟；以及在上述Al系合金鍍鋼板的表面塗佈化學轉化處理液並乾燥，而形成膜厚為0.5 μm~10 μm的化學轉化處理皮膜的步驟，上述化學轉化處理液包含：含氟樹脂，其含有選自由羧基、磺酸基及 這些的鹽所組成群中的親水性官能基0.05質量%~5質量%及F原子7質量%~20質量%、且數量平均分子量為1000~200萬的範圍內；4A族金屬的含氧酸鹽、氟化物、氫氧化物、有機酸鹽、碳酸鹽或過氧化鹽的任一種；以及平均粒徑為0.1 μm~10 μm的樹脂粒子，相對於上述含氟樹脂，上述4A族金屬的含氧酸鹽、氟化物、氫氧化物、有機酸鹽、碳酸鹽或過氧化鹽的量，以金屬換算計為0.1質量%~5質量%的範圍內；相對於上述化學轉化處理液中的固體成分，上述樹脂粒子的量為0.5質量%~20質量%的範圍內。 [9] A method for producing a chemical conversion-treated Al-based steel sheet, comprising: preparing an Al-based alloy-plated steel sheet having an Al-based alloy plating layer containing 85% by mass to 99% by mass of Al; and The surface of the alloy-plated steel sheet is coated with a chemical conversion treatment liquid and dried to form a chemical conversion treatment film having a film thickness of 0.5 μm to 10 μm, wherein the chemical conversion treatment liquid contains a fluorine-containing resin containing a carboxyl group selected from the group consisting of Sulfonic acid group and The hydrophilic functional group in the group of these salts is 0.05% by mass to 5% by mass, and the F atom is 7 mass% to 20% by mass, and the number average molecular weight is in the range of 1,000 to 2,000,000; the oxo acid of the 4A group metal Any one of a salt, a fluoride, a hydroxide, an organic acid salt, a carbonate or a peroxy salt; and a resin particle having an average particle diameter of 0.1 μm to 10 μm, which is contained in the above-mentioned Group 4A metal with respect to the above fluorine-containing resin The amount of the oxyacid salt, the fluoride, the hydroxide, the organic acid salt, the carbonate or the peroxy salt is in the range of 0.1% by mass to 5% by mass in terms of metal; relative to the solid in the above chemical conversion treatment liquid The component is such that the amount of the resin particles is in the range of 0.5% by mass to 20% by mass.
[10]如[9]所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述含氟樹脂所具有的羧基與磺酸基的比率，以羧基/磺酸基的莫耳比計為5~60的範圍內。 [10] The method for producing a chemical conversion-treated Al-based steel sheet according to [9], wherein a ratio of a carboxyl group to a sulfonic acid group of the fluorine-containing resin is 5 in terms of a molar ratio of a carboxyl group/sulfonic acid group. Within the range of ~60.
[11]如[9]或[10]所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述樹脂粒子是在聚乙烯樹脂粒子的表面結合有氟樹脂微粒子的聚乙烯-氟樹脂粒子。 [11] The method for producing a chemical conversion-treated Al-based steel sheet according to [9], wherein the resin particles are polyethylene-fluororesin particles in which fluororesin fine particles are bonded to the surface of the polyethylene resin particles.
[12]如[11]所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述化學轉化處理液進一步含有聚乙烯樹脂粒子。 [12] The method for producing a chemical conversion-treated Al-based steel sheet according to [11], wherein the chemical conversion treatment liquid further contains polyethylene resin particles.
[13]如[9]至[12]中任一項所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述化學轉化處理液進一步含有磷酸鹽；相對於上述含氟樹脂，上述磷酸鹽的量以P換算計為0.05質量%~3質量%的範圍內。 [13] The method for producing a chemical conversion-treated Al-based steel sheet according to any one of [9] to [12] wherein the chemical conversion treatment liquid further contains a phosphate; the phosphate is the same as the fluorine-containing resin The amount is in the range of 0.05% by mass to 3% by mass in terms of P.
[14]如[9]至[13]中任一項所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述化學轉化處理液進一步含有矽 烷偶合劑；相對於上述含氟樹脂，上述矽烷偶合劑的量為0.5質量%~5質量%的範圍內。 [14] The method for producing a chemical conversion-treated Al-based steel sheet according to any one of [9] to [13] wherein the chemical conversion treatment liquid further contains ruthenium An alkane coupling agent; wherein the amount of the decane coupling agent is in the range of 0.5% by mass to 5% by mass based on the fluorine-containing resin.
[15]如[9]至[14]中任一項所述之化學轉化處理鍍Al系鋼板的製造方法，其中上述4A族金屬選自由Ti、Zr、Hf及這些的組合所組成的群。 [15] The method for producing a chemical conversion-treated Al-based steel sheet according to any one of [9] to [14] wherein the Group 4A metal is selected from the group consisting of Ti, Zr, Hf, and a combination thereof.
[16]如[9]至[15]中任一項所述之化學轉化處理鍍Al系鋼板的製造方法，其中在形成上述化學轉化處理皮膜的步驟前，進一步包括：在上述Al系合金鍍鋼板的表面塗佈基底化學轉化處理液並乾燥，而形成基底化學轉化處理皮膜的步驟；上述基底化學轉化處理液含有閥金屬鹽與氟化物離子。 [16] The method for producing a chemical conversion-treated Al-based steel sheet according to any one of [9] to [15] wherein, before the step of forming the chemical conversion treatment film, further comprising: plating the Al-based alloy The surface of the steel sheet is coated with a substrate chemical conversion treatment liquid and dried to form a substrate chemical conversion treatment film; the substrate chemical conversion treatment liquid contains a valve metal salt and a fluoride ion.
根據本發明，可提供耐候性、耐水性、皮膜密接性及加工性均優異的化學轉化處理鍍Al系鋼板。本發明的化學轉化處理鍍Al系鋼板由於耐候性、耐水性、耐蝕性、耐變色性及加工性優異，因此可有效用作例如外包裝建材用鍍鋼板。 According to the present invention, it is possible to provide a chemical conversion-treated Al-based steel sheet which is excellent in weather resistance, water resistance, film adhesion, and workability. The chemical conversion treatment of the Al-based steel sheet of the present invention is excellent in weather resistance, water resistance, corrosion resistance, discoloration resistance, and workability, and therefore can be effectively used as, for example, a plated steel sheet for exterior packaging materials.
本發明的化學轉化處理鍍Al系鋼板包括：Al系合金鍍鋼板(化學轉化處理底板)、形成於Al系合金鍍鋼板的表面的化學轉化處理皮膜。本發明的化學轉化處理鍍Al系鋼板的一個特徵是，化學轉化處理皮膜包含導入了親水性官能基(羧基或磺酸基等)的高分子量的含氟樹脂、4A 族金屬化合物及樹脂粒子(潤滑劑)。 The chemical conversion-treated Al-based steel sheet according to the present invention includes an Al-based alloy-plated steel sheet (chemical conversion-treated substrate) and a chemical conversion-treated film formed on the surface of the Al-based alloy-plated steel sheet. In the chemical conversion treatment of the Al-based steel sheet according to the present invention, the chemical conversion treatment film contains a high molecular weight fluorine-containing resin into which a hydrophilic functional group (carboxyl group or sulfonic acid group or the like) is introduced, 4A. Group metal compounds and resin particles (lubricants).
以下，對本發明的化學轉化處理鍍Al系鋼板的各構成要素進行說明。 Hereinafter, each constituent element of the chemical conversion-treated Al-based steel sheet of the present invention will be described.
化學轉化處理底板是使用耐蝕性及創意性優異的Al系合金鍍鋼板。此處所謂「Al系合金鍍鋼板」，是指包含85質量%~99質量%的Al，其餘部分實質上具有Si-Al系合金鍍敷層的鋼板。Al系合金鍍鋼板的例子包括：熔融Al-9%Si鍍鋼板等。 The chemical conversion treatment substrate is an Al-based alloy plated steel sheet which is excellent in corrosion resistance and creativity. Here, the "Al-based alloy-plated steel sheet" means a steel sheet containing 85% by mass to 99% by mass of Al, and the other portion substantially having a Si-Al-based alloy plating layer. Examples of the Al-based alloy plated steel sheet include a molten Al-9%Si-plated steel sheet or the like.
Al系合金鍍鋼板的基底鋼是使用低碳鋼或中碳鋼、高碳鋼、合金鋼等。在需要加工性時，較佳為低碳加Ti鋼、低碳加Nb鋼等深拉伸用鋼板作為基底鋼。 The base steel of the Al-based alloy plated steel sheet is made of low carbon steel or medium carbon steel, high carbon steel, alloy steel or the like. When workability is required, a steel sheet for deep drawing such as low carbon plus Ti steel or low carbon plus Nb steel is preferable as the base steel.
亦有在用作化學轉化處理底板的Al系合金鍍鋼板的表面，形成包含閥金屬的氧化物或氫氧化物、及閥金屬的氟化物的基底化學轉化處理皮膜的情況。如此，在Al系合金鍍鋼板的表面形成基底化學轉化處理皮膜時，化學轉化處理皮膜介隔基底化學轉化處理皮膜而形成於Al系合金鍍鋼板的表面。 There is also a case where a substrate chemical conversion treatment film containing an oxide or hydroxide of a valve metal and a fluoride of a valve metal is formed on the surface of an Al-based alloy-plated steel sheet used as a chemical conversion treatment substrate. As described above, when the underlying chemical conversion treatment film is formed on the surface of the Al-based alloy-plated steel sheet, the chemical conversion treatment film is formed on the surface of the Al-based alloy-plated steel sheet by interposing the base chemical conversion treatment film.
閥金屬的氧化物及氫氧化物表現高的絕緣電阻。因此，包含閥金屬的氧化物或氫氧化物的基底化學轉化處理皮膜，發揮出作為對電子的移動的電阻體(resistive element)的作用。因此，可抑制環境中的水分所含的溶存氧氣(dissolved oxygen)的還原反應，亦抑制成對的Al 系合金鍍鋼板的氧化反應。其結果可抑制來自成為基材的Al系合金鍍鋼板的金屬成分的溶出(腐蝕)。其中，Ti、Zr、Hf等IV族A元素的4價化合物為穩定的化合物，而形成優異的高絕緣性皮膜。 The oxide and hydroxide of the valve metal exhibit high insulation resistance. Therefore, the underlying chemical conversion treatment film containing the oxide or hydroxide of the valve metal acts as a resistive element for the movement of electrons. Therefore, it is possible to suppress the reduction reaction of dissolved oxygen contained in the moisture in the environment, and also suppress the paired Al. Oxidation reaction of alloy plated steel sheets. As a result, elution (corrosion) of the metal component from the Al-based alloy plated steel sheet to be the substrate can be suppressed. Among them, a tetravalent compound of a Group IV A element such as Ti, Zr or Hf is a stable compound and forms an excellent high insulating film.
另外，化學轉化處理皮膜中，通常在化學轉化處理時或成形加工時不可避免地產生皮膜缺陷。由於在皮膜缺陷部基材露出，因此即便進行化學轉化處理，亦無法期待腐蝕抑制作用。相對於此，上述基底化學轉化處理皮膜由於亦包含閥金屬的氟化物，因此具有自我修復作用。即，閥金屬的氟化物溶出於環境中的水分中後，在自皮膜缺陷部露出的基底鋼的表面成為難溶性氧化物或氫氧化物而再析出。其結果，將皮膜缺陷部填埋，因此發揮出自我修復作用。 Further, in the chemical conversion treatment film, film defects are inevitably generated at the time of chemical conversion treatment or molding processing. Since the base material of the film defect portion is exposed, the corrosion suppression effect cannot be expected even if the chemical conversion treatment is performed. On the other hand, since the above-mentioned base chemical conversion treatment film also contains a fluoride of a valve metal, it has a self-repairing effect. That is, after the fluoride of the valve metal is dissolved in the moisture in the environment, the surface of the base steel exposed from the film defect portion becomes a poorly soluble oxide or hydroxide and is reprecipitated. As a result, the film defect portion is filled, and thus the self-healing effect is exerted.
本發明的化學轉化處理鍍Al系鋼板可藉由對Al系合金鍍鋼板進行化學轉化處理而製造，化學轉化處理前的Al系合金鍍鋼板的耐蝕性不充分。因此在保存或運輸化學轉化處理前的Al系合金鍍鋼板、或進行成形加工的期間，有發生腐蝕的擔憂。因此，藉由預先在化學轉化處理前的Al系合金鍍鋼板上形成基底化學轉化處理皮膜，而可確實地防止化學轉化處理前發生Al系合金鍍鋼板的腐蝕。 The chemical conversion treatment of the Al-based steel sheet of the present invention can be produced by chemical conversion treatment of an Al-based alloy-plated steel sheet, and the Al-based alloy-plated steel sheet before the chemical conversion treatment is insufficient in corrosion resistance. Therefore, there is a concern that corrosion may occur during the storage or transportation of the Al-based alloy plated steel sheet before the chemical conversion treatment or during the forming process. Therefore, by forming the underlying chemical conversion treatment film on the Al-based alloy plated steel sheet before the chemical conversion treatment in advance, corrosion of the Al-based alloy-plated steel sheet before the chemical conversion treatment can be surely prevented.
將形成有基底化學轉化處理皮膜的Al系合金鍍鋼板進行保存、運輸或成形加工(包括溶接等)時，有一部分基底化學轉化處理皮膜剝離、缺損或欠缺的情況。因此Al系合金鍍鋼板的表面會露出，但包含含氟樹脂及4A族金 屬化合物的化學轉化處理皮膜會與該露出面直接接觸。 When the Al-based alloy-plated steel sheet on which the underlying chemical conversion treatment film is formed is stored, transported, or formed (including melting, etc.), some of the underlying chemical conversion treatment film may be peeled, defective, or missing. Therefore, the surface of the Al-based alloy plated steel plate will be exposed, but contains fluorine-containing resin and 4A gold. The chemical conversion treatment film of the compound is in direct contact with the exposed face.
基底化學轉化處理皮膜表現出提高Al系合金鍍鋼板與化學轉化處理皮膜的密接性的作用。因此亦認為，在基底化學轉化處理皮膜剝離的部位所形成的化學轉化處理皮膜，通常其皮膜密接性降低。然而，在化學轉化處理皮膜中，存在自直接接觸的鍍敷層溶出的Al。並且，由於該Al的存在，而化學轉化處理皮膜的耐蝕性或皮膜密接性提高。亦即，即便在表現使Al系合金鍍鋼板與化學轉化處理皮膜的密接性提高的作用的基底化學轉化處理皮膜剝離的部位，亦發揮出化學轉化處理皮膜的耐蝕性或密接性難以降低等效果。另外，關於藉由在化學轉化處理皮膜中存在Al，而使化學轉化處理皮膜的耐蝕性及皮膜密接性提高的機制，於下文進行敍述。 The substrate chemical conversion treatment film exhibits an effect of improving the adhesion between the Al-based alloy plated steel sheet and the chemical conversion treatment film. Therefore, it is considered that the chemical conversion treatment film formed at the portion where the substrate chemical conversion treatment film is peeled off generally has a reduced film adhesion. However, in the chemical conversion treatment film, there is Al eluted from the plating layer which is in direct contact. Further, due to the presence of Al, the corrosion resistance of the chemical conversion treatment film or the film adhesion is improved. In other words, even in the portion where the underlying chemical conversion treatment film which exhibits an effect of improving the adhesion between the Al-based alloy plated steel sheet and the chemical conversion treatment film is peeled off, the corrosion resistance or the adhesion of the chemical conversion treatment film is hardly lowered. . Further, the mechanism for improving the corrosion resistance and the film adhesion of the chemical conversion treatment film by the presence of Al in the chemical conversion treatment film will be described below.
基底化學轉化處理皮膜可藉由使形成於成為基材的Al系合金鍍鋼板的表面的基底化學轉化處理液的塗佈膜乾燥而形成。基底化學轉化處理液包含：閥金屬鹽、氟化物離子、以及作為溶劑的水。藉由使基底化學轉化處理液的塗膜乾燥，而閥金屬鹽成為基底化學轉化處理皮膜所含的閥金屬的氧化物或氫氧化物、或氟化物。 The substrate chemical conversion treatment film can be formed by drying a coating film of a base chemical conversion treatment liquid formed on the surface of the Al-based alloy plated steel sheet to be a substrate. The substrate chemical conversion treatment liquid contains: a valve metal salt, a fluoride ion, and water as a solvent. By drying the coating film of the substrate chemical conversion treatment liquid, the valve metal salt becomes an oxide or hydroxide of a valve metal or a fluoride contained in the substrate chemical conversion treatment film.
