TWI832833B - 金屬材料用表面處理劑、具有表面處理覆膜的金屬材料及其製造方法 - Google Patents
金屬材料用表面處理劑、具有表面處理覆膜的金屬材料及其製造方法 Download PDFInfo
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- TWI832833B TWI832833B TW107146779A TW107146779A TWI832833B TW I832833 B TWI832833 B TW I832833B TW 107146779 A TW107146779 A TW 107146779A TW 107146779 A TW107146779 A TW 107146779A TW I832833 B TWI832833 B TW I832833B
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- metal materials
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- 239000007769 metal material Substances 0.000 title claims abstract description 108
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 238000004381 surface treatment Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- -1 fluoride ions Chemical class 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 58
- 150000002500 ions Chemical class 0.000 claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract 2
- 238000005554 pickling Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 235000021110 pickles Nutrition 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000012528 membrane Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 54
- 150000001491 aromatic compounds Chemical class 0.000 description 27
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 22
- 239000002904 solvent Substances 0.000 description 18
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- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012736 aqueous medium Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003335 secondary amines Chemical group 0.000 description 6
- 150000003512 tertiary amines Chemical group 0.000 description 6
- 150000003141 primary amines Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000005237 degreasing agent Methods 0.000 description 4
- 239000013527 degreasing agent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- WOMTYMDHLQTCHY-UHFFFAOYSA-N 3-methylamino-1,2-propanediol Chemical compound CNCC(O)CO WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 125000004990 dihydroxyalkyl group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 2
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 description 2
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 2
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- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- UZPVVYLJBOXNOH-UHFFFAOYSA-N octyl 2-hydroxyacetate;titanium Chemical compound [Ti].CCCCCCCCOC(=O)CO UZPVVYLJBOXNOH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- JJRUMNJYJCPDQL-UHFFFAOYSA-N tert-butyl(3-triethoxysilylpropyl)carbamic acid Chemical compound CCO[Si](OCC)(OCC)CCCN(C(O)=O)C(C)(C)C JJRUMNJYJCPDQL-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