閥金屬的例子包括：Ti、Zr、Hf、V、Nb、Ta、Mo、及W。基底化學轉化處理液中所添加的閥金屬鹽可為閥金屬的鹵化物或含氧酸鹽等。若所添加的閥金屬鹽為氟化物，則亦可發揮出作為氟化物離子源的作用。 Examples of valve metals include Ti, Zr, Hf, V, Nb, Ta, Mo, and W. The valve metal salt added to the substrate chemical conversion treatment liquid may be a halide or an oxyacid salt of a valve metal or the like. If the added valve metal salt is a fluoride, it can also function as a fluoride ion source.
鈦鹽的例子包括：KnTiF6(K：鹼金屬或鹼土金屬、n： 1或2)、K2[TiO(COO)2]、(NH4)2TiF6、TiCl4、TiOSO4、Ti(SO4)2、及Ti(OH)4等。另一方面，基底化學轉化處理液所含的氟化物離子源可為包含氟原子的閥金屬鹽，亦可為另外的可溶性氟化物(例如(NH4)F等)。 Examples of the titanium salt include: K n TiF 6 (K: alkali metal or alkaline earth metal, n: 1 or 2), K 2 [TiO(COO) 2 ], (NH 4 ) 2 TiF 6 , TiCl 4 , TiOSO 4 , Ti(SO 4 ) 2 , and Ti(OH) 4 and the like. On the other hand, the fluoride ion source contained in the base chemical conversion treatment liquid may be a valve metal salt containing a fluorine atom, or may be another soluble fluoride (for example, (NH 4 )F or the like).
在基底化學轉化處理液中，為了使閥金屬鹽穩定化，較佳為添加具有螯合物(chelate)作用的有機酸。有機酸可將金屬離子螯合物化而使化學轉化處理液穩定。因此，有機酸的添加量以有機酸/金屬離子的莫耳比計可設定為0.02以上。有機酸的例子包括：酒石酸、鞣酸(tannic acid)、檸檬酸、草酸、丙二酸、乳酸、乙酸、及抗壞血酸等。其中，酒石酸等羥基羧酸、或鞣酸等多元酚類會使基底化學轉化處理液穩定化，並且亦表現出補充氟化物的自我修復作用的作用，對密接性的提高亦有效。 In the base chemical conversion treatment liquid, in order to stabilize the valve metal salt, it is preferred to add an organic acid having a chelate action. The organic acid can chelate the metal ion to stabilize the chemical conversion treatment liquid. Therefore, the amount of the organic acid to be added can be set to 0.02 or more in terms of the molar ratio of the organic acid/metal ion. Examples of the organic acid include tartaric acid, tannic acid, citric acid, oxalic acid, malonic acid, lactic acid, acetic acid, and ascorbic acid. Among them, a polyhydric phenol such as tartaric acid or a phenolic acid such as citric acid stabilizes the base chemical conversion treatment liquid, and also exhibits a self-repairing action of the fluoride supplement, and is also effective for improving the adhesion.
基底化學轉化處理液中可添加各種金屬的正磷酸鹽(orthophosphate)或聚磷酸鹽。原因是，化學轉化處理皮膜中含有可溶性或難溶性的金屬磷酸鹽或複合磷酸鹽。 Various metal orthophosphates or polyphosphates may be added to the substrate chemical conversion treatment liquid. The reason is that the chemical conversion treatment film contains a soluble or poorly soluble metal phosphate or complex phosphate.
可溶性金屬磷酸鹽或複合磷酸鹽自基底化學轉化處理皮膜溶出至皮膜缺陷部，與作為基材的Al系合金鍍鋼板的鍍敷成分(Al等)反應，而使不溶性磷酸鹽析出。如此補充鈦氟化物的自我修復作用。另外，在可溶性磷酸鹽解離時，環境會稍稍酸性化，因此會促進鈦氟化物的水解、進而促進難溶性鈦氧化物或氫氧化物的生成。 The soluble metal phosphate or the composite phosphate is eluted from the substrate chemical conversion treatment film to the film defect portion, and reacts with the plating component (Al or the like) of the Al-based alloy plated steel sheet as the substrate to precipitate insoluble phosphate. This complements the self-healing effect of titanium fluoride. Further, when the soluble phosphate is dissociated, the environment is slightly acidic, which promotes hydrolysis of the titanium fluoride and promotes formation of poorly soluble titanium oxide or hydroxide.
可溶性磷酸鹽或複合磷酸鹽的金屬可為鹼金屬、鹼土金屬、及Mn等。可溶性磷酸鹽或複合磷酸鹽能以各種金 屬磷酸鹽的形態添加於基底化學轉化處理液中，亦可將各種金屬鹽、與磷酸、聚磷酸、或磷酸鹽加以組合而添加於化學轉化處理液中。 The metal of the soluble phosphate or complex phosphate may be an alkali metal, an alkaline earth metal, and Mn or the like. Soluble phosphate or complex phosphate can be used in various gold The form of the phosphate is added to the base chemical conversion treatment liquid, and various metal salts, phosphoric acid, polyphosphoric acid, or phosphate may be combined and added to the chemical conversion treatment liquid.
另一方面，難溶性金屬磷酸鹽或複合磷酸鹽分散於基底化學轉化處理皮膜中，會消除皮膜缺陷並提高皮膜強度。難溶性磷酸鹽或複合磷酸鹽的金屬可為Al、Ti、Zr、Hf、Zn等。難溶性磷酸鹽或複合磷酸鹽能以各種金屬磷酸鹽的形態添加於化學轉化處理液中，亦可將各種金屬鹽與磷酸、聚磷酸或磷酸鹽加以組合而添加於化學轉化處理液中。 On the other hand, the poorly soluble metal phosphate or complex phosphate is dispersed in the substrate chemical conversion treatment film, which eliminates film defects and improves film strength. The metal of the poorly soluble phosphate or complex phosphate may be Al, Ti, Zr, Hf, Zn or the like. The poorly soluble phosphate or the composite phosphate may be added to the chemical conversion treatment liquid in the form of various metal phosphates, or may be added to the chemical conversion treatment liquid by combining various metal salts with phosphoric acid, polyphosphoric acid or phosphate.
基底化學轉化處理液中亦可添加氟系、聚乙烯系、苯乙烯系等的有機蠟，或二氧化矽、二硫化鉬、滑石等無機質潤滑劑等。藉由添加這些成分，可提高基底化學轉化處理皮膜的潤滑性。一般認為，低熔點的有機蠟在使基底化學轉化處理液的塗佈膜乾燥時會滲出(bleed)至膜表面，而表現潤滑性。另一方面認為，高熔點的有機蠟或無機系潤滑劑，雖然分散存在於皮膜中，但在皮膜的最表層以島狀分布露出於皮膜表面，從而表現潤滑性。 An organic wax such as fluorine, polyethylene or styrene may be added to the base chemical conversion treatment liquid, or an inorganic lubricant such as cerium oxide, molybdenum disulfide or talc may be added. By adding these components, the lubricity of the substrate chemical conversion treatment film can be improved. It is considered that the low-melting organic wax bleeds to the surface of the film when the coating film of the substrate chemical conversion treatment liquid is dried, and exhibits lubricity. On the other hand, it is considered that the organic wax having a high melting point or the inorganic lubricant is dispersed in the film, but is distributed on the surface of the film in the outermost layer of the film to exhibit lubricity.
若藉由螢光X射線、化學分析電子光譜(Electron Spectroscopy for Chemical Analysis，ESCA)等，對使基底化學轉化處理液的塗佈膜乾燥而得的基底化學轉化處理皮膜進行元素分析，則可測定基底化學轉化處理皮膜所含的O及F的濃度。這些元素濃度比F/O(原子比率)較佳為1/100以上。原因是可抑制所得的化學轉化處理鋼板的腐 蝕。特別是若元素濃度比F/O(原子比率)為1/100以上，則以皮膜缺陷部為起點的腐蝕的發生會大幅減少。其原因推測，在基底化學轉化處理皮膜中含有充分量的鈦氟化物，而發揮出自我修復作用。 When the elemental chemical conversion treatment film obtained by drying the coating film of the base chemical conversion treatment liquid is subjected to elemental analysis by fluorescent X-ray or Electron Spectroscopy for Chemical Analysis (ESCA), the measurement can be performed. The concentration of O and F contained in the film by the chemical conversion treatment of the substrate. The concentration ratio of these elements is preferably 1/100 or more in terms of F/O (atomic ratio). The reason is that the corrosion of the obtained chemical conversion treated steel sheet can be suppressed. eclipse. In particular, when the element concentration ratio F/O (atomic ratio) is 1/100 or more, the occurrence of corrosion starting from the film defect portion is greatly reduced. The reason for this is presumed to be that a sufficient amount of titanium fluoride is contained in the substrate chemical conversion treatment film to exert a self-repairing effect.
化學轉化處理皮膜形成於上述Al系合金鍍鋼板(化學轉化處理底板)的表面。可對化學轉化處理底板的表面進行形成成為基底的皮膜等的基底化學轉化處理，亦可不進行基底化學轉化處理。另外，在不對化學轉化處理底板的表面進行基底化學轉化處理時，在化學轉化處理底板的表面直接形成化學轉化處理皮膜。該化學轉化處理皮膜會提高Al系合金鍍鋼板的耐候性或耐水性、加工性(潤滑性)等。 The chemical conversion treatment film is formed on the surface of the above-described Al-based alloy plated steel sheet (chemical conversion treatment substrate). The surface of the chemical conversion treatment substrate may be subjected to a substrate chemical conversion treatment for forming a film or the like as a substrate, or may not be subjected to a substrate chemical conversion treatment. Further, when the surface chemical conversion treatment is not performed on the surface of the chemical conversion treatment substrate, a chemical conversion treatment film is directly formed on the surface of the chemical conversion treatment substrate. This chemical conversion treatment film improves the weather resistance, water resistance, workability (lubricity), and the like of the Al-based alloy plated steel sheet.
本發明的目的是提高化學轉化處理鍍Al系鋼板的耐候性、耐水性、皮膜密接性及加工性的各特性。如上所述，為了提高化學轉化處理皮膜的耐候性(耐紫外線性)，只要使用含氟樹脂作為有機樹脂即可。含氟樹脂大致分為溶劑系含氟樹脂以及水系含氟樹脂。在使用溶劑系含氟樹脂形成化學轉化處理皮膜時，揮發的溶劑的回收成為問題，但使用水系含氟樹脂時，不會產生此種問題。因此，本發明者嘗試使用操作容易的水系含氟樹脂形成耐候性、耐水性、皮膜密接性及加工性均優異的化學轉化處理鍍Al系鋼板。 An object of the present invention is to improve various characteristics of weather resistance, water resistance, film adhesion, and workability of a chemical conversion-treated Al-based steel sheet. As described above, in order to improve the weather resistance (UV resistance) of the chemical conversion treatment film, a fluorine-containing resin may be used as the organic resin. The fluorine-containing resin is roughly classified into a solvent-based fluorine resin and a water-based fluorine resin. When a chemical conversion treatment film is formed using a solvent-based fluorine-containing resin, recovery of a volatile solvent is problematic, but such a problem does not occur when a water-based fluorine-containing resin is used. Therefore, the inventors of the present invention have attempted to form a chemical conversion-treated Al-based steel sheet having excellent weather resistance, water resistance, film adhesion, and workability by using a water-based fluororesin which is easy to handle.
如上所述，根據本發明者的預備實驗，使用水系含氟 樹脂的乳液形成化學轉化處理皮膜時耐水性降低的原因認為是，製造水系含氟樹脂的乳液時所使用的乳化劑殘存於化學轉化處理皮膜中(參照後述的參考實驗)。因此，本發明者認為，若可幾乎不使用乳化劑來製造水系含氟樹脂的乳液，則可抑制化學轉化處理皮膜的耐水性降低。並且，本發明者對各種水系含氟樹脂進行了研究，結果發現，導入了固定量的親水性官能基的含氟樹脂，幾乎不使用乳化劑便可製造水系乳液，並可容易形成幾乎不含乳化劑的化學轉化處理皮膜。 As described above, according to the preliminary experiment of the present inventors, water-based fluorine is used. The reason why the water resistance of the resin emulsion is reduced when the chemical conversion treatment film is formed is that the emulsifier used in the production of the emulsion of the water-based fluororesin remains in the chemical conversion treatment film (see a reference experiment described later). Therefore, the present inventors have considered that it is possible to suppress a decrease in water resistance of the chemical conversion treatment film if the emulsion of the aqueous fluorine-containing resin can be produced almost without using an emulsifier. In addition, the present inventors have studied various water-based fluororesins and found that a fluorine-containing resin having a fixed amount of a hydrophilic functional group introduced therein can produce an aqueous emulsion almost without using an emulsifier, and can be easily formed into almost no The chemical conversion of the emulsifier treats the film.
另外，本發明者不僅對抑制化學轉化處理皮膜的耐水性降低進行研究，而且亦對提高耐水性進行了研究。並且自各種觀點進行研究，結果發現，藉由增大水系含氟樹脂的分子量、且利用4A族金屬化合物將水系氟樹脂交聯，而可顯著提高化學轉化處理皮膜的耐水性。 Further, the present inventors have not only studied the suppression of the water resistance reduction of the chemical conversion treatment film, but also studied the improvement of the water resistance. Further, it has been found from various viewpoints that it is found that the water resistance of the chemical conversion treatment film can be remarkably improved by increasing the molecular weight of the aqueous fluorine-containing resin and crosslinking the aqueous fluororesin with the Group 4A metal compound.
並且，本發明者發現，藉由在以導入了親水性官能基的高分子量的含氟樹脂為基礎的化學轉化處理液中，進一步調配4A族金屬化合物，而可形成同時具有耐候性、與耐水性及皮膜密接性的化學轉化處理皮膜。 Further, the present inventors have found that a 4A group metal compound can be further prepared by a chemical conversion treatment liquid based on a high molecular weight fluorine-containing resin having a hydrophilic functional group introduced therein, thereby forming weather resistance and water resistance. The chemical conversion treatment of the film and the adhesion of the film.
而且，本發明者對提高化學轉化處理鍍Al系鋼板的加工性(潤滑性)進行了研究。並且，本發明者對各種方法進行了研究，結果發現，藉由使平均粒徑為0.1 μm~10 μm的樹脂粒子分散於化學轉化處理皮膜中，可形成不但耐候性、耐水性及皮膜密接性優異，而且加工性(潤滑性)亦優異的化學轉化處理皮膜。 Further, the inventors of the present invention have studied the improvement of the workability (lubricity) of the chemical conversion-treated Al-based steel sheet. Further, the inventors of the present invention have studied various methods and found that by dispersing resin particles having an average particle diameter of 0.1 μm to 10 μm in a chemical conversion treatment film, weather resistance, water resistance, and film adhesion can be formed. A chemical conversion treatment film which is excellent and excellent in processability (lubricity).
在本發明的化學轉化處理鍍Al系鋼板的化學轉化處理皮膜中，1)藉由調配含氟樹脂(較佳為含氟的烯烴樹脂)而提高耐候性(耐紫外線性)。並且，2)藉由使用導入了親水性官能基的含氟樹脂而極力減少乳液製造時的乳化劑的使用；且3)增大含氟樹脂的分子量；且4)藉由利用4A族金屬化合物將含氟樹脂交聯而提高耐候性(耐紫外線性)及耐水性。並且，5)藉由分散平均粒徑為0.1 μm~10 μm的樹脂粒子而提高加工性(潤滑性)。 In the chemical conversion treatment film of the chemical conversion-treated Al-based steel sheet according to the present invention, 1) the weather resistance (UV resistance) is improved by blending a fluorine-containing resin (preferably a fluorine-containing olefin resin). 2) by using a fluorine-containing resin into which a hydrophilic functional group is introduced, the use of an emulsifier at the time of emulsion production is minimized; and 3) increasing the molecular weight of the fluorine-containing resin; and 4) by using a Group 4A metal compound The fluorine-containing resin is crosslinked to improve weather resistance (UV resistance) and water resistance. Further, 5) the workability (lubricity) is improved by dispersing resin particles having an average particle diameter of 0.1 μm to 10 μm.
以下，對化學轉化處理皮膜所含的各成分進行說明。 Hereinafter, each component contained in the chemical conversion treatment film will be described.