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- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/26—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 hexavalent chromium compounds containing also organic compounds
- C23C22/28—Macromolecular compounds
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- 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
- C23C22/73—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 characterised by the process
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- 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
- C23C22/78—Pretreatment of the material to be coated
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/083—Iron or steel solutions containing H3PO4
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/085—Iron or steel solutions containing HNO3
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
本案提供一種表面處理劑,其可對於各種金屬材料形成無6價鉻化成覆膜,且其能夠形成具有良好耐蝕性的覆膜,此外也提供具有藉由該表面處理劑而獲得的表面處理覆膜的金屬材料及其製造方法。本案之金屬材料用表面處理劑用於對金屬材料進行表面處理,其摻入:至少一種含有三價鉻的離子A的供給源(A);離子B的供給源(B),該離子B係含有鈦的離子以及含有鋯的離子所構成群組中所選擇的至少一種;水溶性或水分散性化合物(C),其具有:烷氧基矽烷基;芳香環;與該芳香環直接鍵結的羥基;由一級胺基、二級胺基、三級胺基及四級胺基所構成群組中所選的至少一種胺基,且其中該烷氧基矽烷基係直接地或是透過亞烷基而鍵結至該胺基的氮原子,含氟化合物(D),其可提供含氟離子,且其中該表面處理劑包含游離氟離子。
Description
本發明係關於使用於金屬材料的表面處理劑、具有基於該表面處理劑所形成表面處理覆膜的金屬材料及其製造方法。
於飛機材料、建築材料、汽車零件等廣泛的領域中,在過去已開發了含有3價鉻的金屬材料用表面處理劑。
例如,專利文獻1當中揭示了一種金屬材料用化成處理液,其含有:成分(A),其係由水溶性3價鉻化合物所構成;成分(B),其係由水溶性鈦化合物、水溶性鋯化合物中所選的至少一種成分所構成;成分(C),其由水溶性硝酸鹽化合物所構成:成分(D),其係由水溶性鋁化合物所構成;成分(E),其由氟化合物所構成,且pH值係控制於2.3至5.0範圍內。
專利文獻2當中揭示了一種化成處理液,其包含特定含量的特定3價鉻、特定的鋯化合物、特定的二羧酸化合物。
專利文獻3當中揭示了一種水性表面處理劑,其含有:特定的水溶性化合物(A);化合物(B),其含有由硼、鈦、鋯及矽所構成群組中所選的至少一種元素。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2006-328501號公報
[專利文獻2]日本特開2006-316334號公報
[專利文獻3]日本特開2009-280889號公報
然而,以在專利文獻1-3當中的金屬材料用表面處理劑來說,要形成對各種金屬材料具有良好耐蝕性的覆膜係為困難。
本發明之目的在於:提供一種金屬材料用表面處理劑,其可形成對於各種金屬材料具有良好耐蝕性的覆膜;具有基於該金屬材料用表面處理劑所形成表面處理覆膜的金屬材料;以及其製造方法。
本案發明人為了要解決上述問題而致力研究的結果,研究出一種金屬材料用表面處理劑,其可形成對於各種金屬材料具有良好耐蝕性的覆膜,進而完成本發明。該金屬材料用表面處理劑摻入:至少一種含有三價鉻的離子A的供給源(A);離子B的供給源(B),該離子B係含有鈦的離子以及含有鋯的離子所構成群組中所選擇的至少一種;特定的水溶性或水分散性化合物(C);以及含氟化合物(D),其可提供含氟離子。
為了解決上述問題的本發明為:
(1)一種金屬材料用表面處理劑,用於對金屬材料進行表面處理,其摻入:至少一種含有三價鉻的離子A的供給源(A);離子B的供給源(B),該離子B係含有
鈦的離子以及含有鋯的離子所構成群組中所選擇的至少一種;水溶性或水分散性化合物(C),其具有:烷氧基矽烷基;芳香環;與該芳香環直接鍵結的羥基;由一級胺基、二級胺基、三級胺基及四級胺基所構成群組中所選的至少一種胺基,且該烷氧基矽烷基係直接地或是透過亞烷基而鍵結至該胺基的氮原子,含氟化合物(D),其可提供含氟離子,且其中,該表面處理劑包含游離氟離子。
(2)如(1)所述之金屬材料用表面處理劑,其中,該離子A的鉻換算質量及該離子B的金屬換算質量的合計質量相對於該化合物(C)的固態含量質量的比[(A+B)/C)]係於0.03~100範圍內。
(3)一種具有表面處理覆膜的金屬材料之製造方法,其包含:接觸製程,其係使如(1)或(2)所述之金屬材料用表面處理劑接觸金屬材料的表面或是表面上。
(4)於如(3)所述之具有表面處理覆膜的金屬材料之製造方法,其包含:酸洗製程,其係於該接觸製程之前,以酸洗處理液對金屬材料進行酸洗,且該酸洗處理液摻入由含氟化合物、硫酸化合物、硝酸化合物、磷酸化合物、羥基羧酸化合物及過氧化氫化合物所構成群組中所選的至少一種成分。
(5)一種金屬材料,其具有藉著使如(1)或(2)所述之金屬材料用表面處理劑接觸金屬材料的表面或是表面上而形成的表面處理覆膜。
根據本發明,可提供:可形成對各種金屬材料具良好耐蝕性覆膜的金屬材料用表面處理劑;具有基於該金屬材料用表面處理劑所形成的表面處理覆膜之金屬材料以及其製造方法。
以下說明本發明的實施型態。
<<金屬材料用表面處理劑>>
本實施型態之表面處理劑係為用於對金屬材料進行表面處理的藥劑。該表面處理劑亦可作為化成處理劑來使用。該表面處理劑係摻入:至少一種含有三價鉻的離子A的供給源(A);離子B的供給源(B),該離子B係由含有鈦的離子以及含有鋯的離子所構成群組中所選擇的至少一種;水溶性或水分散性化合物(C),其具有:烷氧基矽烷基;芳香環;與該芳香環直接鍵結的羥基;由一級胺基、二級胺基、三級胺基及四級胺基所構成群組中所選的至少一種胺基,且該烷氧基矽烷基係直接地或是透過亞烷基而鍵結至該胺基的氮原子;含氟化合物(D),其可提供含氟離子。其結果為成為了包含游離氟離子之物。雖然金屬材料用表面處理劑亦可為僅將此等成分摻入至水性媒介之物,但也可為摻入其他成分之物。以下詳細敘述各種成分、組成(添加量、添加比)以及液性。此外,作為含有金屬的離子,可舉例例如金屬離子、氧化物離子、氫氧化物離子、錯離子等。此外,雖然可包含,也可不包含6價鉻,但若考慮對於環境之影響,以實質上不包含6價鉻的型態為佳。
(供給源A)
金屬材料用表面處理劑當中的供給源(A)只要為藉著混合至水性媒介而提供離子A者即可,並不需要特別限制。作為供給源(A),可列舉例如:氟化鉻(III)、硝酸鉻(III)、硫酸鉻(III)、磷酸鉻(III)。此等供給源(A)可僅使用一種,亦可使用兩種以上。金屬材料用表面處理劑當中離子(A)的含量並不需特別限制,以鉻換算質量濃度來說通常在10~500mg/L範圍內,其中以25~300mg/L範圍內為佳。
(供給源B)
關於金屬材料用表面處理劑當中的供給源(B),只要是藉由混合於水性媒介來提供離子B者即可,並不需特別限制。作為供給源(B),可列舉例如:硫酸鈦、硫酸氧鈦、硫酸鈦銨、硝酸鈦、硝酸氧鈦、硝酸鈦銨、六氟鈦酸、六氟鈦錯鹽、硫酸鋯、硫酸氧鋯、硫酸鋯銨、硝酸鋯、硝酸氧鋯、硝酸鋯銨、六氟鋯酸、六氟鋯錯鹽、乳酸鈦、乙醯丙酮鈦、鈦酸三乙醇胺(titanium triethanol aminate)、鈦酸乙醇酸辛酯(titanium octyl glycolate)、鈦酸四異丙酯、鈦酸四正丁酯、乙酸氧鋯、乳酸氧鋯、四乙醯基丙酮基鋯、三丁氧基乙醯基丙酮基鋯、四正丁氧基鋯、四正丙氧基鋯等。此等的供給源B可僅使用一種,亦可使用兩種以上。金屬材料用表面處理劑當中離子B的含量並不需特別限定,惟金屬換算質量濃度(當混合兩種以上供給源時,合計的金屬換算質量濃度)通常為10~500mg/L範圍內,其中以25~300mg/L範圍內為佳。
(化合物C)
金屬材料表面處理劑當中的化合物(C)係為水溶性或是水分散性的化合物,且具有:烷氧基矽烷基;芳香環;直接與該芳香環鍵結的羥基;由一級胺基、二級胺基、三級胺基及四級胺基所組成群組中所選的至少一胺基,且其中該烷氧基矽烷基係直接鍵結至該胺基的氮原子。化合物(C)可為單體、均聚物或共聚物。
於此,該烷氧基矽烷基只要是具有矽原子以及直接鍵合至該矽原子的烷氧基即可;其中以具有矽原子及至少兩個直接連接至矽原子的烷氧基的基團為佳;其中又以具有矽原子及三個直接連接至矽原子的烷氧基的基團為較佳。作為該烷氧基,以碳數量1-10的烷氧基為佳;其中又以甲氧基或乙氧基為較佳。而該烷氧基矽烷基所具有的,烷氧基以外的基團,並不特別限定,可列舉例如以氫原子、碳數量1-10的烷基等為佳。作為該烷氧基矽烷基,具體來說可列舉例如:二甲基甲氧基矽烷基、甲基二甲氧基矽烷基、三甲氧基矽烷基、二乙基乙氧基矽烷基、乙基二乙氧基矽烷基、三乙氧基矽烷基等。
當化合物(C)為均聚物或是共聚物時(主鏈中具有重複單元時),關於化合物(C),以化合物(C)的每重複單元具有0.01-4個烷氧基矽烷基為佳;其中以0.05-2個為較佳;又以0.1-1.5個為更佳。
此外,當化合物(C)為單體時,以1分子中具有1-4個烷氧基矽烷基為佳;其中以具有1-3個為較佳;又以具有1-2個為更佳。
關於芳香環並不需特別限定,可列舉例如以苯環、萘環、蒽環,其中以苯環為佳。
化合物(C)係具有至少一種選自一級胺基、二級胺基、三級胺基、四級胺基之群組的胺基之物。其中,以具有二級胺基、三級胺基為較佳,又以具有三級胺基為更佳。
於此,化合物(C)係藉由例如以下述第一方法或第二方法而得的化合物。第一方法為:使芳香族化合物(a1)、胺基矽烷(a2)、甲醛進行反應之方法,其中芳香族化合物(a1)為具有直接鍵結到芳香環的至少一個羥基一即酚性羥基(phenolic hydroxy)的芳香族化合物;第二方法為:使芳香族化合物(a1)、胺基矽烷(a2)、胺化合物(a3)進行反應之方法,其中芳香族化合物(a1)為具有至少一個酚性羥基的芳香族化合物。
以第一方法及第二方法獲得的化合物(C)具有著一結構,此結構係藉由所謂曼尼希反應(Mannich reaction)而使得胺基透過甲醛衍生的亞甲基作為取代基而鍵結至該芳香族化合物(a1)所具有的芳香環上的結構。此化合物(C)的取代基的位置並不需特別限定,惟以芳香環的羥基的鄰位及/或對位被取代者為佳。
作為該芳香族化合物(a1),只要是至少一個羥基直接鍵結至芳香環者即可,並不需特別限制,可列舉例如:苯酚、雙酚A、對乙烯基苯酚、萘酚、鄰甲酚、間甲酚、對甲酚等。此外,亦可使用此等化合物的均聚物。聚合方法並不需特別限制,可採用習知的聚合方法,例如自由基聚合、陽離子聚合、縮聚。除此等以外,該芳香族化合物(a1)亦可使用苯酚-甲酚酚醛共聚物、乙烯基苯酚-苯乙烯共聚物等。此外,上述芳香族化合物(a1)亦可使用藉由如環氧氯丙烷等的鹵代環氧化物、如乙酸等的羧酸類、酯類、醯胺類、如三甲基矽
烷基氯等的有機矽烷類、醇類、如硫酸二甲酯等的烷基化物等而進行改性之物。此等芳香族化合物(a1)可單獨使用,亦可組合使用兩種以上。