化學轉化處理皮膜包含含氟樹脂、更具體為含氟的烯烴樹脂作為主成分。化學轉化處理皮膜中作為主成分而含有的含氟樹脂的量，較佳為70質量%~99質量%的範圍內。如上所述，藉由使用含氟樹脂作為構成化學轉化處理皮膜的有機樹脂，而可提高化學轉化處理皮膜的耐候性(耐紫外線性)。 The chemical conversion treatment film contains a fluorine-containing resin, more specifically a fluorine-containing olefin resin as a main component. The amount of the fluorine-containing resin contained as a main component in the chemical conversion treatment film is preferably in the range of 70% by mass to 99% by mass. As described above, by using a fluorine-containing resin as the organic resin constituting the chemical conversion treatment film, the weather resistance (UV resistance) of the chemical conversion treatment film can be improved.
含氟樹脂較佳為比有機溶劑系氟樹脂容易操作的水系含氟樹脂。所謂「水系含氟樹脂」，是指具有親水性官能基的含氟樹脂。親水性官能基的較佳例包括：羧基、磺酸基及這些的鹽。羧基或磺酸基的鹽的例子包括：銨鹽、胺鹽、鹼金屬鹽等。 The fluorine-containing resin is preferably a water-based fluorine resin which is easier to handle than an organic solvent-based fluororesin. The "aqueous fluorine-containing resin" means a fluorine-containing resin having a hydrophilic functional group. Preferred examples of the hydrophilic functional group include a carboxyl group, a sulfonic acid group, and a salt of these. Examples of the salt of a carboxyl group or a sulfonic acid group include an ammonium salt, an amine salt, an alkali metal salt and the like.
較佳的水系含氟樹脂(較佳為含氟的烯烴樹脂)具有0.05質量%~5質量%的親水性官能基。具有0.05質量%~5質量%的親水性官能基的含氟樹脂，即便幾乎不使用 乳化劑亦可製成水系乳液。幾乎不含乳化劑的化學轉化處理皮膜可製成耐水性優異的化學轉化處理皮膜。 A preferred water-based fluororesin (preferably a fluorine-containing olefin resin) has a hydrophilic functional group of 0.05% by mass to 5% by mass. a fluorine-containing resin having a hydrophilic functional group of 0.05% by mass to 5% by mass, even if it is hardly used The emulsifier can also be made into an aqueous emulsion. The chemical conversion treatment film containing almost no emulsifier can be made into a chemical conversion treatment film excellent in water resistance.
水系含氟樹脂中的親水性官能基的含量，只要將水系含氟樹脂所含的親水性官能基的總莫耳質量除以水系含氟樹脂的數量平均分子量而求出即可。羧基的莫耳質量為45，磺酸基的莫耳質量為81，因此分別求出水系含氟樹脂所含的羧基及磺酸基的數量，並分別乘以莫耳質量，藉此求出水系含氟樹脂所含的親水性官能基的總莫耳質量。水系含氟樹脂的數量平均分子量藉由凝膠滲透層析法(gel permeation chromatography，GPC)進行測定。 The content of the hydrophilic functional group in the aqueous fluorine-containing resin may be determined by dividing the total molar mass of the hydrophilic functional group contained in the aqueous fluorine-containing resin by the number average molecular weight of the aqueous fluorine-containing resin. Since the molar mass of the carboxyl group is 45 and the molar mass of the sulfonic acid group is 81, the number of the carboxyl group and the sulfonic acid group contained in the aqueous fluorine-containing resin is determined and multiplied by the molar mass to determine the water system. The total molar mass of the hydrophilic functional group contained in the fluorine-containing resin. The number average molecular weight of the aqueous fluorine-containing resin was measured by gel permeation chromatography (GPC).
水系含氟樹脂中的羧基與鍍敷層表面形成氫鍵等而有助於提高化學轉化處理皮膜與鍍敷層表面的密接性，但由於H+難以解離，因此難以發生與4A族金屬化合物的交聯反應。另一方面，水系含氟樹脂中的磺酸基雖然H+容易解離，但若不與4A族金屬化合物進行交聯反應而以未反應的狀態殘存於皮膜中，則有由於水分子的吸附作用強而導致皮膜的耐水性明顯降低的擔憂。因此，為了有效利用各特徵，較佳為在水系含氟樹脂中包含羧基及磺酸基這兩者。此時，羧基與磺酸基的比率，以羧基/磺酸基的莫耳比計較佳為5~60的範圍內。 The carboxyl group in the water-based fluororesin forms a hydrogen bond with the surface of the plating layer, and contributes to improving the adhesion between the chemical conversion treatment film and the surface of the plating layer. However, since H + is difficult to dissociate, it is difficult to occur with the Group 4A metal compound. Cross-linking reaction. On the other hand, a sulfonic acid group in the aqueous fluorine-containing resin, although H + to dissociate readily, but if cross-linking reaction with a Group 4A metal compound to remain in the unreacted state in the film, there is adsorption of water molecules due Strong concern that the water resistance of the film is significantly lowered. Therefore, in order to utilize various features efficiently, it is preferable to contain both a carboxyl group and a sulfonic acid group in the water-based fluorine-containing resin. In this case, the ratio of the carboxyl group to the sulfonic acid group is preferably in the range of 5 to 60 in terms of the molar ratio of the carboxyl group to the sulfonic acid group.
化學轉化處理皮膜所含的水系含氟樹脂(較佳為含氟的烯烴樹脂)的數量平均分子量，較佳為1000以上，更佳為1萬以上，特佳為20萬以上。 The number average molecular weight of the aqueous fluorine-containing resin (preferably fluorine-containing olefin resin) contained in the chemical conversion treatment film is preferably 1,000 or more, more preferably 10,000 or more, and particularly preferably 200,000 or more.
若化學轉化處理皮膜所含的水系含氟樹脂的分子量過 小，則無法充分提高化學轉化處理皮膜的透水性及耐水性。此種情況下，濕氣或腐蝕性氣體等容易貫通化學轉化處理皮膜而到達鍍鋼板，因此有導致鍍鋼板容易腐蝕的擔憂。另外，在使用分子量小的水系含氟樹脂時，因光能量等的作用而產生的自由基容易作用於聚合物鏈的末端，因此有藉由水等的協同作用而導致水系含氟樹脂容易水解的擔憂。為了防止這些問題，只要將化學轉化處理皮膜所含的水系含氟樹脂的分子量增大到某種程度、或在水系含氟樹脂間形成交聯結構即可。藉由增大水系含氟樹脂的分子量，而分子間力增強，化學轉化處理皮膜的凝聚力提高，因此耐水性提高。另外，由於水系含氟樹脂的主鏈中的原子間的鍵穩定化，而亦難以產生水解。 If the molecular weight of the water-based fluororesin contained in the chemical conversion treatment film is too If it is small, the water permeability and water resistance of the chemical conversion treatment film cannot be sufficiently improved. In this case, moisture or a corrosive gas or the like easily penetrates the chemical conversion treatment film to reach the plated steel sheet, which may cause corrosion of the plated steel sheet. In addition, when a water-based fluororesin having a small molecular weight is used, a radical generated by the action of light energy or the like easily acts on the end of the polymer chain, so that the water-based fluororesin is easily hydrolyzed by the synergistic action of water or the like. Worry. In order to prevent these problems, the molecular weight of the aqueous fluorine-containing resin contained in the chemical conversion treatment film may be increased to some extent or a crosslinked structure may be formed between the aqueous fluorine-containing resins. By increasing the molecular weight of the aqueous fluorine-containing resin, the intermolecular force is enhanced, and the cohesive force of the chemical conversion treatment film is improved, so that the water resistance is improved. Further, since the bonds between the atoms in the main chain of the aqueous fluororesin are stabilized, hydrolysis is hard to occur.
另一方面，化學轉化處理皮膜所含的水系含氟樹脂的數量平均分子量較佳為200萬以下。在數量平均分子量超過200萬時，有凝膠化等處理液穩定性產生問題的擔憂。 On the other hand, the number average molecular weight of the water-based fluororesin contained in the chemical conversion treatment film is preferably 2,000,000 or less. When the number average molecular weight exceeds 2,000,000, there is a concern that the stability of the treatment liquid such as gelation may cause problems.
化學轉化處理皮膜所含的水系含氟樹脂中的F原子的含量較佳為7質量%~20質量%的範圍內。在F原子的含量小於7質量%時，無法充分提高化學轉化處理皮膜的耐候性。另一方面，在F原子的含量超過20質量%時，有難以塗料化、且密接性及乾燥性降低的擔憂。水系含氟樹脂中的F原子的含量可藉由使用螢光X射線分析裝置而進行測定。 The content of the F atom in the aqueous fluorine-containing resin contained in the chemical conversion treatment film is preferably in the range of 7 mass% to 20 mass%. When the content of the F atom is less than 7% by mass, the weather resistance of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of the F atom exceeds 20% by mass, there is a concern that coating is difficult to form and adhesion and drying properties are lowered. The content of the F atom in the aqueous fluorine-containing resin can be measured by using a fluorescent X-ray analyzer.
水系含氟樹脂的例子包括：氟烯烴與含親水性官能基的單體的共聚物。所謂含親水性官能基的單體，是含羧基 的單體或含磺酸基的單體。 Examples of the aqueous fluororesin include a copolymer of a fluoroolefin and a hydrophilic functional group-containing monomer. The monomer containing a hydrophilic functional group is a carboxyl group. Monomer or sulfonic acid group-containing monomer.
氟烯烴的例子包括：四氟乙烯、三氟乙烯、氯三氟乙烯、六氟丙烯、氟乙烯、偏二氟乙烯、五氟丙烯、2,2,3,3-四氟丙烯、3,3,3-三氟丙烯、溴三氟乙烯、1-氯-1,2-二氟乙烯、1,1-二氯-2,2-二氟乙烯等。這些氟烯烴可單獨使用，亦可將2種以上加以組合而使用。就耐候性(耐紫外線性)的觀點而言，這些氟烯烴中較佳為四氟乙烯、六氟丙烯等全氟烯烴、或偏二氟乙烯等。氯三氟乙烯等含氯的氟烯烴有因氯離子而產生腐蝕的擔憂，因此欠佳。 Examples of the fluoroolefin include: tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, pentafluoropropylene, 2,2,3,3-tetrafluoropropene, 3,3 , 3-trifluoropropene, bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene, 1,1-dichloro-2,2-difluoroethylene, and the like. These fluoroolefins may be used singly or in combination of two or more. From the viewpoint of weather resistance (UV resistance), among these fluoroolefins, a perfluoroolefin such as tetrafluoroethylene or hexafluoropropylene or vinylidene fluoride is preferable. Chlorine-containing fluoroolefins such as chlorotrifluoroethylene have a concern that corrosion may occur due to chloride ions, which is not preferable.
含羧基的單體的一例包括：以下式(1)所示的不飽和羧酸、或這些羧酸的酯或酸酐等不飽和羧酸類。 Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids represented by the following formula (1), or unsaturated carboxylic acids such as esters or acid anhydrides of these carboxylic acids.
(式中，R1、R2及R3相同或不同，均為氫原子、烷基、羧基或酯基。n為0~20的範圍內。) (wherein R 1 , R 2 and R 3 are the same or different and each is a hydrogen atom, an alkyl group, a carboxyl group or an ester group. n is in the range of 0 to 20.)
上述式(1)所示的不飽和羧酸的例子包括：丙烯酸、甲基丙烯酸、乙烯基乙酸、丁烯酸、桂皮酸、衣康酸、衣康酸單酯、順丁烯二酸、順丁烯二酸單酯、反丁烯二酸、反丁烯二酸單酯、5-己烯酸、5-庚烯酸、6-庚烯酸、7-辛烯酸、8-壬烯酸、9-癸烯酸、10-十一碳烯酸、11-十二碳烯酸、17-十八碳烯酸、油酸等。 Examples of the unsaturated carboxylic acid represented by the above formula (1) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, and cis. Butenedioic acid monoester, fumaric acid, fumaric acid monoester, 5-hexenoic acid, 5-heptenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-decenoic acid , 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 17-octadecenoic acid, oleic acid, and the like.
含羧基的單體的其他例子包括：以下式(2)所示的含羧基的乙烯醚單體。 Other examples of the carboxyl group-containing monomer include a carboxyl group-containing vinyl ether monomer represented by the following formula (2).
(式中，R4及R5相同或不同，均為飽和或不飽和的直鏈或環狀烷基。n為0或1。m為0或1。) (wherein R 4 and R 5 are the same or different and each is a saturated or unsaturated linear or cyclic alkyl group. n is 0 or 1. m is 0 or 1.)
上述式(2)所示的含羧基的乙烯醚單體的例子包括：3-(2-烯丙氧基乙氧基羰基)丙酸、3-(2-烯丙氧基丁氧基羰基)丙酸、3-(2-乙烯氧基乙氧基羰基)丙酸、3-(2-乙烯氧基丁氧基羰基)丙酸等。 Examples of the carboxyl group-containing vinyl ether monomer represented by the above formula (2) include 3-(2-allyloxyethoxycarbonyl)propionic acid and 3-(2-allyloxybutoxycarbonyl). Propionic acid, 3-(2-vinyloxyethoxycarbonyl)propionic acid, 3-(2-vinyloxybutoxycarbonyl)propionic acid, and the like.
含磺酸基的單體的例子包括：乙烯基磺酸、烯丙基磺酸、甲基烯丙基磺酸、苯乙烯磺酸、2-丙烯醯胺-2-甲基丙磺酸、2-甲基丙烯醯氧基乙磺酸、3-甲基丙烯醯氧基丙磺酸、4-甲基丙烯醯氧基丁磺酸、3-甲基丙烯醯氧基-2-羥基丙磺酸、3-丙烯醯氧基丙磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、異戊二烯磺酸、3-烯丙氧基-2-羥基丙磺酸等。 Examples of the sulfonic acid group-containing monomer include: vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, 2 -Methyl propylene methoxy ethane sulfonic acid, 3-methyl propylene methoxy propylene sulfonic acid, 4-methyl propylene methoxy butyl sulfonic acid, 3-methyl propylene oxy oxy hydroxy sulfonic acid , 3-propenyloxypropanesulfonic acid, allyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, isoprenesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, etc. .
根據需要，氟烯烴與含親水性官能基的單體的共聚物，亦可進一步與可共聚合的其他單體共聚合。可共聚合的其他單體的例子包括：羧酸乙烯酯類、烷基乙烯醚類、非氟系烯烴類等。 The copolymer of the fluoroolefin and the hydrophilic functional group-containing monomer may be further copolymerized with other monomers copolymerizable as needed. Examples of other monomers copolymerizable include vinyl carboxylates, alkyl vinyl ethers, non-fluorine olefins, and the like.
羧酸乙烯酯類可提高相溶性及光澤、或提高玻璃轉移 溫度。羧酸乙烯酯類的例子包括：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、特戊酸乙烯酯、己酸乙烯酯、特十碳酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、環己基甲酸乙烯酯、苯甲酸乙烯酯、對第三丁基苯甲酸乙烯酯等。 Vinyl carboxylates improve compatibility and gloss, or increase glass transfer temperature. Examples of the vinyl carboxylate include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl hexanoate, tetraethylene carbonate, vinyl laurate , vinyl stearate, vinyl cyclohexate, vinyl benzoate, p-tert-butyl benzoate, and the like.
烷基乙烯醚類可提高光澤及柔軟性。烷基乙烯醚類的例子包括：甲基乙烯醚、乙基乙烯醚、丁基乙烯醚等。 Alkyl vinyl ethers improve gloss and softness. Examples of the alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like.
非氟系烯烴類可提高可撓性。非氟系烯烴類的例子包括：乙烯、丙烯、正丁烯、異丁烯等。 Non-fluorinated olefins can improve flexibility. Examples of the non-fluorine olefins include ethylene, propylene, n-butene, isobutylene and the like.
藉由利用公知的聚合法將上述單體共聚合，而可獲得具有親水性官能基的氟烯烴共聚物。此時，藉由以氟烯烴共聚物具有0.05質量%~5質量%的親水性官能基的方式，調整原料單體組成物中的氟烯烴的量，從而幾乎不使用乳化劑便可製造氟烯烴共聚物的水系乳液。使用幾乎不含乳化劑(1質量%以下)的氟烯烴共聚物的乳液而形成的化學轉化處理皮膜中，幾乎不含乳化劑。 The fluoroolefin copolymer having a hydrophilic functional group can be obtained by copolymerizing the above monomers by a known polymerization method. In this case, by adjusting the amount of the fluoroolefin in the raw material monomer composition so that the fluoroolefin copolymer has a hydrophilic functional group of 0.05% by mass to 5% by mass, the fluoroolefin can be produced with almost no emulsifier. An aqueous emulsion of a copolymer. The chemical conversion treatment film formed using an emulsion containing a fluoroolefin copolymer containing almost no emulsifier (1 mass% or less) contains almost no emulsifier.
如此，藉由使用具有親水性官能基的含氟樹脂作為構成化學轉化處理皮膜的水系含氟樹脂，而可容易形成幾乎不含乳化劑的化學轉化處理皮膜。如此形成的化學轉化處理皮膜幾乎見不到因乳化劑的殘留引起的耐水性的劣化，而發揮優異的耐水性。 By using a fluorine-containing resin having a hydrophilic functional group as the aqueous fluorine-containing resin constituting the chemical conversion treatment film, a chemical conversion treatment film containing almost no emulsifier can be easily formed. In the chemical conversion treatment film thus formed, deterioration of water resistance due to the residual of the emulsifier is hardly observed, and excellent water resistance is exhibited.
化學轉化處理皮膜包含4A族金屬化合物。4A族金屬化合物容易與水系含氟樹脂中的羧基或磺酸基等官能基反 應，而促進水系含氟樹脂的硬化或交聯反應。因此，即便藉由低溫乾燥亦可提高化學轉化處理皮膜的耐水性。 The chemical conversion treatment film contains a Group 4A metal compound. The Group 4A metal compound is easily reversed from a functional group such as a carboxyl group or a sulfonic acid group in the aqueous fluorine-containing resin. It should promote the hardening or crosslinking reaction of the aqueous fluorine-containing resin. Therefore, the water resistance of the chemical conversion treatment film can be improved even by low-temperature drying.
在使用三聚氰胺樹脂或異氰酸酯樹脂等時，含氟樹脂的交聯存在容易發生耐候劣化的問題。例如在使用三聚氰胺樹脂進行硬化的化學轉化處理皮膜中，由於酯鍵或甲醚鍵等氧化、水解而立即導致耐候劣化。另外，由於酸雨中所含的硫酸離子或硝酸離子等酸性物質而切割交聯結構，從而亦導致耐候劣化。在使用異氰酸酯樹脂進行硬化的化學轉化處理皮膜中，交聯部分所形成的胺基甲酸酯鍵比F鍵弱，因此導致優先切割交聯結構，而導致耐候劣化。 When a melamine resin, an isocyanate resin, or the like is used, crosslinking of the fluorine-containing resin has a problem that weathering deterioration easily occurs. For example, in a chemical conversion treatment film which is cured by using a melamine resin, weathering deterioration is immediately caused by oxidation or hydrolysis of an ester bond or a methyl ether bond. Further, the crosslinked structure is cleaved due to an acidic substance such as sulfate ions or nitrate ions contained in the acid rain, which also causes weather resistance deterioration. In the chemical conversion treatment film which is hardened using an isocyanate resin, the urethane bond formed by the crosslinked portion is weaker than the F bond, and thus the crosslinked structure is preferentially cleaved, resulting in weathering deterioration.
相對於此，藉由在含氟樹脂的交聯中使用4A族金屬化合物，而可避免此種問題，並且亦可提高耐候性。 On the other hand, by using a Group 4A metal compound in the crosslinking of the fluorine-containing resin, such a problem can be avoided, and weather resistance can be improved.
另外，4A族金屬化合物亦會提高皮膜密接性及耐水性。即，存在於Al系合金鍍鋼板的表面的牢固的Al氧化物，會降低化學轉化處理皮膜的密接性，但藉由使化學轉化處理皮膜含有4A族金屬化合物，而可抑制因該Al氧化物引起的皮膜密接性的降低。另外，4A族金屬化合物亦成為與藉由蝕刻反應而溶出的Al離子發生反應的4A族金屬離子的供給源。反應產物在鍍敷層與化學轉化處理皮膜的界面濃化而提高初始的耐蝕性。4A族金屬的例子包括：Ti或Zr、Hf等。 In addition, the Group 4A metal compound also improves film adhesion and water resistance. In other words, the strong Al oxide present on the surface of the Al-based alloy-plated steel sheet reduces the adhesion of the chemical conversion coating film, but the chemical conversion coating film contains a Group 4A metal compound, thereby suppressing the Al oxide. The resulting adhesion of the film is reduced. Further, the Group 4A metal compound also serves as a supply source of Group 4A metal ions which react with Al ions eluted by an etching reaction. The reaction product is concentrated at the interface between the plating layer and the chemical conversion treatment film to improve the initial corrosion resistance. Examples of the Group 4A metal include: Ti or Zr, Hf, and the like.
化學轉化處理皮膜中的4A族金屬化合物的含量，相對於含氟樹脂以金屬換算計較佳為0.1質量%~5質量%的範圍內。在含量以金屬換算計小於0.1質量%時，無法充 分抑制因Al氧化物的濃化引起的不良影響，並且無法使水系含氟樹脂充分地交聯，結果無法充分提高化學轉化處理皮膜的耐水性。另一方面，在含量以金屬換算超過5質量%時，化學轉化處理皮膜變成多孔質狀，而有加工性、耐候性降低的擔憂。 The content of the Group 4A metal compound in the chemical conversion treatment film is preferably in the range of 0.1% by mass to 5% by mass based on the fluorine-containing resin in terms of metal. When the content is less than 0.1% by mass in terms of metal, it cannot be charged. The adverse effect due to the concentration of the Al oxide is suppressed, and the water-based fluororesin cannot be sufficiently crosslinked, and as a result, the water resistance of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content is more than 5% by mass in terms of metal, the chemical conversion treatment film becomes porous, and there is a concern that workability and weather resistance are lowered.
化學轉化處理皮膜中的4A族金屬化合物的金屬換算量，可藉由使用螢光X射線分析裝置來進行測定。 The metal equivalent amount of the Group 4A metal compound in the chemical conversion treatment film can be measured by using a fluorescent X-ray analyzer.
如上所述在化學轉化處理皮膜中存在自鍍敷層溶出的Al。該Al有助於提高耐蝕性。由於Al的存在而提高耐蝕性的原因推測為以下的機制。即，1)由於化學轉化處理液為弱鹼性，因此塗佈化學轉化處理液時，鍍敷層所含的Al的氧化物及金屬Al選擇性地溶出至化學轉化處理液中。2)在化學轉化處理液的pH域中，Al以Al(OH)4 -的狀態溶解於化學轉化處理液中。3)使化學轉化處理液乾燥而形成化學轉化處理皮膜時，化學轉化處理液中的Al藉由脫水縮合等而摻入至化學轉化處理皮膜中。4)結果是化學轉化處理皮膜的絕緣性或緻密度等提高，並且耐蝕性提高。 As described above, Al which is eluted from the plating layer exists in the chemical conversion treatment film. This Al helps to improve corrosion resistance. The reason why the corrosion resistance is improved by the presence of Al is presumed to be the following mechanism. That is, 1) since the chemical conversion treatment liquid is weakly alkaline, when the chemical conversion treatment liquid is applied, the Al oxide and the metal Al contained in the plating layer are selectively eluted into the chemical conversion treatment liquid. 2) In the pH range of the chemical conversion treatment liquid, Al is dissolved in the chemical conversion treatment liquid in the state of Al(OH) 4 - . 3) When the chemical conversion treatment liquid is dried to form a chemical conversion treatment film, Al in the chemical conversion treatment liquid is incorporated into the chemical conversion treatment film by dehydration condensation or the like. 4) As a result, the insulation property or the density of the chemical conversion treatment film is improved, and the corrosion resistance is improved.
3)樹脂粒子 3) Resin particles
化學轉化處理皮膜包含樹脂粒子。樹脂粒子分散於化學轉化處理皮膜中，至少其一部分露出(突起)於化學轉化處理皮膜的表面(參照圖3C)。化學轉化處理皮膜的表面突起的樹脂粒子，在成形加工時如「滾子」般發揮功能，藉此提高化學轉化處理皮膜表面的潤滑性。其結果可提高化學轉化處理鍍Al系鋼板的加工性。 The chemical conversion treatment film contains resin particles. The resin particles are dispersed in the chemical conversion treatment film, and at least a part thereof is exposed (protruded) on the surface of the chemical conversion treatment film (see FIG. 3C). The resin particles on the surface of the chemical conversion treatment film function as a "roller" during the molding process, thereby improving the lubricity of the surface of the chemical conversion treatment film. As a result, the workability of the chemical conversion-treated Al-based steel sheet can be improved.
樹脂粒子的平均粒徑較佳為0.1μm~10μm的範圍內。在樹脂粒子的平均粒徑小於0.1μm時，會導致大部分的樹脂粒子埋沒在化學轉化處理皮膜中，因此無法高效地提高化學轉化處理皮膜表面的潤滑性。另一方面，在樹脂粒子的平均粒徑超過10μm時，有成形加工時樹脂粒子容易脫落的擔憂。若如此導致樹脂粒子脫落，則會導致化學轉化處理皮膜產生缺陷，並導致耐蝕性降低。另外，本說明書中，所謂樹脂粒子的平均粒徑，是指藉由雷射繞射散射法測定的粒徑分布中的累計值50%時的粒徑(中值粒徑)。 The average particle diameter of the resin particles is preferably in the range of 0.1 μm to 10 μm. When the average particle diameter of the resin particles is less than 0.1 μm, most of the resin particles are buried in the chemical conversion treatment film, and thus the lubricity of the surface of the chemical conversion treatment film cannot be efficiently improved. On the other hand, when the average particle diameter of the resin particles exceeds 10 μm, there is a concern that the resin particles are likely to fall off during the molding process. If the resin particles are detached as described above, the chemical conversion treatment film is defective, and the corrosion resistance is lowered. In the present specification, the average particle diameter of the resin particles means a particle diameter (median diameter) when the integrated value in the particle diameter distribution measured by the laser diffraction scattering method is 50%.
化學轉化處理皮膜中的樹脂粒子的含量，以化學轉化處理皮膜的表面中的樹脂粒子的面積佔有率為0.1面積%以上的方式進行調整。在樹脂粒子的面積佔有率小於0.1面積%時，無法充分提高化學轉化處理皮膜的潤滑性。化學轉化處理皮膜的表面中的樹脂粒子的面積佔有率可藉由利用掃描型電子顯微鏡(scanning electron microscope，SEM)觀察化學轉化處理皮膜的表面而求出。 The content of the resin particles in the chemical conversion treatment film is adjusted so that the area ratio of the resin particles in the surface of the chemical conversion treatment film is 0.1 area% or more. When the area occupation ratio of the resin particles is less than 0.1 area%, the lubricity of the chemical conversion treatment film cannot be sufficiently improved. The area occupation ratio of the resin particles in the surface of the chemical conversion treatment film can be determined by observing the surface of the chemical conversion treatment film by a scanning electron microscope (SEM).
樹脂粒子的種類並無特別限定，就耐熱性及分散性的觀點而言，較佳為聚乙烯-氟樹脂粒子。 The type of the resin particles is not particularly limited, and from the viewpoint of heat resistance and dispersibility, polyethylene-fluororesin particles are preferred.
聚乙烯樹脂粒子因比重小(例如為0.95)而在化學轉化處理液中的分散性優異，但因熔點低(例如為123℃)而耐熱性劣化。如此使用耐熱性低的樹脂粒子時，為了形成化學轉化處理皮膜而將化學轉化處理液加熱乾燥時，有無法維持粒子的形狀的擔憂。具體而言，若以140℃~ 180℃左右對化學轉化處理液進行加熱乾燥，則會導致聚乙烯樹脂粒子熔融。若如此導致樹脂粒子熔融，則樹脂粒子無法發揮出作為「滾子」的功能，而無法促進潤滑性的提高。 The polyethylene resin particles are excellent in dispersibility in a chemical conversion treatment liquid because the specific gravity is small (for example, 0.95), but the heat resistance is deteriorated because the melting point is low (for example, 123 ° C). When the resin particles having low heat resistance are used as described above, when the chemical conversion treatment liquid is heated and dried to form the chemical conversion treatment film, the shape of the particles may not be maintained. Specifically, if it is 140 ° C~ Heating and drying the chemical conversion treatment liquid at about 180 ° C causes the polyethylene resin particles to melt. When the resin particles are melted in this manner, the resin particles cannot function as a "roller", and the improvement in lubricity cannot be promoted.
另一方面，氟樹脂粒子因熔點高(例如為330℃)而耐熱性優異，但因比重大(例如為2.2)而在化學轉化處理液中的分散性劣化。如此使用化學轉化處理液中的分散性低的樹脂粒子時，難以使樹脂粒子均勻地分散於化學轉化處理皮膜中。 On the other hand, the fluororesin particles have a high melting point (for example, 330 ° C) and are excellent in heat resistance, but the dispersibility in the chemical conversion treatment liquid is deteriorated due to a large specific gravity (for example, 2.2). When the resin particles having low dispersibility in the chemical conversion treatment liquid are used in this manner, it is difficult to uniformly disperse the resin particles in the chemical conversion treatment film.
聚乙烯-氟樹脂粒子是藉由使氟樹脂微粒子與經加熱而軟化的聚乙烯樹脂粒子接觸，而使氟樹脂微粒子結合(吸附)於聚乙烯樹脂粒子的表面而成。藉由在聚乙烯樹脂粒子的表面結合氟樹脂微粒子，而可同時具有：即便以140℃~180℃左右加熱亦可維持粒子的形狀的程度的耐熱性、以及在化學轉化處理液中的分散性(比重：例如1.1)。另外，藉由在聚乙烯樹脂粒子的表面結合氟樹脂微粒子，而亦可提高耐候性。 The polyethylene-fluororesin particles are obtained by bringing the fluororesin fine particles into contact with the polyethylene resin particles softened by heating, and bonding (adsorbing) the fluororesin fine particles to the surface of the polyethylene resin particles. By incorporating fluororesin fine particles on the surface of the polyethylene resin particles, it is possible to simultaneously have heat resistance and dispersibility in the chemical conversion treatment liquid even when heated at about 140 ° C to 180 ° C to maintain the shape of the particles. (specific gravity: for example, 1.1). Further, by incorporating fluororesin fine particles on the surface of the polyethylene resin particles, weather resistance can be improved.
圖1是加熱至50℃或150℃的包含聚乙烯樹脂粒子或聚乙烯-氟樹脂粒子的化學轉化處理皮膜的SEM像(俯視)。圖1A是將包含聚乙烯樹脂粒子的化學轉化處理液塗佈於鍍鋼板的表面，以50℃進行乾燥而形成的化學轉化處理皮膜的SEM像。圖1B是將包含聚乙烯樹脂粒子的化學轉化處理液塗佈於鍍鋼板的表面，以150℃進行乾燥而形成的化學轉化處理皮膜的SEM像。圖1C是將包含聚乙烯 -氟樹脂粒子的化學轉化處理液塗佈於鍍鋼板的表面，以50℃進行乾燥而形成的化學轉化處理皮膜的SEM像。圖1D是將包含聚乙烯-氟樹脂粒子的化學轉化處理液塗佈於鍍鋼板的表面，以150℃進行乾燥而形成的化學轉化處理皮膜的SEM像。 Fig. 1 is an SEM image (plan view) of a chemical conversion treatment film containing polyethylene resin particles or polyethylene-fluororesin particles heated to 50 ° C or 150 ° C. Fig. 1A is an SEM image of a chemical conversion treatment film formed by applying a chemical conversion treatment liquid containing polyethylene resin particles to the surface of a plated steel sheet and drying at 50 °C. Fig. 1B is an SEM image of a chemical conversion treatment film formed by applying a chemical conversion treatment liquid containing polyethylene resin particles to the surface of a plated steel sheet and drying at 150 °C. Figure 1C will contain polyethylene The SEM image of the chemical conversion treatment film formed by applying a chemical conversion treatment liquid of the fluororesin particles to the surface of the plated steel sheet and drying at 50 ° C. 1D is an SEM image of a chemical conversion treatment film formed by applying a chemical conversion treatment liquid containing polyethylene-fluororesin particles to the surface of a plated steel sheet and drying at 150 °C.
如圖1A所示，在將包含聚乙烯樹脂粒子的化學轉化處理液以50℃進行乾燥時，可維持聚乙烯樹脂粒子的形狀，並且聚乙烯樹脂粒子自化學轉化處理皮膜的表面突起(參照圖中「PE」)。另一方面，如圖1B所示，在將包含聚乙烯樹脂粒子的化學轉化處理液以150℃進行乾燥時，導致聚乙烯樹脂粒子熔融，並且聚乙烯樹脂均勻地分布於化學轉化處理皮膜的表面(參照圖中「PE」)。 As shown in FIG. 1A, when the chemical conversion treatment liquid containing the polyethylene resin particles is dried at 50 ° C, the shape of the polyethylene resin particles can be maintained, and the polyethylene resin particles are lifted from the surface of the chemical conversion treatment film (refer to the figure). Medium "PE"). On the other hand, as shown in FIG. 1B, when the chemical conversion treatment liquid containing the polyethylene resin particles is dried at 150 ° C, the polyethylene resin particles are melted, and the polyethylene resin is uniformly distributed on the surface of the chemical conversion treatment film. (Refer to "PE" in the figure).