該芳香族化合物(a1)係以選自苯酚、雙酚A、對乙烯基苯酚、萘酚、酚醛清漆樹酯、聚雙酚A、聚對乙烯基苯酚及苯酚-萘縮聚物所構成群組當中所選出的至少一種為佳;其中以酚醛清漆樹酯、聚雙酚A、聚對乙烯基苯酚及苯酚-萘縮聚物所構成群組當中所選出的至少一者為較佳;又以聚對乙烯基苯酚為更佳。
於此,於本說明書當中,該聚雙酚A係意指以下式表示的化合物。
上式當中,s係1-2000的整數,其中以5-1000的整數為佳。
此外,該聚對乙烯基苯酚係意指以下式表示的化合物。作為聚對乙烯基苯酚,可使用以習知聚合方法來將乙烯基苯酚進行聚合而成之物,亦
可使用市售品。作為市售品,可列舉例如丸善石油化學公司製的MARUKA LYNCUR等。
上式當中,t係1-4000的整數,其中以10-2000的整數為佳。
該芳香族化合物(a1)的重量平均分子量並不需特別限定,以200-1,000,000為佳;以500-500,000為較佳;又以1,000-200,000為更佳。此外,於本說明書當中,除另有說明之外,重量平均分子量係指藉由GPC(凝膠滲透色譜法)來測量,並以聚苯乙烯換算之值。
該胺基矽烷(a2)只要是具有:一級胺基及/或二級胺基(亞胺基);以及烷氧基矽烷基的化合物即可,並不需特別限定。例如可列舉例如以下式(2)所表示化合物為佳。
[化3]R3-NH-(CH2)n-SiR4 3-m(OR5)m (2)
式(2)當中,R3係氫原子、烷基、烯基、炔基、芐基、芳基、羥基烷基、二羥基烷基、三羥基烷基、胺基烷基、烷基胺基烷基、二烷基胺基烷
基、乙醯基或烷基羰基。作為烷基,可列舉例如以碳數量1-10的烷基為佳,其中,以甲基、乙基、異丙基、叔丁基為較佳。作為烯基,可列舉例如以碳數量1-10的烯基為佳,其中可列舉例如烯丙基為較佳。作為炔基,可列舉例如碳數量1-10的炔基為佳,其中以丙炔基為較佳。
作為芳基,可列舉例如以碳數量1-10的芳基為佳,其中以苯基、甲苯基、二甲苯基、萘基為較佳,其中又以苯基為更佳。作為羥基烷基,可列舉例如碳數量1-10的羥基烷基,其中可列舉2-羥基乙基為較佳。作為二羥基烷基,可列舉碳數量1-10的二羥基烷基為佳,又以雙(羥基乙基)為較佳。作為三羥基烷基,以碳數量1-10的三羥基烷基為佳,其中可列舉三(羥基乙基)為較佳。作為胺基烷基,以碳數量1-10的胺基烷基為佳,其中可列舉胺基乙基。
作為烷基胺基烷基,以碳數量1-10的烷基胺基烷基為佳,其中可列舉如2-甲基胺基乙烯為較佳。做為二烷基胺基烷基,可列舉以碳數量1-10的二烷基胺基烷基為佳,其中以二甲基胺基乙烯為較佳。作為烷基羰基,以碳數量1-10的烷基羰基為佳,其中可列舉乙醯基為較佳。
式(2)當中,R4及R5分別為烷基,其中以碳原子數1-10的烷基為佳,又以甲基、乙基為較佳。複數個的R4及R5分別可為相同或不同。
式(2)當中,n為1-3的整數;其中以2-3的整數為佳;又以3為較佳。
式(2)當中以m為1-3的整數為佳;其中以2或3為較佳;又以3為更佳。
作為胺基矽烷(a2),具體來說可列舉例如:γ-(苯基胺基)丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽
烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-[2-(N-乙烯基芐基胺基)乙基]-3-胺基丙基三甲氧基矽烷、N-[2-(N-乙烯基芐基胺基)乙基]-3-胺基丙基甲基二甲氧基矽烷、N-[2-(N-乙烯基芐基胺基)乙基]-3-胺基丙基三乙氧基矽烷、N-[2-(N-乙烯基芐基胺基)乙基]-3-胺基丙基甲基二乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基甲基二甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、γ-苯胺丙基甲基二乙氧基矽烷、N-雙[3-(三甲氧基矽烷基)丙基]-2-胺基乙烯基三甲氧基矽烷、N-(3-丙烯醯氧基-2-羥基丙基)-3-胺基丙基三乙氧基矽烷、N-(3-甲基丙烯醯氧基-2-羥基丙基)-3-胺基丙基三乙氧基矽烷、N-4-[(2-胺基乙基)胺基甲基]苯乙基三甲氧基矽烷、3-(2-胺基乙基胺基)異丁基二甲基甲氧基矽烷、3-(n-丁基胺基)丙基三甲氧基矽烷、3-(乙基胺基)異丁基三甲氧基矽烷、N-甲基-3-胺基丙基三甲氧基矽烷、N-烯丙基-3-胺基丙基三甲氧基矽烷、N-環己基-3-胺基丙基三甲氧基矽烷、N-苯基胺基甲基三乙氧基矽烷、N-甲基-3-胺基丙基甲基二甲氧基矽烷、雙[3-(三甲氧基矽烷基)丙基]胺、N,N'-雙[3-(三甲氧基矽烷基)丙基]乙二胺、N,N'-雙[3-(三乙氧基矽烷基)丙基]脲、雙[3-(甲基二乙氧基矽烷基)丙基]胺、3脲基丙基三乙氧基矽烷、3-脲基丙基三甲氧基矽烷、N,N-二辛基-N'-[3-(三乙氧基矽烷基)丙基]脲、N-(3-三乙氧基矽烷基丙基)葡糖醯胺、N-(3-三乙氧基矽烷基丙基)-叔丁基胺基甲酸酯、N-[3-(三乙氧基矽烷基)丙基]胺基甲酸酯、1,3-二乙烯基四甲基二矽氮烷、N-[3-(三甲氧基矽烷基)丙基]聚次乙亞胺、3-(2,4-二硝基苯基胺基)丙基三乙氧基矽烷、N-[3-(三乙氧基矽烷基)丙基]-對硝基苯胺等。此等成分可單獨使用,
亦可組合使用兩種以上。於此等成分當中,又以使用選自:γ-(苯基胺基)丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-甲基-3-胺基丙基三甲氧基矽烷、N-環己基-3-胺基丙基三甲氧基矽烷、雙[3-(三甲氧基矽烷基)丙基]胺,以及N-烯丙基-3-胺基丙基三甲氧基矽烷所構成群組當中的至少一種的胺基矽烷為佳。
第一方法當中該胺基矽烷(a2)的使用量係以相對於芳香族化合物(a1)100質量份為1-1200質量份為佳;其中以2-600質量份為較佳;又以3-300質量份為更佳。
第二方法當中胺基矽烷(a2)的使用量係以相對於芳香族化合物(a1)100質量份為1-1200質量份為佳;其中以2-600質量份為較佳;又以3-300質量份為更佳。
胺化合物(a3)只要為具有一級胺基及/或二級胺基(亞胺基)的化合物即可,不需特別限定,可列舉例如以下式(1)所表示的化合物為佳。
式(1)當中,R1與R2各與式(2)中的R3相同,但R1及R2亦可互相鍵結而形成嗎啉基(morpholino)。
作為胺化合物(a3),具體來說,可使用例如:如甲胺、乙胺、異丙胺、二甲胺、二乙胺、二異丙基胺等的烷基胺;如單乙醇胺、二乙醇胺、
2-甲基胺基乙醇、2-乙基胺基乙醇、3-甲基胺基-1,2-丙二醇、N-甲基葡糖胺等的烷醇胺;如苯胺、對甲基苯胺、N-甲基苯胺等的芳香族胺;如乙烯胺、烯丙胺的不飽和胺;如吡咯、吡咯烷、咪唑、吲哚、嗎啉、哌嗪等的多環胺;乙二胺;N-N-二甲基乙二胺;對-二甲基乙二胺;1,6六亞甲基二胺;1,3-丙二胺等。此等成分可單獨使用,亦可併用兩種以上。此等成分當中又以由2-甲基胺基乙醇、單乙醇胺、二乙醇胺、3-甲基胺基-1,2-丙二醇、N-甲基葡糖胺、N-甲基-1,3-丙二胺、N-甲基苯胺、乙胺、二乙胺、烯丙胺、芐胺、2-乙基胺基乙醇、乙二胺、對-二甲基乙基胺、嗎啉所構成之群組當中所選擇的至少一種胺化合物為佳。
第二方法當中胺化合物(a3)的使用量係以相對於芳香族化合物(a)100質量份為0.2-360質量份為佳;其中以0.4-270質量份為較佳;又以0.6-180質量份為更佳。
作為使用於反應的甲醛,可使用以溶劑稀釋而成之物。
作為溶劑只要是不參與反應者即可,並不需特別限定。可列舉例如:水;如甲醇、乙醇等醇類溶劑;如四氫呋喃、1,4-二噁烷的醚類溶劑;如二氯甲烷、三氯甲烷等的鹵素溶劑;如丙酮的酮類溶劑等。
第一方法當中甲醛的使用量,係以甲醛相對於胺基矽烷(a2)的胺基之莫耳比(甲醛/胺基)為1-100為佳;其中以2-50為較佳。
第二方法當中甲醛的使用量,係以甲醛相對於胺基矽烷(a2)中胺基以及胺化合物(a3)中胺基之合計的莫耳比(甲醛/胺基)為1-100為佳;其中以2-50為較佳。
作為化合物(C),係以下式(3)所表示包含重複單元的聚合物為較佳態樣之一。
式(3)當中,R6係與式(2)中的R3相同。R7係單鍵或是亞烷基;其中以碳數量1-10的亞烷基為佳,其中又以三亞甲基(-(CH2)3-)為較佳。R8及R9分別為烷基,其中以碳數量為1-10的烷基為佳;其中又以甲基、乙基為較佳。複數個的R8及R9可分別為相同或是不同。R10及R11分別與式(2)中的R3相同,但R10與R11亦可互相鍵和而形成嗎啉基。p為1-3之整數,其中以2或3為佳,其中又以3為更佳。
聚合物亦可包含以式(3)所示重複單元以外的重複單元。該聚合物係以由上式(3)所示重複單元、下式(5)所示重複單元、下式(6)所示重複單元、下式(7)所示重複單元、下式(8)所示重複單元、下式(9)所示重複單元所構成群組中所選至少一種重複單元所構成聚合物為較佳態樣之一。聚合物亦可進一步包含式(3)、式(5)-(9)中任一者所示重複單元之外的重複單元。
式(5)及式(9)當中,R6、R7、R8、R9、R10、R11及p係分別與式(3)當中R6、R7、R8、R9、R10、R11及p為相同。
作為聚合物的製造方法,並不需特別限定,可列舉例如以使聚對乙烯基苯酚、胺基矽烷(a2)、胺化合物(a3)、甲醛進行反應而得到聚合物之方法為佳。
作為聚合物,具體來說,可列舉例如包含以下式(4)所示重複單元之聚合物(以下稱為「第一態樣之化合物」)為佳。
第一態樣之化合物係以包含式(4)所示重複單元以外的重複單元為佳。第一態樣之化合物係以由式(4)所示重複單元、式(10)所示重複單元、式(11)所示重複單元、式(12)所示重複單元、式(13)所示重複單元及式(14)所示重複單元所構成群組當中所選的至少一種重複單元所構成聚合物為較佳態樣之一。本發明中第一態樣之化合物亦可進一步地包含式(4)及式(10)-(14)中任一者所示重複單元以外的重複單元。
第一態樣之化合物的製造方法並不需特別限定,可列舉例如使聚對乙烯基苯酚、γ-(苯基胺基)丙基三甲氧基矽烷、2-甲基胺基乙醇、甲醛進行反應而得到聚合物之方法為佳。
作為化合物(C)的其他較佳態樣,可列舉例如使:聚對乙烯基苯酚;如γ-(苯基胺基)丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-甲基-3-胺基丙基三甲氧基矽烷、N-環己基-3-胺基丙基三甲氧基矽烷、雙[3-(三甲氧基矽烷)丙基]胺、N-烯丙基-3-胺基丙基三甲氧基矽烷所構成群組中所選至少一種的胺基矽烷;如2-甲基胺基乙醇、單乙醇胺、二乙醇胺、3-甲基胺基-1,2-丙二醇、N-甲基葡糖胺、N-甲基-1,3-丙二胺、N-甲基苯胺、乙胺、二乙胺、烯丙胺、芐胺、2-乙基胺基乙醇、乙二胺、對-二甲基乙胺、嗎啉所構成群組當中所選至少一種的胺化合物;甲醛等成分於溶劑中進行反應而獲得化合物(以下稱為「第二態樣之化合物」)。
作為第二態樣之化合物的製造方法,並不需要特別限定,可列舉例如以使聚對乙烯基苯酚、胺基矽烷、胺基化合物、甲醛等成分於溶劑中進行反應而獲得第二態樣之化合物的方法為佳。作為第二態樣之化合物,其具有著一結構,此結構係藉由所謂曼尼希反應而使得胺基透過甲醛衍生的亞甲基作為取代基而鍵結至聚對乙烯基苯酚所具有的芳香環上的結構。第二態樣之化合物當中,芳香環的取代基位置並不需特別限制,以酚性羥基的鄰位被取代者為佳。
此外,關於反應當中的胺基矽烷的使用量相對於聚對乙烯基苯酚100質量份以1-1200質量份為佳;其中以2-600質量份為較佳;又以3-300質量份為更佳。於反應當中胺化合物的使用量,以相對於聚對乙烯基苯酚100質量份為0.2-360質量份為佳;其中以0.4-270質量份為較佳;又以0.6-180質量份為更佳。於反應當中的甲醛的使用量係以相對於聚對乙烯基苯酚100質量部為0.3-300質量份為佳;其中以0.6-200質量份為較佳;又以0.9-150質量份為更佳。
作為溶劑只要是不參與反應者即可,並不需特別限定。可列舉例如:水;如甲醇、乙醇等醇類溶劑;如四氫呋喃、1,4-二噁烷的醚類溶劑;如二氯甲烷、三氯甲烷等的鹵素溶劑;如丙酮的酮類溶劑。
溶劑的使用量係以相對於聚對乙烯基苯酚100質量份為0-10,000質量份為佳,其中以10-5,000質量份為較佳。
於第二態樣之化合物的製造方法當中,亦可藉著進一步添加催化劑,以提升反應速度,可縮短反應時間。作為催化劑,可列舉例如酸催化劑、鹼催化劑、路易斯酸催化劑等。