如圖1C所示，將包含聚乙烯-氟樹脂粒子的化學轉化處理液以50℃進行乾燥時，可維持聚乙烯-氟樹脂粒子的形狀，並且聚乙烯-氟樹脂粒子自化學轉化處理皮膜的表面突起(參照圖中「PE-F」)。另外，如圖1D所示，將包含聚乙烯-氟樹脂粒子的化學轉化處理液以150℃進行乾燥時，雖然一部分的聚乙烯-氟樹脂粒子(氟樹脂微粒子的附著量少的聚乙烯-氟樹脂粒子)熔融(參照圖中「PE」)，但其餘部分的聚乙烯-氟樹脂(氟樹脂微粒子的附著量多的聚乙烯-氟樹脂)不熔融(參照圖中「PE-F」)。 As shown in FIG. 1C, when the chemical conversion treatment liquid containing the polyethylene-fluororesin particles is dried at 50 ° C, the shape of the polyethylene-fluororesin particles can be maintained, and the polyethylene-fluororesin particles are chemically converted into a film. Surface protrusion (refer to "PE-F" in the figure). In addition, as shown in FIG. 1D, when the chemical conversion treatment liquid containing the polyethylene-fluororesin particles is dried at 150 ° C, a part of the polyethylene-fluororesin particles (polyethylene-fluorine having a small amount of the fluororesin particles adhered) The resin particles are melted (see "PE" in the drawing), but the remaining polyethylene-fluororesin (polyethylene-fluororesin having a large amount of fluororesin particles adhered) is not melted (see "PE-F" in the drawing).
如此，在乾燥溫度低的情況下，即便是聚乙烯樹脂粒子亦無問題，但在乾燥溫度高的情況下，較佳為使用聚乙烯-氟樹脂粒子。另外，就耐候性的觀點而言，亦較佳為使 用聚乙烯-氟樹脂粒子。 As described above, when the drying temperature is low, there is no problem even if the polyethylene resin particles are used. However, when the drying temperature is high, polyethylene-fluororesin particles are preferably used. In addition, from the viewpoint of weather resistance, it is also preferable to make Polyethylene-fluororesin particles are used.
構成聚乙烯-氟樹脂粒子的聚乙烯樹脂粒子的平均粒徑，若是聚乙烯-氟樹脂粒子的平均粒徑為0.1 μm~10 μm的範圍內，則並無特別限定。可使用的聚乙烯樹脂粒子的市售品的例子包括：HYTEC E-9016、HYTEC E-1000(均為東邦化學股份有限公司)、CJ-172B、CJ-137(均為興洋化學股份有限公司)、PERMARIN KUE-4、PERMARIN KUE-5(均為三洋化成工業股份有限公司)等。另一方面，構成聚乙烯-氟樹脂粒子的氟樹脂微粒子的平均粒徑，只要根據聚乙烯樹脂粒子的平均粒徑進行適當設定即可。例如氟樹脂微粒子的平均粒徑較佳為0.3 μm以下。 The average particle diameter of the polyethylene resin particles constituting the polyethylene-fluororesin particles is not particularly limited as long as the average particle diameter of the polyethylene-fluororesin particles is in the range of 0.1 μm to 10 μm. Examples of commercially available polyethylene resin particles that can be used include: HYTEC E-9016, HYTEC E-1000 (both Toho Chemical Co., Ltd.), CJ-172B, and CJ-137 (all are Xingyang Chemical Co., Ltd. ), PERMARIN KUE-4, PERMARIN KUE-5 (all are Sanyo Chemical Industry Co., Ltd.). On the other hand, the average particle diameter of the fluororesin fine particles constituting the polyethylene-fluororesin particles may be appropriately set in accordance with the average particle diameter of the polyethylene resin particles. For example, the average particle diameter of the fluororesin fine particles is preferably 0.3 μm or less.
聚乙烯-氟樹脂粒子中的氟樹脂的比例較佳為5質量%~40質量%的範圍內。在氟樹脂的比例小於5質量%時，有無法充分發揮因附著氟樹脂產生的效果的擔憂。另一方面，在氟樹脂的比例超過40質量%時，有聚乙烯-氟樹脂粒子容易自化學轉化處理皮膜脫落的擔憂。聚乙烯-氟樹脂粒子中的氟樹脂的比例可藉由使用螢光X射線分析裝置進行測定。 The proportion of the fluororesin in the polyethylene-fluororesin particles is preferably in the range of 5 mass% to 40 mass%. When the proportion of the fluororesin is less than 5% by mass, the effect due to adhesion of the fluororesin may not be sufficiently exhibited. On the other hand, when the ratio of the fluororesin exceeds 40% by mass, there is a concern that the polyethylene-fluororesin particles are likely to fall off from the chemical conversion treatment film. The ratio of the fluororesin in the polyethylene-fluororesin particles can be measured by using a fluorescent X-ray analyzer.
在化學轉化處理皮膜包含聚乙烯-氟樹脂粒子時，化學轉化處理皮膜較佳為進一步包含聚乙烯樹脂。通常，聚乙烯樹脂被覆化學轉化處理皮膜的表面中聚乙烯-氟樹脂粒子未突起的區域的全部或一部分(參照圖2C)。被覆該化學轉化處理皮膜的表面的聚乙烯樹脂是在製造步驟中滲出 至化學轉化處理皮膜的表面的聚乙烯樹脂。聚乙烯樹脂粒子會與聚乙烯-氟樹脂粒子一起提高化學轉化處理皮膜表面的潤滑性，藉此進一步提高化學轉化處理鍍Al系鋼板的加工性。 When the chemical conversion treatment film contains polyethylene-fluororesin particles, the chemical conversion treatment film preferably further contains a polyethylene resin. Usually, the polyethylene resin coats all or a part of the region where the polyethylene-fluororesin particles are not protruded on the surface of the chemical conversion treatment film (see FIG. 2C). The polyethylene resin covering the surface of the chemical conversion treatment film is exuded in the manufacturing step A polyethylene resin to the surface of the chemical conversion treatment film. The polyethylene resin particles together with the polyethylene-fluororesin particles improve the lubricity of the surface of the chemical conversion treatment film, thereby further improving the processability of the chemical conversion-treated Al-based steel sheet.
化學轉化處理皮膜中的聚乙烯樹脂的含量，相對於化學轉化處理皮膜較佳為0.1質量%~16質量%的範圍內。在聚乙烯樹脂的含量小於0.1質量%時，無法充分發揮聚乙烯樹脂的效果。另一方面，在聚乙烯樹脂的含量超過16質量%時，有導致耐候性降低的擔憂。 The content of the polyethylene resin in the chemical conversion treatment film is preferably in the range of 0.1% by mass to 16% by mass based on the chemical conversion treatment film. When the content of the polyethylene resin is less than 0.1% by mass, the effect of the polyethylene resin cannot be sufficiently exhibited. On the other hand, when the content of the polyethylene resin exceeds 16% by mass, there is a concern that the weather resistance is lowered.
化學轉化處理皮膜較佳為進一步包含磷酸鹽。磷酸鹽與Al系合金鍍鋼板的鍍敷層表面反應，而提高化學轉化處理皮膜對Al系合金鍍鋼板的密接性。 The chemical conversion treatment film preferably further comprises a phosphate. The phosphate reacts with the surface of the plating layer of the Al-based alloy-plated steel sheet to improve the adhesion of the chemical conversion coating to the Al-based alloy-plated steel sheet.
磷酸鹽的種類若為具有磷酸陰離子的化合物，且為水溶性的化合物，則並無特別限定。磷酸鹽的例子包括：磷酸鈉、磷酸銨、磷酸鎂、磷酸鉀、磷酸錳、磷酸鋅、正磷酸、偏磷酸、焦磷酸(二磷酸)、三磷酸、四磷酸等。這些磷酸鹽可單獨使用，亦可將2種以上加以組合而使用。 The type of the phosphate is not particularly limited as long as it is a compound having a phosphate anion and is a water-soluble compound. Examples of the phosphate include sodium phosphate, ammonium phosphate, magnesium phosphate, potassium phosphate, manganese phosphate, zinc phosphate, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid (diphosphoric acid), triphosphoric acid, tetraphosphoric acid, and the like. These phosphates may be used singly or in combination of two or more.
化學轉化處理皮膜中的磷酸鹽的含量，相對於含氟樹脂以P換算量計較佳為0.05質量%~3質量%的範圍內。在P換算量小於0.05質量%時，與鍍敷層表面的反應不足，而無法充分提高化學轉化處理皮膜的密接性。另一方面，在P換算量超過3質量%時，與4A族金屬化合物的反應過度進行，而導致損及4A族金屬化合物的交聯效果。 The content of the phosphate in the chemical conversion treatment film is preferably in the range of 0.05% by mass to 3% by mass based on the amount of the fluorine-containing resin in terms of P. When the P conversion amount is less than 0.05% by mass, the reaction with the surface of the plating layer is insufficient, and the adhesion of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the amount of P conversion exceeds 3% by mass, the reaction with the Group 4A metal compound proceeds excessively, and the crosslinking effect of the Group 4A metal compound is impaired.
化學轉化處理皮膜中的磷酸鹽的P換算量可藉由使用螢光X射線分析裝置進行測定。 The P conversion amount of the phosphate in the chemical conversion treatment film can be measured by using a fluorescent X-ray analyzer.
化學轉化處理皮膜較佳為進一步包含矽烷偶合劑。藉由調配矽烷偶合劑，而可進一步提高化學轉化處理皮膜的密接性。矽烷偶合劑可使用：包含胺基、環氧基、巰基、丙烯醯氧基、甲基丙烯醯氧基、烷氧基、乙烯基、苯乙烯基、異氰酸酯基、氯丙基等官能基中的1種或2種以上的矽烷化合物。 The chemical conversion treatment film preferably further comprises a decane coupling agent. By blending the decane coupling agent, the adhesion of the chemical conversion coating film can be further improved. The decane coupling agent can be used: in the functional group including an amine group, an epoxy group, a decyl group, an acryloxy group, a methacryloxy group, an alkoxy group, a vinyl group, a styryl group, an isocyanate group, a chloropropyl group or the like. One or more kinds of decane compounds.
化學轉化處理皮膜中的矽烷偶合劑的含量，相對於含氟樹脂較佳為0.5質量%~5質量%的範圍內。在矽烷偶合劑的含量小於0.5質量%時，無法充分提高化學轉化處理皮膜的密接性。另一方面，在矽烷偶合劑的含量超過5質量%時，皮膜密接性飽和，而見不到其以上的提高。 The content of the decane coupling agent in the chemical conversion treatment film is preferably in the range of 0.5% by mass to 5% by mass based on the fluorine-containing resin. When the content of the decane coupling agent is less than 0.5% by mass, the adhesion of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of the decane coupling agent exceeds 5% by mass, the film adhesion is saturated, and the above improvement is not observed.
化學轉化處理皮膜中的矽烷偶合劑的含量可藉由使用螢光X射線分析裝置進行測定。 The content of the decane coupling agent in the chemical conversion treatment film can be measured by using a fluorescent X-ray analyzer.
化學轉化處理皮膜的膜厚較佳為0.5 μm~10 μm的範圍內。在膜厚小於0.5 μm時，無法充分賦予耐蝕性或耐變色性等。另一方面，即便使膜厚超過10 μm，亦無法期待膜厚的增加所伴隨的性能提高。 The film thickness of the chemical conversion treatment film is preferably in the range of 0.5 μm to 10 μm. When the film thickness is less than 0.5 μm, corrosion resistance, discoloration resistance, and the like cannot be sufficiently imparted. On the other hand, even if the film thickness exceeds 10 μm, the performance improvement accompanying the increase in the film thickness cannot be expected.
本發明的化學轉化處理鍍Al系鋼板的製造方法並無特別限定，例如可藉由以下方法製造。 The method for producing the chemical conversion-treated Al-based steel sheet according to the present invention is not particularly limited, and can be produced, for example, by the following method.
本發明的化學轉化處理鍍Al系鋼板的製造方法包 括：1)準備Al系合金鍍鋼板(化學轉化處理底板)的第1步驟、2)準備化學轉化處理液的第2步驟、3)在Al系合金鍍鋼板的表面形成化學轉化處理皮膜的第3步驟。另外，在介隔基底化學轉化處理皮膜而在Al系合金鍍鋼板的表面形成化學轉化處理皮膜時，在形成化學轉化處理皮膜的第3步驟前，進一步包括：在Al系合金鍍鋼板的表面形成基底化學轉化處理皮膜的步驟。 Method for producing chemical conversion-treated Al-based steel sheet according to the present invention 1) a first step of preparing an Al-based alloy plated steel sheet (chemical conversion treatment substrate), 2) a second step of preparing a chemical conversion treatment liquid, and 3) forming a chemical conversion treatment film on the surface of the Al-based alloy-plated steel sheet 3 steps. Further, when the chemical conversion treatment film is formed on the surface of the Al-based alloy-plated steel sheet by interposing the substrate chemical conversion treatment film, before the third step of forming the chemical conversion treatment film, further comprising: forming on the surface of the Al-based alloy-plated steel sheet The step of chemically transforming the substrate to treat the film.
第1步驟中，準備上述Al系合金鍍鋼板作為化學轉化處理底板。 In the first step, the above-described Al-based alloy plated steel sheet was prepared as a chemical conversion treatment substrate.
第2步驟中，準備包含具有上述親水性官能基的含氟樹脂(較佳為含氟的烯烴樹脂)、4A族金屬化合物及樹脂粒子的化學轉化處理液。 In the second step, a chemical conversion treatment liquid containing a fluorine-containing resin (preferably a fluorine-containing olefin resin) having a hydrophilic functional group, a Group 4A metal compound, and resin particles is prepared.
化學轉化處理液可藉由在具有上述親水性官能基的含氟樹脂(較佳為含氟的烯烴樹脂)的水系乳液中，添加4A族金屬化合物及樹脂粒子(例如聚乙烯-氟樹脂粒子)而製備。添加於化學轉化處理液中的4A族金屬化合物可使用：4A族金屬的含氧酸鹽或氟化物、氫氧化物、有機酸鹽、碳酸鹽、過氧化鹽等。含氧酸鹽的例子包括：氫酸鹽、銨鹽、鹼金屬鹽、鹼土金屬鹽等。化學轉化處理液中根據需要可進一步添加聚乙烯樹脂粒子或磷酸鹽、矽烷偶合劑等。 The chemical conversion treatment liquid may be added with a Group 4A metal compound and resin particles (for example, polyethylene-fluororesin particles) in an aqueous emulsion of a fluorine-containing resin (preferably a fluorine-containing olefin resin) having the above hydrophilic functional group. And prepared. As the Group 4A metal compound to be added to the chemical conversion treatment liquid, an oxoacid salt or a fluoride, a hydroxide, an organic acid salt, a carbonate, a peroxy salt or the like of a Group 4A metal can be used. Examples of the oxyacid salt include a hydrogenate, an ammonium salt, an alkali metal salt, an alkaline earth metal salt, and the like. Further, if necessary, a polyethylene resin particle, a phosphate, a decane coupling agent or the like may be added to the chemical conversion treatment liquid.
水系乳液所含的含氟樹脂的數量平均分子量較佳為1000以上，更佳為1萬以上，特佳為20萬以上。原因是 如上所述，對化學轉化處理皮膜賦予耐水性。另一方面，就處理液的穩定性的觀點而言，含氟樹脂的數量平均分子量較佳為200萬以下。 The number average molecular weight of the fluorine-containing resin contained in the aqueous emulsion is preferably 1,000 or more, more preferably 10,000 or more, and particularly preferably 200,000 or more. The reason is As described above, water resistance is imparted to the chemical conversion treatment film. On the other hand, the number average molecular weight of the fluorine-containing resin is preferably 2,000,000 or less from the viewpoint of the stability of the treatment liquid.
含氟樹脂就幾乎不使用乳化劑便可製備水系乳液的觀點而言，較佳為具有0.05質量%~5質量%的親水性官能基。 The fluorine-containing resin preferably has a hydrophilic functional group of 0.05% by mass to 5% by mass from the viewpoint of preparing an aqueous emulsion using almost no emulsifier.