作為酸催化劑,具體來說,可列舉例如:如鹽酸、氯化氫氣體、硫酸、發煙硫酸、硝酸、濃硝酸、磷酸等的無機酸;如對甲苯磺酸、三氟甲磺酸、甲酸、乙酸等有機酸等。作為鹼催化劑,具體來說可列舉例如氫氧化鈉、氫氧化鉀、氫化鈉、吡啶、三乙胺、二異丙基胺基鋰等。
作為路易斯酸催化劑,具體來說,可列舉例如:氯化鋁、氯化鈦、三氟甲磺酸鑭、三氟甲磺酸鈧、三氟甲磺酸釔等。
催化劑的添加量並不需要特別限定,以相對於聚對乙烯基苯酚100質量份為1-300質量份為佳,其中以2-150質量份為較佳。
第二態樣之化合物的製造方法當中的反應溫度並不需特別限定,以0-150℃為佳,其中以20℃-100℃為較佳。
第二態樣之化合物的製造方法當中的反應時間並不需特別限定,惟可舉例例如以反應溫度於80℃情況下以約為24小時為佳。此外,當反應溫度為23℃時,以約7日為佳。
以下具體說明第二態樣之化合物的製造方法。惟,本發明的第二態樣之製造方法並不限定為此方法。首先,使聚對乙烯基苯酚與溶劑混和並且充分地溶解。接著,依序將胺化合物、胺基矽烷、甲醛及視需要而加入的催化劑於室溫下依序一邊攪拌一邊滴加進此混和液。將此混合液加溫至80℃並攪拌24小時之後,可獲得本實施型態之化合物。於此,添加胺基矽烷、胺基化合物、甲醛及催化劑之順序並不需要特別限定,以添加胺基矽烷及胺基化合物之後添加甲醛為佳。催化劑係以添加甲醛後添加為佳。
以此方法所獲得的第二態樣之化合物,係可藉由習知方式來進行純化。可藉由例如:基於不會溶解目標化合物的溶劑的沉澱法;基於常壓或減壓之蒸餾法;或是色譜法等方式,來進行純化。
化合物(C)的分子量或是重量平均分子量並不需特別限定,以20-1,000,000為佳;其中又以500-500,000為較佳,又以1,000-200,000為更佳。
化合物(C)的製造方法並不需要特別限定,可列舉例以如上述第二方法當中第一態樣及第二態樣之化合物的製造方法為佳。
關於金屬材料用表面處理劑當中化合物(C)的含量,離子A的鉻換算質量及離子B的金屬換算質量的合計質量相對於化合物(C)的固態含量質量的比[(A+B)/C)]係於0.03~100範圍內;其中以0.1-50範圍內為佳;又以0.1-24範圍內為更佳。最佳的合計質量比[(A+B)/C)]係大於3的範圍。於各範圍內可獲得較佳的覆膜性能。
(含氟化合物D)
作為含氟化合物(D),只要是能夠在混和至水性介質時能夠提供含氟離子的化合物即可,不需要特別限制,可列舉例如:氫氟酸、氟化銨、氟化鉻、六氟鈦酸、六氟鈦錯鹽、六氟鋯酸、六氟鋯錯鹽、氟化鎂、氟化鋁、六氟矽酸、氟化鈉、氟化鉀等。此等含氟化合物(D)可僅使用一種,亦可使用兩種以上。
游離氟離子可藉著供給源(A)及/或供給源(B)來提供。此情形之下,供給源(A)及/或供給源(B)成為與含氟化合物(D)相同的化合物。此外,亦可為於含氟化合物(D)基礎上還有與含氟化合物(D)係不同的化合物之供給源(A)及/或供給源(B)來予以提供。也就是說,含氟化合物(D)的一部分或是全部可與供
給源(A)及/或(B)的至少一部份為共通。金屬材料用表面處理劑當中的游離氟離子的氟換算質量濃度以3-100mg/L為佳,其中以5-70mg/L為較佳。於此,游離氟離子濃度係以日本專利公報特公平06-095086號公報(特開昭58-211644號公報)所記載方法而測量出的值。
(其他成分E)
關於其他成分(E)只要在不損及本發明效果範圍內即可,並不需要特別限制,可列舉例如包含釩、鉬、鎢、錳、鈰、鎂、鈣、鈷、鎳、鍶、鋰、鈮、釔、鉍等金屬元素的化合物或是pH值調節劑。此等成分可僅使用一種,亦可使用兩種以上。
此外,也可意圖性地摻加於接觸到金屬材料用表面處理劑時,因金屬材料的蝕刻所產生的鐵、鋁等金屬材料衍生成分。
本發明中的金屬材料用表面處理劑的pH值並不需要特別限制,以2.3-5.0為佳,其中以3.0-4.5為較佳。於此,本說明書當中的pH值係指使金屬材料用表面處理劑或是後述的酸洗處理液接觸金屬材料的表面或是表面上時溫度下的值。pH值的測量可藉由手持式導電率暨pH值測量儀(WM-32EP(東亞DKK股份有限公司製))等來進行。
<<金屬材料用表面處理劑的製造方法>>
本發明所請的金屬材料用表面處理劑可藉由將離子A的供給源(A)、離子B的供給源(B)、化合物(C)、含氟化合物(D)以適量摻入水性介質中並且攪拌而獲得。此外,於製造時,亦可將固體之供給源摻入至水性介質中,亦可以將固體
之供給源事先溶解於水性介質中之後作為水性介質溶液之方式來摻加。此外,金屬材料用表面處理劑之pH值係以使用硝酸、氫氟酸、碳酸氫銨、氨水等pH值調節劑來作調整為佳,惟並不限於此等成分。此外,pH值調節劑亦可使用一種或是兩種以上。
作為水性介質,可使用例如水或是水與水混溶性有機溶劑而成的混合液,其使用含50質量%以上的水。作為水混溶性有機溶劑,只要是與水之間具混溶性的有機溶劑即可,並不需特別限制,可列舉例如:如甲醇、乙醇等的醇類溶劑;丙酮等的酮類溶劑;如N-N’-二甲基甲醯胺、二甲基乙醯胺等的醯胺類溶劑;如乙二醇單丁醚、乙二醇單己醚等的醚類溶劑;如1-甲基-2-吡咯烷酮、1-甲基-2-吡咯烷酮等的吡咯烷酮類溶劑等。可將此等水混溶性有機溶劑混合其一種於水,亦可將兩種以上與水混溶。
<<具有表面處理覆膜的金屬材料製造方法>>
本實施型態中的具有表面處理覆膜的金屬材料之製造方法,係包含接觸製程,其係使本實施形態中的金屬材料用表面處理劑接觸金屬材料的表面或是表面上。藉此可於金屬材料的表面或是表面上形成表面處理覆膜。此外,於接觸製程之前可進行脫脂製程或酸洗製程等前處理製程。此外,可於各製程之後進行水洗製程,亦可於水洗製程之後進行乾燥製程。
(脫脂製程)
於本實施型態中的具有表面處理覆膜之金屬材料的製造方法當中,較佳地,可於進行接觸製程之前進行脫脂製程,也就是使習知的脫脂劑接觸金屬材
料的表面或表面上。作為進行脫脂製程的方法並不需特別限定,可舉例例如溶劑脫脂、鹼性脫脂等。
(酸洗製程)