含氟樹脂的水系乳液中的乳化劑的含量較佳為1質量%以下。在乳化劑超過1質量%時，在第3步驟中形成化學轉化處理皮膜時，有導致乳化劑因乾燥溫度而殘存於化學轉化處理皮膜中的擔憂。若如此導致乳化劑殘存於化學轉化處理皮膜中，則會導致化學轉化處理皮膜的耐水性顯著降低，因此欠佳。如上所述，若為具有親水性官能基的含氟樹脂，則即便將乳化劑的量設為1質量%以下，亦可製備水系乳液。 The content of the emulsifier in the aqueous emulsion of the fluorine-containing resin is preferably 1% by mass or less. When the emulsifier is more than 1% by mass, when the chemical conversion treatment film is formed in the third step, there is a concern that the emulsifier remains in the chemical conversion treatment film due to the drying temperature. If the emulsifier remains in the chemical conversion treatment film as described above, the water resistance of the chemical conversion treatment film is remarkably lowered, which is not preferable. As described above, in the case of the fluorine-containing resin having a hydrophilic functional group, the aqueous emulsion can be prepared even when the amount of the emulsifier is 1% by mass or less.
就耐候性及耐水性的觀點而言，含氟樹脂的水系乳液中可含有的乳化劑較佳為全氟辛酸的銨鹽、全氟壬酸的銨鹽等氟系乳化劑。此外，公知的氟系界面活性劑亦可用作乳化劑。 The emulsifier which can be contained in the aqueous emulsion of the fluorine-containing resin is preferably a fluorine-based emulsifier such as an ammonium salt of perfluorooctanoic acid or an ammonium salt of perfluorodecanoic acid, from the viewpoint of weather resistance and water resistance. Further, a known fluorine-based surfactant can also be used as an emulsifier.
化學轉化處理液中的含氟樹脂的含量，相對於水100質量份較佳為10質量份~70質量份的範圍內。在含氟樹脂的含量小於10質量份時，在乾燥過程中水的蒸發量變多，而有化學轉化處理皮膜的成膜性及緻密性降低的擔憂。另一方面，在含氟樹脂的含量超過70質量份時，有化學轉化處理液的保存穩定性降低的擔憂。 The content of the fluorine-containing resin in the chemical conversion treatment liquid is preferably in the range of 10 parts by mass to 70 parts by mass based on 100 parts by mass of the water. When the content of the fluorine-containing resin is less than 10 parts by mass, the amount of evaporation of water during drying increases, and the film forming property and compactness of the chemical conversion coating film may be lowered. On the other hand, when the content of the fluorine-containing resin exceeds 70 parts by mass, the storage stability of the chemical conversion treatment liquid may be lowered.
化學轉化處理液中的4A族金屬的氧酸鹽、氟化物、氫氧化物、有機酸鹽、碳酸鹽或過氧化鹽的含量，相對於含氟樹脂100質量份，以金屬換算計較佳為0.1質量份~5質量份的範圍內。在這些鹽的含量小於0.1質量份時，交聯反應及與鍍敷層表面的反應不足，而無法充分提高化學轉化處理皮膜的耐水性及皮膜密接性。另一方面，這些鹽的含量超過5質量份時，有進行交聯反應而化學轉化處理液的保存穩定性降低的擔憂。 The content of the oxyacid salt, the fluoride, the hydroxide, the organic acid salt, the carbonate or the peroxy salt of the Group 4A metal in the chemical conversion treatment liquid is preferably 0.1 in terms of metal with respect to 100 parts by mass of the fluorine resin. Within the range of ~5 parts by mass. When the content of these salts is less than 0.1 part by mass, the crosslinking reaction and the reaction with the surface of the plating layer are insufficient, and the water resistance and the film adhesion of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of these salts exceeds 5 parts by mass, the crosslinking reaction may be carried out, and the storage stability of the chemical conversion treatment liquid may be lowered.
化學轉化處理液中的樹脂粒子(例如聚乙烯-氟樹脂粒子)的含量，相對於固體成分(含氟樹脂或4A族金屬化合物等)100質量份，較佳為0.5質量份~20質量份的範圍內。如上所述，在樹脂粒子的含量小於0.5質量%時，無法充分提高化學轉化處理皮膜的潤滑性。另一方面，在樹脂粒子的含量超過20質量%時，有導致化學轉化處理皮膜的耐候性降低的擔憂。 The content of the resin particles (for example, polyethylene-fluororesin particles) in the chemical conversion treatment liquid is preferably 0.5 parts by mass to 20 parts by mass based on 100 parts by mass of the solid content (such as a fluorine-containing resin or a Group 4A metal compound). Within the scope. As described above, when the content of the resin particles is less than 0.5% by mass, the lubricity of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of the resin particles exceeds 20% by mass, the weather resistance of the chemical conversion treatment film may be lowered.
除了聚乙烯-氟樹脂粒子外，進一步將聚乙烯樹脂粒子添加於化學轉化處理液中的情況下，化學轉化處理液中的聚乙烯樹脂粒子的含量，相對於固體成分100質量份，較佳為0.1質量份~16質量份的範圍內。如上所述，在聚乙烯樹脂粒子的含量小於0.1質量%時，無法充分發揮聚乙烯樹脂的效果。另一方面，在添加量超過16質量%時，有導致化學轉化處理皮膜的耐候性降低的擔憂。另外，聚乙烯樹脂粒子的平均粒徑較佳為0.1 μm~10 μm的範圍內。在平均粒徑小於0.1 μm時，會導致大部分的聚乙烯樹脂粒 子埋沒在化學轉化處理皮膜中，而無法使聚乙烯樹脂滲出至化學轉化處理皮膜的表面。另一方面，在平均粒徑超過10 μm時，有在使化學轉化處理液乾燥的期間導致聚乙烯樹脂粒子脫落的擔憂。 When the polyethylene resin particles are further added to the chemical conversion treatment liquid in addition to the polyethylene-fluororesin particles, the content of the polyethylene resin particles in the chemical conversion treatment liquid is preferably 100 parts by mass based on the solid content. Within the range of 0.1 parts by mass to 16 parts by mass. As described above, when the content of the polyethylene resin particles is less than 0.1% by mass, the effect of the polyethylene resin cannot be sufficiently exhibited. On the other hand, when the amount added exceeds 16% by mass, there is a concern that the weather resistance of the chemical conversion treatment film is lowered. Further, the average particle diameter of the polyethylene resin particles is preferably in the range of 0.1 μm to 10 μm. When the average particle size is less than 0.1 μm, most of the polyethylene resin particles are caused. The sub-layer is buried in the chemical conversion treatment film, and the polyethylene resin cannot be exuded to the surface of the chemical conversion treatment film. On the other hand, when the average particle diameter exceeds 10 μm, there is a concern that the polyethylene resin particles fall off during the drying of the chemical conversion treatment liquid.
在化學轉化處理液中添加磷酸鹽時，化學轉化處理液中的磷酸鹽的含量，相對於含氟樹脂100質量份，以P換算計較佳為0.05質量份~3質量份的範圍內。在磷酸鹽的含量小於0.05質量份時，無法充分提高化學轉化處理皮膜的密接性。另一方面，在磷酸鹽的含量超過3質量份時，有與4A族金屬化合物的反應過度進行，而損及4A族金屬化合物的交聯效果的擔憂。 When the phosphate is added to the chemical conversion treatment liquid, the content of the phosphate in the chemical conversion treatment liquid is preferably in the range of 0.05 parts by mass to 3 parts by mass in terms of P based on 100 parts by mass of the fluorine-containing resin. When the content of the phosphate is less than 0.05 parts by mass, the adhesion of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of the phosphate exceeds 3 parts by mass, the reaction with the Group 4A metal compound proceeds excessively, which may impair the crosslinking effect of the Group 4A metal compound.
在化學轉化處理液中添加矽烷偶合劑時，化學轉化處理液中的矽烷偶合劑的含量，相對於含氟樹脂100質量份，較佳為0.5質量份~5質量份的範圍內。在矽烷偶合劑的含量小於0.5質量份時，無法充分提高化學轉化處理皮膜的密接性。另一方面，在矽烷偶合劑的含量超過5質量份時，皮膜密接性飽和，而見不到其以上的提高。另外，亦有導致化學轉化處理液的穩定性降低的擔憂。 When the decane coupling agent is added to the chemical conversion treatment liquid, the content of the decane coupling agent in the chemical conversion treatment liquid is preferably in the range of 0.5 parts by mass to 5 parts by mass based on 100 parts by mass of the fluorine-containing resin. When the content of the decane coupling agent is less than 0.5 part by mass, the adhesion of the chemical conversion treatment film cannot be sufficiently improved. On the other hand, when the content of the decane coupling agent exceeds 5 parts by mass, the film adhesion is saturated, and the above improvement is not observed. Further, there is a concern that the stability of the chemical conversion treatment liquid is lowered.
化學轉化處理液中，根據需要亦可添加蝕刻劑或無機化合物、無機潤滑劑、著色顏料、染料等作為其他成分。蝕刻劑可使用氟化物等。蝕刻劑藉由將鍍敷層表面活化而進一步提高化學轉化處理皮膜的密接性。Mg或Ca、Sr、V、W、Mn、B、Si、Sn等的無機化合物(氧化物、磷酸鹽等)，會使化學轉化處理皮膜緻密化而提高耐水性。二硫 化鉬或滑石等無機潤滑劑會自化學轉化處理液被帶入皮膜，而進一步提高化學轉化處理皮膜的潤滑性、以及化學轉化處理鍍Al系鋼板的加工性。另外，藉由調配無機顏料或有機顏料、有機染料等，而可對化學轉化處理皮膜賦予特定的色調。 In the chemical conversion treatment liquid, an etchant or an inorganic compound, an inorganic lubricant, a coloring pigment, a dye or the like may be added as an additional component as needed. Fluoride or the like can be used as the etchant. The etchant further enhances the adhesion of the chemical conversion treatment film by activating the surface of the plating layer. Inorganic compounds (oxides, phosphates, etc.) such as Mg or Ca, Sr, V, W, Mn, B, Si, Sn, etc., make the chemical conversion treatment film denser and improve water resistance. Disulfide The inorganic lubricant such as molybdenum or talc is brought into the film from the chemical conversion treatment liquid, and the lubricity of the chemical conversion treatment film and the processability of the chemical conversion treatment of the Al-based steel sheet are further improved. Further, by blending an inorganic pigment, an organic pigment, an organic dye or the like, a specific color tone can be imparted to the chemical conversion treatment film.
在第3步驟中，在第1步驟中所準備的Al系合金鍍鋼板的表面形成化學轉化處理皮膜。為了形成化學轉化處理皮膜，只要將第2步驟中所準備的化學轉化處理液塗佈於第1步驟中所準備的Al系合金鍍鋼板的表面並乾燥即可。 In the third step, a chemical conversion treatment film is formed on the surface of the Al-based alloy plated steel sheet prepared in the first step. In order to form a chemical conversion treatment film, the chemical conversion treatment liquid prepared in the second step may be applied to the surface of the Al-based alloy-plated steel sheet prepared in the first step and dried.
化學轉化處理液的塗佈方法並無特別限定，自公知的方法中適當選擇即可。此種塗佈方法的例子包括：輥塗法或淋幕式塗裝(curtain flow)法、旋塗法、噴霧法、浸漬提拉法等。 The method of applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method, and the like.
化學轉化處理液的乾燥可為常溫乾燥，但若考慮到連續作業，則較佳為保持於50℃以上而縮短乾燥時間。但是在保持於超過300℃時，存在有機成分熱分解而使化學轉化處理皮膜的性能降低的擔憂。在本發明的製造方法中，由於化學轉化處理液中所含的乳化劑的含量少，因此即便將乾燥溫度設為50℃左右，亦可幾乎不含乳化劑而形成耐水性優異的化學轉化處理皮膜。 The drying of the chemical conversion treatment liquid can be carried out at room temperature. However, in consideration of continuous operation, it is preferably kept at 50 ° C or higher to shorten the drying time. However, when it is kept at more than 300 ° C, there is a concern that the organic component is thermally decomposed to lower the performance of the chemical conversion treatment film. In the production method of the present invention, since the content of the emulsifier contained in the chemical conversion treatment liquid is small, even if the drying temperature is about 50 ° C, the chemical conversion treatment excellent in water resistance can be formed without containing an emulsifier. Membrane.
圖2是表示化學轉化處理皮膜的形成過程的剖面示意圖。圖2中表示塗佈添加了聚乙烯-氟樹脂粒子及聚乙烯樹脂粒子的化學轉化處理液的形態。 Fig. 2 is a schematic cross-sectional view showing a process of forming a chemical conversion treatment film. Fig. 2 shows a form in which a chemical conversion treatment liquid to which polyethylene-fluororesin particles and polyethylene resin particles are added is applied.
首先，在Al系合金鍍鋼板110的表面塗佈化學轉化處理液，而形成化學轉化處理液的塗膜120(參照圖2A)。化學轉化處理液的塗膜120中分散有聚乙烯-氟樹脂粒子122及聚乙烯樹脂粒子124。 First, a chemical conversion treatment liquid is applied to the surface of the Al-based alloy plated steel sheet 110 to form a coating film 120 of a chemical conversion treatment liquid (see FIG. 2A). Polyethylene-fluororesin particles 122 and polyethylene resin particles 124 are dispersed in the coating film 120 of the chemical conversion treatment liquid.
接著，若提高溫度至50℃左右，則水分蒸發而形成化學轉化處理皮膜120'(參照圖2B)。此時，聚乙烯-氟樹脂粒子122及聚乙烯樹脂粒子124的大部分自化學轉化處理皮膜120'的表面突起。圖3A是將化學轉化處理液的塗膜以50℃進行乾燥後的化學轉化處理皮膜的SEM像(俯視)。雖然無法區別聚乙烯-氟樹脂粒子與聚乙烯樹脂粒子，但可知這些粒子自化學轉化處理皮膜的表面突起(參照圖中「PE-F或PE」)。 Next, when the temperature is raised to about 50 ° C, water is evaporated to form a chemical conversion treatment film 120 ′ (see FIG. 2B ). At this time, most of the polyethylene-fluororesin particles 122 and the polyethylene resin particles 124 protrude from the surface of the chemical conversion treatment film 120'. 3A is an SEM image (plan view) of a chemical conversion treatment film obtained by drying a coating film of a chemical conversion treatment liquid at 50 °C. Although the polyethylene-fluororesin particles and the polyethylene resin particles could not be distinguished, it was found that these particles protruded from the surface of the chemical conversion treatment film (see "PE-F or PE" in the drawing).
接著，若提高溫度至150℃左右，則聚乙烯樹脂粒子124熔融，聚乙烯樹脂滲出至表面(參照圖2C)。滲出的聚乙烯樹脂124'被覆化學轉化處理皮膜120'的表面的全部或一部分。另一方面，聚乙烯-氟樹脂粒子122不熔融而維持原來的狀態。圖3B是將化學轉化處理液的塗膜以150℃進行乾燥後的化學轉化處理皮膜的SEM像(俯視)。可知僅聚乙烯-氟樹脂粒子自化學轉化處理皮膜的表面突起(參照圖中「PE-F」)。圖3C是自化學轉化處理皮膜的表面突起的聚乙烯-氟樹脂粒子的SEM像(剖面視)。可藉由螢光X射線分析確認自該化學轉化處理皮膜的表面突起的粒子為聚乙烯-氟樹脂粒子。圖4是自化學轉化處理皮膜的表面突起的聚乙烯-氟樹脂粒子的螢光X射線光譜。 Next, when the temperature is raised to about 150 ° C, the polyethylene resin particles 124 are melted, and the polyethylene resin oozes to the surface (see FIG. 2C). The exuded polyethylene resin 124' is coated with all or a portion of the surface of the chemical conversion treated film 120'. On the other hand, the polyethylene-fluororesin particles 122 are not melted and remain in the original state. 3B is an SEM image (plan view) of the chemical conversion treatment film obtained by drying the coating film of the chemical conversion treatment liquid at 150 °C. It is understood that only the polyethylene-fluororesin particles are protruded from the surface of the chemical conversion treatment film (see "PE-F" in the drawing). Fig. 3C is an SEM image (cross-sectional view) of polyethylene-fluororesin particles protruding from the surface of the chemical conversion treatment film. The particles protruding from the surface of the chemical conversion treatment film were confirmed to be polyethylene-fluororesin particles by fluorescent X-ray analysis. Fig. 4 is a fluorescent X-ray spectrum of polyethylene-fluororesin particles protruding from the surface of the chemical conversion treatment film.
根據以上的順序，可製造耐候性、耐水性、皮膜密接性及加工性均優異的本發明的化學轉化處理鍍Al系鋼板。 According to the above procedure, the chemical conversion-treated Al-based steel sheet of the present invention which is excellent in weather resistance, water resistance, film adhesion, and workability can be produced.