於本實施型態中的具有表面處理覆膜之金屬材料的製造方法當中,較佳地,可於進行接觸製程之前,執行酸洗製程,即以特定的酸洗處理液接觸金屬材料的表面或是表面上。具體來說,作為酸洗處理液,可舉例例如使用摻入由含氟化合物、硫酸化合物、硝酸化合物、磷酸化合物、羥基羧酸、過氧化氫化合物所構成群組當中所選的至少一種的酸洗處理液為佳,其中以(α)硫酸化合物、硝酸化合物、磷酸化合物、羥基羧酸化合物及/或過氧化氫化合物;(β)含氟化合物之組合為較佳。於此,含氟化合物係與含氟化合物(D)為相同的化合物,可舉例以氫氟酸及水溶性氫氟酸鹽為佳,又以氫氟酸為較佳。硫酸化合物係為可將硫酸離子提供至酸洗處理液中的化合物,可列舉如硫酸、硫酸鹽、硫酸酯,其中可舉硫酸為佳。硝酸化合物係將硝酸離子提供至酸洗處理液中之物,可列舉例如硝酸、硝酸鹽、硝酸酯,其中可舉硝酸為佳。磷酸化合物係將磷酸離子提供至酸洗處理液當中之物,可列舉例如磷酸、磷酸鹽、磷酸酯,其中可舉磷酸為佳。關於羥基羧酸化合物,可列舉例如羥基羧酸、羥基羧酸酸鹽,其中可舉如羥基羧酸為佳。作為過氧化氫化合物,可列舉例如過氧化氫、過氧化氫鹽等,其中可舉如過氧化氫為較佳。此外,酸洗處理液的pH值係以25℃情況下的值為1-5為佳。
進行酸洗製程的方法上並無特別的限定,舉例例如浸漬法、噴塗法、淋塗法等。關於酸洗處理液的濃度、酸洗處理液與金屬材料之間接觸時
間上並不需特別的限定,惟以將與酸洗處理液接觸所致金屬材料每單位面積的蝕刻重量控制在0.1-10.0mg2範圍內為佳,其中以控制於0.1-5.0g/m2範圍內為較佳。
(接觸製程)
關於本實施型態中,具有使用金屬材料表面處理劑的表面處理覆膜的金屬材料之製造方法當中的接觸製程,其係使金屬材料用表面處理劑以40-70℃、10-600秒來接觸金屬材料的表面或是表面的製程。此外,於此製程之後,亦可視所需而進行水洗、去離子沖洗,其後亦可進行乾燥。關於乾燥溫度並不需特別限制,以50-140℃為較佳範圍。此外,作為使金屬材料用表面處理劑接觸金屬材料的表面或是表面上的接觸方法並不需特別限定,可舉例例如浸漬法、噴塗法、淋塗法等。
(對象金屬材料)
關於本發明中金屬材料用表面處理劑所作為對象的金屬材料,並不需要特別限定,可列舉例如:鋁、鋁合金、冷軋鋼板、熱軋鋼板、熔融鍍鋅鋼板、電鍍鋅鋼板、熔融鍍合金化鋅鋼板、鍍鋁鋼板、鍍鋁-鋅合金化鋼板、不鏽鋼板、銅板、鈦板、鎂板、鎳板等。其中以鋁及鋁合金,特別是對於表面氧化膜厚且於表面上偏析著多種合金成份的鋁壓鑄材料係為有效。
<<具有表面處理覆膜的金屬材料>>
藉著由本發明之具有表面處理覆膜的金屬材料之製造方法所製造出的-具有表面處理覆膜的金屬材料,其中的表面處理覆膜的附著量係每單位面積之碳換算質量(M)為1-100mg/m2,其中以每單位面積的Cr、Ti、Zr的合計質量(N)為1-200mg/m2為佳。
本實施型態中的具有表面處理覆膜的金屬材料雖然說不需要特別於表面處理上進行塗佈的塗佈製程也具有良好的耐蝕性,但仍可進行塗佈製程。
於此,塗佈製程並不需特別限定,可使用習知的塗料組成物並藉著水性塗佈、溶劑塗佈、粉末塗佈、陰離子電沉積塗佈、陽離子電沉積塗佈等塗佈方法來進行。
[實施例]
以下說明本發明的實施例以及比較例。此外,本發明並不限定於實施例內容。
<<金屬材料用表面處理劑之製造>>
<化合物(C)之合成>
將下表1所示量的芳香族化合物(a1)及溶劑投入攪拌機所附的反應裝置(1L可拆式燒瓶),使其充分溶解。於室溫下,依序地將下表1所示量的胺化合物(a1)、胺基矽烷(a2)、37質量%甲醛水溶液、催化劑滴下添加至此混合液當中,於80℃攪拌48小時。之後,加入水,僅沉澱聚合物成份並且過濾進行純化,以得到對應化合物(C)的各化合物C1-C3。此外,表1所示的C4-C6係不對應本發明之金屬材料用表面處理劑中的化合物(C)的化合物。
表1中的符號的意思如下。
a1:聚對乙烯基苯酚(MARUKA LYNCUR,丸善石油化學)
a2:γ-(苯基胺基)丙基三甲氧基矽烷
a3:2-甲基胺基乙醇
a4:乙醇
a5:乙酸
<金屬材料用表面處理劑的調製上所使用的各種成分>
如表2所示,使用原料A1-A3作為離子A的供給源(A);使用原料B1、B2作為離子B的供給源(B);使用原料D1作為含氟化合物(D);使用原料E1-E4以作為成份(E)。
<金屬材料用表面處理劑>
使用使表1-2所示原料,將各種原料摻入水中予以混合,使其為表3所示濃度,以得到實施例1-20及比較例1-8中的金屬材料用表面處理劑。
此外,表中所示供給源(A)的添加量係為鉻換算值量濃度,而示於表中的供給源(B)的添加量為金屬換算值量濃度;於表所示成份(E)的添加量係金屬換算質量濃度;於表所示游離氟離子濃度係氟換算質量濃度。關於游離氟離子濃度的測量如下所示。此外,將各種處理液的pH值示於表3中。
<游離氟離子濃度之測量>
游離氟離子濃度係使用市售的氟離子測量儀(離子電極:氟化物離子複合電極F-2021(東亞DKK股份有限公司製造))來測量。
<<具有表面處理覆膜金屬材料之製造>>
使用實施例1-20及比較例1-8的金屬材料用表面處理劑,並且使用以下的金屬材料來製造具有表面處理覆膜的金屬材料,以作為製造實施例1-25、製造比較例1-8。
處理方法以及處理條件係如下所示。
此外,關於在製造實施例1-25、製造比較例1-8所製造具有表面處理覆膜的金屬材料,關於其表面處理覆膜的附著量,係用以下方法來測量每單位面積的金屬合計質量及碳換算質量。將測量結果示於表4。此外,於表4當中,(N)係Cr、Ti及Zr的合計質量,(M)係碳換算質量。
另外,關於於製造實施例1-25、製造比較例1-8所製造的具有表面處理覆膜的金屬材料係如下所示般,實施耐蝕性(未塗佈規格),並評測表面處理覆膜。其結果如表5所示。
再者,如下所示般,於表面處理覆膜之上進行塗佈之後,實施耐蝕性(塗佈規格)的測試,評測關於塗佈品的耐蝕性。其結果如表5所示。
<金屬材料>
鋁壓鑄材料(JIS-ADC12)
<脫脂劑>
使用鹼性脫脂劑(Fine cleaner 315E(日本帕卡瀨精股份有限公司製))的20g/L水溶液。
<酸洗處理液>
使用硫酸的質量濃度為5g/L、氫氟酸質量濃度為1g/L的酸洗處理液(混合液)。
<<各種參數之測量>>
<每單位面積的金屬質量>
每單位面積的金屬質量(Cr、Ti、Zr)係使用掃描型螢光X射線分析裝置(ZSX primus II(理學股份有限公司製))來進行測量。
<每單位面積的碳換算質量>
每單位面積的碳換算質量係使用總有機碳量測量器(TOC-L(島津製作所股份有限公司製))來進行測量。
<<具有表面處理覆膜金屬材料之製造>>
將金屬材料以60℃浸漬於脫脂劑中2分鐘,接著以自來水將表面沖洗乾淨。接著,關於進行酸洗製程的實施例,將金屬材料以常溫浸漬於酸洗處理液中2分鐘,接著以自來水將表面沖洗乾淨。之後進行接觸製程,其藉由以表4所示溫度,以特定的接觸時間,來噴塗實施例及比較例的金屬材料用表面處理劑於金屬材料的表面或表面上。其後,以自來水進行流水清洗(常溫,30秒),並且以去離子水進行水洗(常溫,30秒)之後以電烘箱進行乾燥(80℃5分鐘),以製造具有表面處理覆膜的金屬材料。
<<評測方法>>
<耐蝕性(未塗佈規格)>
針對具有表面處理覆膜的金屬材料進行中性鹽水噴霧測試(JIS-Z2371:2015)並且進行240小時。乾燥之後,目視測量金屬材料之表面所產生的白鏽比例。白鏽的比例係白鏽產生面積相對於觀察部位的面積的的比例。評測基準如下所示。評測結果如表5所示。
<評測基準>
5 白鏽比例 10%以下
4 白鏽比例 大於10%-30%以下
3 白鏽比例 大於30%-50%以下
2 白鏽比例 大於50%-70%以下
1 白鏽比例 大於70%
<耐蝕性(塗佈規格)>
於具有表面處理覆膜的金屬材料之表面上塗佈溶劑類塗料(胺基醇酸類)形成塗膜,並且使乾燥之後的塗膜厚度為20μm,以製作塗佈材料。其後,於塗佈材料的塗佈面上,使用壓克力切割器劃出兩條觸及金屬基底的對角線。針對塗佈材料進行480小時的中性鹽水噴霧測試(JIS-Z2371:2015)。乾燥之後進行剝離膠帶,測量切割部分當中塗膜單面的最大剝離寬度。評測基準如下所示。評測結果示於表5。
<評測基準>
5 剝離寬度0.5mm以下
4 剝離寬度大於0.5-1.0mm以下
3 剝離寬度大於1.0-2.0mm以下
2 剝離寬度大於2.0-3.0mm以下
1 剝離寬度大於3.0mm
此外,關於本發明雖參照具體實施例作詳細地說明,然而在不脫然本發明主旨及範圍情況下可施加各種變更及改變,此對於本發明所屬技術領域中具通常知識者來說係顯而易見之事。
Claims (4)
- 一種金屬材料用表面處理劑,用於對金屬材料進行表面處理,其摻入:至少一種含有三價鉻的離子A的供給源(A);離子B的供給源(B),該離子B係含有鈦的離子以及含有鋯的離子所構成群組中所選擇的至少一種;水溶性或水分散性化合物(C),其具有:烷氧基矽烷基;芳香環;與該芳香環直接鍵結的羥基;由一級胺基、二級胺基、三級胺基及四級胺基所構成群組中所選的至少一種胺基,且其中該烷氧基矽烷基係直接地或是透過亞烷基而鍵結至該胺基的氮原子,含氟化合物(D),其可提供含氟離子,且其中,該表面處理劑包含游離氟離子;該離子A的鉻換算質量及該離子B的金屬換算質量的合計質量相對於該化合物(C)的固態含量質量的比[(A+B)/C)]係於大於3~24以下的範圍內。
- 一種具有表面處理覆膜的金屬材料之製造方法,其包含:接觸製程,其係使如請求項1所述之金屬材料用表面處理劑接觸金屬材料的表面或是表面上。
- 如請求項2所述之具有表面處理覆膜的金屬材料之製造方法,其包含: 酸洗製程,其係於該接觸製程之前,以酸洗處理液對金屬材料進行酸洗,且其中該酸洗處理液摻入由含氟化合物、硫酸化合物、硝酸化合物、磷酸化合物、羥基羧酸化合物及過氧化氫化合物所構成群組中所選的至少一種成分。
- 一種金屬材料,其具有藉著使如請求項1所述之金屬材料用表面處理劑接觸金屬材料的表面或是表面上而形成的表面處理覆膜。
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WO2007100135A1 (ja) * | 2006-03-03 | 2007-09-07 | Dipsol Chemicals Co., Ltd. | 亜鉛又は亜鉛合金上に黒色の3価クロム化成皮膜を形成するための処理水溶液及び黒色3価クロム化成皮膜の形成方法 |
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EP1992718A1 (en) * | 2006-03-08 | 2008-11-19 | Nippon Paint Co., Ltd. | Metal surface treating agent |
US20090280253A1 (en) * | 2008-05-07 | 2009-11-12 | Bulk Chemicals, Inc. | Process and composition for treating metal surfaces using trivalent chromium compounds |
JP2009280889A (ja) * | 2008-05-26 | 2009-12-03 | Nippon Parkerizing Co Ltd | 水系表面処理剤、プレコート金属材料の下地処理方法、プレコート金属材料の製造方法およびプレコート金属材料 |
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EP3733929A1 (en) | 2020-11-04 |
US11603592B2 (en) | 2023-03-14 |
CN111511963A (zh) | 2020-08-07 |
US20200362461A1 (en) | 2020-11-19 |
TW201928116A (zh) | 2019-07-16 |
WO2019131436A1 (ja) | 2019-07-04 |
CN115992351A (zh) | 2023-04-21 |
KR102525723B1 (ko) | 2023-04-26 |
MX2020006742A (es) | 2020-08-24 |
PH12020550984A1 (en) | 2021-04-26 |
JP6873274B2 (ja) | 2021-05-19 |
JPWO2019131436A1 (ja) | 2020-12-10 |
KR20200094776A (ko) | 2020-08-07 |
EP3733929A4 (en) | 2021-11-03 |
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