在形成基底化學轉化處理皮膜的步驟中，在形成化學轉化處理皮膜前，在第1步驟中所準備的Al系合金鍍鋼板的表面塗佈基底化學轉化處理液而形成塗佈膜。基底化學轉化處理液例如可藉由輥塗法、旋塗法、噴霧法等等進行塗佈。基底化學轉化處理液的塗佈量較佳為以閥金屬附著量為1 mg/m2以上的方式進行調整。原因是，對所得的化學轉化處理鋼板賦予充分的耐蝕性。另外，基底化學轉化處理液的塗佈量較佳為以所形成的基底化學轉化處理皮膜的厚度為3 nm以上1000 nm以下的方式進行調整。在厚度為3 nm以上時，會表現出充分的耐蝕性，若厚度超過1000 nm，則欲對鋼板進行成形加工時，有因應力而產生龜裂的擔憂。 In the step of forming the substrate chemical conversion treatment film, before the chemical conversion treatment film is formed, the substrate chemical conversion treatment liquid is applied onto the surface of the Al-based alloy plated steel sheet prepared in the first step to form a coating film. The substrate chemical conversion treatment liquid can be applied, for example, by a roll coating method, a spin coating method, a spray method, or the like. The coating amount of the substrate chemical conversion treatment liquid is preferably adjusted so that the valve metal adhesion amount is 1 mg/m 2 or more. The reason is that the obtained chemical conversion treated steel sheet is provided with sufficient corrosion resistance. Further, the coating amount of the base chemical conversion treatment liquid is preferably adjusted so that the thickness of the formed base chemical conversion treatment film is 3 nm or more and 1000 nm or less. When the thickness is 3 nm or more, sufficient corrosion resistance is exhibited. When the thickness exceeds 1000 nm, there is a fear that cracks may occur due to stress when the steel sheet is to be formed.
不將形成於Al系合金鍍鋼板的表面的塗佈膜進行水洗而進行乾燥，藉此可形成基底化學轉化處理皮膜。亦可在常溫下乾燥，若考慮到連續作業，則較佳為保持於50℃以上而縮短乾燥時間。但是在超過200℃的乾燥溫度下，有化學轉化處理被膜所含的有機成分發生熱分解，而損及由有機成分賦予的特性的情況。 The coating film formed on the surface of the Al-based alloy plated steel sheet is not washed with water and dried, whereby a substrate chemical conversion treatment film can be formed. It can also be dried at normal temperature. If continuous operation is considered, it is preferable to keep it at 50 ° C or more to shorten the drying time. However, at a drying temperature exceeding 200 ° C, the organic component contained in the chemical conversion treatment film is thermally decomposed to impair the properties imparted by the organic component.
以下，參照實例對本發明進行詳細地說明，但本發明並不限定於這些實例。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
將板厚0.8 mm的SPCC作為基材，而製作熔融Al-9質量%Si合金鍍鋼板(鍍敷附著量45 g/m2)。本實例中，使用該鍍鋼板作為化學轉化處理底板。 A SP2.5 having a thickness of 0.8 mm was used as a substrate to prepare a molten Al-9 mass% Si alloy plated steel sheet (plating adhesion amount: 45 g/m 2 ). In this example, the plated steel sheet was used as a chemical conversion treatment substrate.
在熔融Al-9質量%Si合金鍍鋼板的表面塗佈表1所示的組成的化學轉化處理液，以到達板溫140℃進行加熱乾燥，而形成膜厚2.0 μm的化學轉化處理皮膜。 The chemical conversion treatment liquid having the composition shown in Table 1 was applied onto the surface of the molten Al-9 mass% Si alloy plated steel sheet, and dried at a plate temperature of 140 ° C to form a chemical conversion treatment film having a film thickness of 2.0 μm.
表1所示的處理液No.1~No.12的化學轉化處理液，是在包含特定量的具有羧基及磺酸基的含氟樹脂、與乳化劑的水系乳液(不揮發成分25質量%；參照表2)中，添加4A族金屬化合物、聚乙烯-氟樹脂粒子(樹脂粒子)等而製備。處理液No.13的化學轉化處理液是在包含胺基甲酸酯樹脂與乳化劑的水系乳液(不揮發成分25質量%；參照表2)中，添加4A族金屬化合物、聚乙烯-氟樹脂粒子(樹脂粒子)等而製備。 The chemical conversion treatment liquid of the treatment liquid No. 1 to No. 12 shown in Table 1 is a water-based emulsion containing a specific amount of a fluorine-containing resin having a carboxyl group and a sulfonic acid group, and an emulsifier (nonvolatile content: 25% by mass) Referring to Table 2), a Group 4A metal compound, polyethylene-fluororesin particles (resin particles), or the like is added. The chemical conversion treatment liquid of the treatment liquid No. 13 is a water-based emulsion containing a urethane resin and an emulsifier (25% by mass of a nonvolatile component; see Table 2), and a 4A group metal compound or a polyethylene-fluororesin is added. It is prepared by particles (resin particles) or the like.
含有含氟樹脂的水系乳液可藉由在水溶劑中添加特定量的氟烯烴、含羧基的單體、含磺酸基的單體及乳化劑，使這些成分進行共聚合反應而得。包含胺基甲酸酯樹脂的水系乳液是使用PR135(住化拜耳氨酯(Sumika Bayer Urethane)股份有限公司)。矽烷偶合劑是使用A-1891(邁圖高新材料日本有限公司(Momentive Performance Materials Japan))。 The aqueous emulsion containing a fluorine-containing resin can be obtained by subjecting a component to a copolymerization reaction by adding a specific amount of a fluoroolefin, a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, and an emulsifier to an aqueous solvent. An aqueous emulsion containing a urethane resin is PR135 (Sumika Bayer Urethane Co., Ltd.). The decane coupling agent was A-1891 (Momentive Performance Materials Japan).
使用螢光X射線分析裝置，測定各化學轉化處理鍍Al系鋼板的化學轉化處理皮膜中相對於有機樹脂的4A族金屬、磷酸鹽及矽烷偶合劑的量。磷酸鹽及矽烷偶合劑的含量根據P及Si的測定值而算出。另外，使用掃描型電子顯微鏡，測定各化學轉化處理鍍Al系鋼板的化學轉化處理皮膜的表面中聚乙烯-氟樹脂粒子的面積佔有率。對於各化學轉化處理液，將所形成的化學轉化處理皮膜中相對於有機樹脂的4A族金屬、磷酸鹽及矽烷偶合劑的量、以及化學轉化處理皮膜的表面中聚乙烯-氟樹脂粒子的面積佔有率表示於表3。 The amount of the Group 4A metal, phosphate, and decane coupling agent relative to the organic resin in the chemical conversion treatment film of each of the chemical conversion-treated Al-based steel sheets was measured using a fluorescent X-ray analyzer. The content of the phosphate and decane coupling agent was calculated from the measured values of P and Si. In addition, the area occupation ratio of the polyethylene-fluororesin particles in the surface of the chemical conversion treatment film of each of the chemical conversion treatment-coated Al-based steel sheets was measured using a scanning electron microscope. For each chemical conversion treatment liquid, the amount of the Group 4A metal, phosphate and decane coupling agent relative to the organic resin in the formed chemical conversion treatment film, and the area of the polyethylene-fluororesin particles in the surface of the chemical conversion treatment film. The occupancy rate is shown in Table 3.
自各化學轉化處理鍍Al系鋼板切出試驗片，依據JIS K5600-7-7：2008實施促進耐候性試驗(氙燈法)。本試驗 中，將在照射氙弧燈的光120分鐘的期間噴射18分鐘的水的步驟設為1個循環(2小時)，將該步驟重複0個循環~1000個循環(0個循環、500個循環、1000個循環)。 The test piece was cut out from each of the chemical conversion-treated Al-based steel sheets, and the weather resistance test (xenon lamp method) was carried out in accordance with JIS K5600-7-7:2008. This test In the middle, the step of spraying the water for 18 minutes during the irradiation of the xenon arc lamp for 120 minutes is set to one cycle (2 hours), and the step is repeated from 0 cycles to 1000 cycles (0 cycles, 500 cycles). , 1000 cycles).
藉由剖面顯微鏡檢查，對各化學轉化處理鍍Al系鋼板測定促進耐候試驗前後的化學轉化處理皮膜的厚度，而求出塗膜殘存率。對於各化學轉化處理鍍Al系鋼板，將塗膜殘存率為95%以上的情形評價為「◎」，將塗膜殘存率為80%以上且小於95%的情形評價為「○」，將塗膜殘存率為60%以上且小於80%的情形評價為「△」，將塗膜殘存率為30%以上且小於60%的情形評價為「▲」，將塗膜殘存率小於30%的情形評價為「×」。 The thickness of the chemical conversion treatment film before and after the weathering test was measured for each chemical conversion-treated Al-based steel sheet by cross-sectional microscopy, and the coating film residual ratio was determined. In the case of the chemical conversion treatment of the Al-based steel sheet, the coating film residual ratio was 95% or more, and it was evaluated as "?", and the coating film residual ratio was 80% or more and less than 95%, and it was evaluated as "○". When the film residual ratio is 60% or more and less than 80%, it is evaluated as "△", and when the coating film residual ratio is 30% or more and less than 60%, it is evaluated as "▲", and the residual film rate is less than 30%. The evaluation is "X".
對於各化學轉化處理鍍Al系鋼板，使用促進耐候試驗前後的試驗片(尺寸：30 mm×150 mm)，進行拉深筋(draw bead)試驗(模具的筋高度：4 mm、加壓力：1.0 kN)後，計測模具滑動的部分的皮膜殘存率。對於各化學轉化處理鍍Al系鋼板，將皮膜殘存率為95%以上的情形評價為「◎」，將皮膜殘存率為80%以上且小於95%的情形評價為「○」，將皮膜殘存率為60%以上且小於80%的情形評價為「△」，將皮膜殘存率為30%以上且小於60%的情形評價為「▲」，將皮膜殘存率小於30%的情形評價為「×」。 For each chemical conversion-treated Al-based steel sheet, a test piece (size: 30 mm × 150 mm) before and after the accelerated weathering test was used, and a draw bead test was performed (the rib height of the mold: 4 mm, pressure: 1.0) After kN), the residual rate of the film at the portion where the mold was slid was measured. In the case of the chemical conversion treatment of the Al-based plated steel sheet, the film residual ratio was 95% or more, and the film residual rate was 80% or more and less than 95%, and the film residual rate was evaluated as "○". When it is 60% or more and less than 80%, it is evaluated as "△", and when the film residual ratio is 30% or more and less than 60%, it is evaluated as "▲", and when the film residual ratio is less than 30%, it is evaluated as "×". .
對於各化學轉化處理鍍Al系鋼板，使用促進耐候試驗 後的試驗片進行鹽水噴霧試驗(依據JIS Z2371；120小時)，並評價平坦部的白鏽產生面積率。對於各化學轉化處理鍍Al系鋼板，將白鏽產生面積率為5%以下的情形評價為「◎」，將白鏽產生面積率超過5%且10%以下的情形評價為「○」，將白鏽產生面積率超過10%且30%以下的情形評價為「△」，將白鏽產生面積率超過30%且50%以下的情形評價為「▲」，將白鏽產生面積率超過50%的情形評價為「×」。 For each chemical conversion treatment of Al-plated steel sheets, the use of accelerated weathering test The subsequent test piece was subjected to a salt spray test (in accordance with JIS Z2371; 120 hours), and the area ratio of white rust generation in the flat portion was evaluated. In the case of the chemical conversion treatment of the Al-based steel sheet, the white rust generation area ratio was 5% or less, and the white rust generation area ratio was more than 5% and 10% or less, and it was evaluated as "○". When the area ratio of white rust generation is more than 10% and 30% or less, it is evaluated as "△", and when the area ratio of white rust is more than 30% and 50% or less, it is evaluated as "▲", and the area ratio of white rust is more than 50%. The situation is evaluated as "X".
自各化學轉化處理鍍Al系鋼板切出寬度30 mm、長度300 mm的試驗片。使SKD11製模具與各試驗片的兩面接觸，介隔模具一邊施加600 kgf的負荷一邊以100 mm/分鐘的速度拉抽試驗片。測定此時的拉抽力(drawing force)，並評價潤滑性。對於各化學轉化處理鍍Al系鋼板，將拉抽力為200 kgf以下的情形評價為「◎」，將拉抽力超過200 kgf且250 kgf以下的情形評價為「○」，將拉抽力超過250 kgf且300 kgf以下的情形評價為「△」，將拉抽力超過300 kgf且400 kgf以下的情形評價為「▲」，將拉抽力超過400 kgf的情形評價為「×」。 A test piece having a width of 30 mm and a length of 300 mm was cut out from each of the chemical conversion-treated Al-based steel sheets. The SKD11 mold was brought into contact with both sides of each test piece, and the test piece was pulled at a speed of 100 mm/min while applying a load of 600 kgf through the mold. The drawing force at this time was measured, and the lubricity was evaluated. For each of the chemical conversion-treated Al-based steel sheets, the case where the pulling force is 200 kgf or less is evaluated as "◎", and the case where the drawing force exceeds 200 kgf and 250 kgf or less is evaluated as "○", and the pulling force is exceeded. The case of 250 kgf and 300 kgf or less was evaluated as "△", and the case where the pulling force exceeded 300 kgf and 400 kgf or less was evaluated as "▲", and the case where the pulling force exceeded 400 kgf was evaluated as "x".
將對各化學轉化處理鍍Al系鋼板(實例1~實例7、比較例1~比較例6)所使用的處理液的種類、以及耐候性試驗、皮膜密接性試驗、平坦部耐蝕性試驗及潤滑性試驗的評價結果表示於表4。 The types of the treatment liquid used for the Al-based steel sheets (Examples 1 to 7 and Comparative Examples 1 to 6) for each chemical conversion treatment, and the weather resistance test, the film adhesion test, the flat portion corrosion resistance test, and the lubrication were performed. The evaluation results of the sex test are shown in Table 4.
耐候性是藉由促進耐候性試驗後的化學轉化處理皮膜的塗膜殘存率進行評價。在形成包含胺基甲酸酯樹脂的化學轉化處理皮膜的比較例6的化學轉化處理鍍Al系鋼板中，在500個循環(相當於在屋外暴露5年)時，導致化學轉化處理皮膜消失。另外，在形成包含過大的聚乙烯-氟樹脂粒子的化學轉化處理皮膜的比較例4的化學轉化處理鍍Al系鋼板中，亦導致聚乙烯-氟樹脂粒子自化學轉化處理皮膜脫落，因此耐候性劣化。另一方面，在形成包含特定量的具有親水性官能基的含氟樹脂及4A族金屬化合物的化學轉化處理皮膜的實例1~實例7的化學轉化處理鍍Al系鋼板中，在重複1000個循環(相當於在屋外暴露10年)後，化學轉化處理皮膜的膜厚亦幾乎無變化。 The weather resistance was evaluated by promoting the residual film coating rate of the chemical conversion treatment film after the weather resistance test. In the chemical conversion-treated Al-based steel sheet of Comparative Example 6 in which the chemical conversion treatment film containing the urethane resin was formed, the chemical conversion treatment film disappeared in 500 cycles (corresponding to exposure for 5 years outside the house). Further, in the chemical conversion-treated Al-based steel sheet of Comparative Example 4 in which the chemical conversion treatment film containing the excessively large polyethylene-fluororesin particles was formed, the polyethylene-fluororesin particles were also peeled off from the chemical conversion treatment film, and thus the weather resistance was exhibited. Deterioration. On the other hand, in the chemical conversion-treated Al-based steel sheet of Examples 1 to 7 which forms a chemical conversion treatment film containing a specific amount of a fluorine-containing resin having a hydrophilic functional group and a Group 4A metal compound, 1000 cycles are repeated. (Equivalent to exposure to outside the house for 10 years), the film thickness of the chemical conversion treatment film hardly changed.
皮膜密接性是藉由拉深筋試驗後的皮膜殘存率進行評價。在形成包含胺基甲酸酯樹脂的化學轉化處理皮膜的比較例6的化學轉化處理鍍Al系鋼板中，在500個循環(相當於在屋外暴露5年)時，導致化學轉化處理皮膜幾乎消失，因此拉深筋試驗後亦不存在皮膜。另一方面，在形成包含特定量的具有親水性官能基的含氟樹脂、4A族金屬化合物及聚乙烯-氟樹脂粒子的化學轉化處理皮膜的實例1~實例7的化學轉化處理鍍Al系鋼板中，在重複1000個循環(相當於屋外暴露10年)後，皮膜的密接性亦良好。 The film adhesion was evaluated by the residual rate of the film after the draw rib test. In the chemical conversion treatment-plated Al-based steel sheet of Comparative Example 6 in which a chemical conversion treatment film containing a urethane resin was formed, the chemical conversion treatment film almost disappeared in 500 cycles (corresponding to exposure for 5 years outside the house). Therefore, there is no film after the drawstring test. On the other hand, the chemical conversion-treated Al-based steel sheet of Examples 1 to 7 in which a chemical conversion treatment film containing a specific amount of a fluorine-containing resin having a hydrophilic functional group, a Group 4A metal compound, and a polyethylene-fluororesin particle is formed is formed. In the case of repeating 1000 cycles (equivalent to 10 years of exposure to the outside of the house), the adhesion of the film was also good.
耐蝕性是藉由鹽水噴霧試驗後的白鏽產生面積率進行評價。在形成包含胺基甲酸酯樹脂的化學轉化處理皮膜的比較例6的化學轉化處理鍍Al系鋼板中，雖然促進耐候性 試驗前耐蝕性良好，但隨著皮膜消失而導致耐蝕性明顯降低。另外，在形成包含過多量或過少量的具有親水性官能基的含氟樹脂的化學轉化處理皮膜的比較例1及比較例2的化學轉化處理鍍Al系鋼板、以及形成不含4A族金屬化合物的化學轉化處理皮膜的比較例3及比較例5的化學轉化處理鍍Al系鋼板中，自促進耐候性試驗前起耐蝕性劣化。另一方面，在形成包含特定量的具有親水性官能基的含氟樹脂及4A族金屬化合物的化學轉化處理皮膜的實例1~實例7的化學轉化處理鍍Al系鋼板中，在重複1000個循環(相當於屋外暴露10年)後，耐蝕性亦良好。 The corrosion resistance was evaluated by the area ratio of white rust generated after the salt spray test. In the chemical conversion-treated Al-based steel sheet of Comparative Example 6 in which a chemical conversion treatment film containing a urethane resin is formed, although weather resistance is promoted The corrosion resistance was good before the test, but the corrosion resistance was significantly reduced as the film disappeared. Further, the chemical conversion treatment of the Al-based steel sheet of Comparative Example 1 and Comparative Example 2, which comprises a chemical conversion treatment film containing an excessive amount or a small amount of a fluorine-containing resin having a hydrophilic functional group, and formation of a metal compound not containing a Group 4A In the chemical conversion treatment of the chemical conversion treatment of Comparative Example 3 and Comparative Example 5, the Al-based steel sheet was deteriorated in corrosion resistance from the accelerated weather resistance test. On the other hand, in the chemical conversion-treated Al-based steel sheet of Examples 1 to 7 which forms a chemical conversion treatment film containing a specific amount of a fluorine-containing resin having a hydrophilic functional group and a Group 4A metal compound, 1000 cycles are repeated. (Equivalent to 10 years of exposure outside the house), the corrosion resistance is also good.
潤滑性是藉由將施加負荷的試驗片拉抽時所需要的拉抽力進行評價。比較例1的化學轉化處理鍍Al系鋼板由於化學轉化處理皮膜中的聚乙烯-氟樹脂粒子的量少，因此潤滑性劣化。同樣，不含聚乙烯-氟樹脂粒子的比較例5的化學轉化處理鍍Al系鋼板的潤滑性亦劣化。另外，比較例6的化學轉化處理鍍Al系鋼板由於聚乙烯-氟樹脂粒子的平均粒徑小，並且埋沒在化學轉化處理皮膜中，因此潤滑性劣化。另一方面，在形成包含特定量的平均粒徑為特定範圍內的聚乙烯-氟樹脂粒子的化學轉化處理皮膜的實例1~實例7的化學轉化處理鍍Al系鋼板中，潤滑性良好。 The lubricity was evaluated by the pulling force required when the test piece to which the load was applied was drawn. In the chemical conversion treatment of the Al-based steel sheet of Comparative Example 1, since the amount of the polyethylene-fluororesin particles in the chemical conversion treatment film is small, the lubricity is deteriorated. Similarly, the chemical conversion-treated Al-based steel sheet of Comparative Example 5 containing no polyethylene-fluororesin particles was also deteriorated in lubricity. Further, in the chemical conversion treatment of the Al-based steel sheet of Comparative Example 6, since the average particle diameter of the polyethylene-fluororesin particles is small and is buried in the chemical conversion treatment film, the lubricity is deteriorated. On the other hand, in the chemical conversion-treated Al-based steel sheet of Examples 1 to 7 in which a specific chemical conversion coating film containing a specific amount of the polyethylene-fluororesin particles having a specific particle diameter within a specific range was formed, the lubricity was good.
根據以上結果可知，本發明的化學轉化處理鍍Al系鋼板的耐候性、耐蝕性、皮膜密接性及加工性(潤滑性)優異。 According to the above results, the chemical conversion-treated Al-based steel sheet of the present invention is excellent in weather resistance, corrosion resistance, film adhesion, and workability (lubricity).
參考實驗是表示調查氟樹脂皮膜中的4A族金屬化合物的量及乳化劑的量、與透濕度的關係的結果。 The reference experiment is a result of investigating the relationship between the amount of the Group 4A metal compound in the fluororesin film, the amount of the emulsifier, and the moisture permeability.
在以成為1質量%的方式添加含親水性官能基的單體、以成為1質量%的方式添加乳化劑而製作的具有親水性官能基的含氟樹脂的水系乳液中，添加特定量的4A族金屬化合物，將所製備的化學轉化處理液藉由棒塗機塗佈於鍍鋼板的表面，以到達板溫140℃進行加熱乾燥，而形成膜厚30 μm的氟樹脂皮膜。將該氟樹脂皮膜自鍍鋼板剝離，切出特定大小而製成試驗片。對各試驗片(游離氟樹脂皮膜)依據JIS Z0208測定透濕度(測定條件、溫度40℃±0.5℃、相對濕度90%±2%、24小時)。 A specific amount of 4A is added to an aqueous emulsion containing a hydrophilic functional group-containing monomer and a fluorine-containing resin having a hydrophilic functional group prepared by adding an emulsifier to 1% by mass. As the group metal compound, the prepared chemical conversion treatment liquid was applied onto the surface of the plated steel sheet by a bar coater, and dried at a plate temperature of 140 ° C to form a fluororesin film having a film thickness of 30 μm. The fluororesin film was peeled off from the plated steel sheet, and cut to a specific size to prepare a test piece. The moisture permeability (measurement conditions, temperature: 40 ° C ± 0.5 ° C, relative humidity: 90% ± 2%, 24 hours) was measured for each test piece (free fluororesin film) in accordance with JIS Z0208.
圖5是表示氟樹脂皮膜中4A族金屬的量與透濕度的關係的圖表。根據該圖表可知，藉由將氟樹脂皮膜中的4A族金屬的量設為0.1質量%以上，而可顯著降低氟樹脂皮膜的透濕度。 Fig. 5 is a graph showing the relationship between the amount of the Group 4A metal and the moisture permeability in the fluororesin film. According to the graph, the moisture permeability of the fluororesin film can be remarkably reduced by setting the amount of the Group 4A metal in the fluororesin film to 0.1% by mass or more.
在以成為1質量%的方式添加含親水性官能基的單體、並添加特定量的乳化劑而製作的具有親水性官能基的含氟樹脂的水系乳液中，以最終濃度以金屬換算計為1質量%的方式添加4A族金屬化合物，將所製備的化學轉化處理液藉由棒塗機塗佈於鍍鋼板的表面，以到達板溫140℃進行加熱乾燥，而形成膜厚30 μm的氟樹脂皮膜。將該氟樹脂皮膜自鍍鋼板剝離，切出特定的大小而製成試驗片。對各試驗片(游離氟樹脂皮膜)依據JIS Z0208測定透濕度(測定條件、溫度40℃±0.5℃、相對濕度 90%±2%、24小時)。 In an aqueous emulsion containing a hydrophilic functional group-containing fluororesin prepared by adding a hydrophilic functional group-containing monomer to a content of 1% by mass and adding a specific amount of an emulsifier, the final concentration is expressed in terms of metal. The 4A metal compound was added in a 1% by mass manner, and the prepared chemical conversion treatment liquid was applied onto the surface of the plated steel sheet by a bar coater, and dried at a plate temperature of 140 ° C to form a fluorine having a film thickness of 30 μm. Resin film. The fluororesin film was peeled off from the plated steel sheet, and cut to a specific size to prepare a test piece. For each test piece (free fluororesin film), the moisture permeability was measured in accordance with JIS Z0208 (measurement conditions, temperature: 40 ° C ± 0.5 ° C, relative humidity) 90% ± 2%, 24 hours).
圖6是表示含氟樹脂的水系乳液中的乳化劑的濃度與氟樹脂皮膜的透濕度的關係的圖表。根據該圖表可知，藉由將乳液中的乳化劑的濃度設為1質量%以下，而可顯著降低氟樹脂皮膜的透濕度。 Fig. 6 is a graph showing the relationship between the concentration of the emulsifier in the aqueous emulsion of the fluorine resin and the moisture permeability of the fluororesin film. According to this graph, the moisture permeability of the fluororesin film can be remarkably lowered by setting the concentration of the emulsifier in the emulsion to 1% by mass or less.
根據以上的結果可知，4A族金屬化合物的量多、且乳化劑的殘存量少的氟樹脂皮膜的耐水性優異。 From the above results, it is understood that the fluororesin film having a large amount of the Group 4A metal compound and having a small amount of the emulsifier remaining is excellent in water resistance.
本申請主張基於2011年9月14日申請的日本專利特願2011-200654的優先權。該申請說明書及圖式中所記載的內容全部引用至本案說明書中。 The present application claims priority based on Japanese Patent Application No. 2011-200654 filed on Sep. 14, 2011. The contents described in the specification and drawings of the application are all incorporated in the specification.
本發明的化學轉化處理鍍Al系鋼板由於耐候性、耐水性、皮膜密接性、耐蝕性及加工性優異，因此有效用於外包裝建材等各種用途。例如本發明的化學轉化處理鍍Al系鋼板可較佳地用於：1)塑膠棚(vinyl house)或農業棚用鋼管、型鋼、支柱、梁、搬送用構件；2)遮音壁、防音壁、吸音壁、防雪壁、護軌、高欄、防護柵、支柱；3)軌道車輛用構件、架線用構件、電氣設備用構件、安全環境用構件、構造用構件、太陽光架台等用途。 The chemical conversion-treated Al-based steel sheet of the present invention is excellent in weather resistance, water resistance, film adhesion, corrosion resistance, and workability, and thus is effectively used for various applications such as packaging materials. For example, the chemical conversion-treated Al-based steel sheet of the present invention can be preferably used for: 1) a plastic house or a steel pipe for agricultural sheds, a steel, a pillar, a beam, and a conveying member; 2) a sound insulating wall, a soundproof wall, and a sound absorbing sound. Wall, snow-proof wall, guard rail, high-column, protective grille, pillar; 3) rail vehicle components, wire-hanging components, electrical equipment components, safety environment components, structural members, solar gantry, etc.
Al系合金鍍鋼板在高溫高濕下與塗膜充分地密接，並且耐蝕性優異。因此，本發明的化學轉化處理鍍Al系鋼板特別適合用作高溫高濕環境下所使用的外包裝用材料。 The Al-based alloy plated steel sheet is sufficiently adhered to the coating film under high temperature and high humidity, and is excellent in corrosion resistance. Therefore, the chemical conversion-treated Al-based steel sheet of the present invention is particularly suitable for use as an outer packaging material used in a high-temperature and high-humidity environment.
110‧‧‧Al系合金鍍鋼板 110‧‧‧Al alloy plated steel plate
120‧‧‧化學轉化處理液的塗膜 120‧‧‧ Coating film of chemical conversion treatment liquid
120'‧‧‧化學轉化處理皮膜 120'‧‧‧Chemical conversion treatment film
122‧‧‧聚乙烯-氟樹脂粒子 122‧‧‧Polyethylene-fluororesin particles
124‧‧‧聚乙烯樹脂粒子 124‧‧‧ Polyethylene resin particles
124'‧‧‧滲出的聚乙烯樹脂 124'‧‧‧Exuded polyethylene resin
圖1A~圖1D是經特定溫度加熱的包含聚乙烯樹脂粒 子或聚乙烯-氟樹脂粒子的化學轉化處理皮膜的SEM像。 1A to 1D are polyethylene resin pellets heated at a specific temperature SEM image of the film by chemical conversion of the sub- or polyethylene-fluororesin particles.
圖2A~圖2C是表示化學轉化處理皮膜的形成過程的剖面示意圖。 2A to 2C are schematic cross-sectional views showing a process of forming a chemical conversion treatment film.
圖3A~圖3C是表示化學轉化處理皮膜的形成過程的SEM像。 3A to 3C are SEM images showing a process of forming a chemical conversion treatment film.
圖4是化學轉化處理皮膜中的聚乙烯-氟樹脂粒子的螢光X射線光譜。 Fig. 4 is a fluorescence X-ray spectrum of polyethylene-fluororesin particles in a chemical conversion treated film.
圖5是表示氟樹脂皮膜中的4A族金屬的量與透濕度的關係的圖表。 Fig. 5 is a graph showing the relationship between the amount of the Group 4A metal and the moisture permeability in the fluororesin film.
圖6是表示含氟樹脂的乳液中的乳化劑的濃度與氟樹脂皮膜的透濕度的關係的圖表。 Fig. 6 is a graph showing the relationship between the concentration of the emulsifier in the emulsion of the fluorine resin and the moisture permeability of the fluororesin film.
110‧‧‧Al系合金鍍鋼板 110‧‧‧Al alloy plated steel plate
120‧‧‧化學轉化處理液的塗膜 120‧‧‧ Coating film of chemical conversion treatment liquid
122‧‧‧聚乙烯-氟樹脂粒子 122‧‧‧Polyethylene-fluororesin particles
124‧‧‧聚乙烯樹脂粒子 124‧‧‧ Polyethylene resin particles
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011200654A JP5674606B2 (en) | 2011-09-14 | 2011-09-14 | Chemical conversion treated steel sheet and method for producing the same |
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| TW201323658A TW201323658A (en) | 2013-06-16 |
| TWI531678B true TWI531678B (en) | 2016-05-01 |
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| JP (1) | JP5674606B2 (en) |
| IN (1) | IN2014MN00664A (en) |
| TW (1) | TWI531678B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0328380A (en) * | 1989-06-26 | 1991-02-06 | Kawasaki Steel Corp | Surface treated steel sheet having excellent lubricity and corrosion resistance |
| JPH06248227A (en) * | 1993-02-24 | 1994-09-06 | Asahi Glass Co Ltd | Fluororesin coating composition |
| JP3365366B2 (en) * | 1999-09-06 | 2003-01-08 | ダイキン工業株式会社 | Crosslinkable fluororesin aqueous dispersion composition |
| WO2001098392A1 (en) * | 2000-06-22 | 2001-12-27 | Pohang Iron & Steel Co., Ltd. | Preparation of aqueous urethane resin composition |
| JP2003105555A (en) * | 2001-07-23 | 2003-04-09 | Nkk Corp | Surface treated steel sheet excellent in white rust resistance and method for producing the same |
| JP2003293169A (en) * | 2002-04-04 | 2003-10-15 | Furukawa Electric Co Ltd:The | Fluorine resin coated Al material |
| JP2004250560A (en) * | 2003-02-19 | 2004-09-09 | Nippon Yushi Basf Coatings Kk | Water-based paint composition |
| JP2005138294A (en) * | 2003-11-04 | 2005-06-02 | Nisshin Steel Co Ltd | Coated metal sheet excellent in lubricity and processability |
| JP2005162993A (en) * | 2003-12-05 | 2005-06-23 | Daikin Ind Ltd | Aqueous fluorine-containing curable composition |
| JP4324096B2 (en) * | 2004-12-24 | 2009-09-02 | 新日本製鐵株式会社 | Painted metal plate with excellent reflectivity and formability and method for producing the same |
| JP3846807B1 (en) * | 2005-10-06 | 2006-11-15 | 株式会社神戸製鋼所 | Pre-coated metal plate and manufacturing method thereof |
| US8895153B2 (en) * | 2010-06-18 | 2014-11-25 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
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| JP2013060641A (en) | 2013-04-04 |
| IN2014MN00664A (en) | 2015-07-03 |
| TW201323658A (en) | 2013-06-16 |
| JP5674606B2 (en) | 2015-02-25 |
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