TWI392769B - 可沖洗的金屬預處理方法及組合物 - Google Patents
可沖洗的金屬預處理方法及組合物 Download PDFInfo
- Publication number
- TWI392769B TWI392769B TW095101228A TW95101228A TWI392769B TW I392769 B TWI392769 B TW I392769B TW 095101228 A TW095101228 A TW 095101228A TW 95101228 A TW95101228 A TW 95101228A TW I392769 B TWI392769 B TW I392769B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- group
- phosphonic acid
- phosphonate
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 45
- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 239000002184 metal Substances 0.000 title claims description 20
- 238000002203 pretreatment Methods 0.000 title 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 38
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- AJSDTRXBGITXHM-UHFFFAOYSA-N (4-bromophenyl)methylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=C(Br)C=C1 AJSDTRXBGITXHM-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- VBWLIUWQKLTQKM-UHFFFAOYSA-N (4-tert-butylphenyl)methylphosphonic acid Chemical compound CC(C)(C)C1=CC=C(CP(O)(O)=O)C=C1 VBWLIUWQKLTQKM-UHFFFAOYSA-N 0.000 claims description 4
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 4
- 150000001204 N-oxides Chemical class 0.000 claims description 4
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- RRIUIVQAMFPDAL-UHFFFAOYSA-N (4-bromophenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC=C(Br)C=C1 RRIUIVQAMFPDAL-UHFFFAOYSA-N 0.000 claims description 3
- ZHBRSHSRMYZHLS-UHFFFAOYSA-N (4-hydroxyphenyl)methylphosphonic acid Chemical compound OC1=CC=C(CP(O)(O)=O)C=C1 ZHBRSHSRMYZHLS-UHFFFAOYSA-N 0.000 claims description 3
- HIIOYVOBADMCAS-UHFFFAOYSA-N (4-methylphenyl)methylphosphonic acid Chemical compound CC1=CC=C(CP(O)(O)=O)C=C1 HIIOYVOBADMCAS-UHFFFAOYSA-N 0.000 claims description 3
- FZNXRFYRXBFQMX-UHFFFAOYSA-N (4-nitrophenyl)methylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=C([N+]([O-])=O)C=C1 FZNXRFYRXBFQMX-UHFFFAOYSA-N 0.000 claims description 3
- OXYRLNBFAYYOPG-UHFFFAOYSA-N 4-(phosphonomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CP(O)(O)=O)C=C1 OXYRLNBFAYYOPG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 21
- 229910052726 zirconium Inorganic materials 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 13
- 238000009472 formulation Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 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 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical compound OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- -1 C 1 -C 5 alkyl Inorganic materials 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical class CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 1
- SYOFLEWUZXUEKC-UHFFFAOYSA-N (4-tert-butylphenyl)phosphonic acid Chemical compound CC(C)(C)C1=CC=C(P(O)(O)=O)C=C1 SYOFLEWUZXUEKC-UHFFFAOYSA-N 0.000 description 1
- ISQSUCKLLKRTBZ-UHFFFAOYSA-N (phosphonomethylamino)methylphosphonic acid Chemical compound OP(O)(=O)CNCP(O)(O)=O ISQSUCKLLKRTBZ-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- QZNQSIHCDAGZIA-UHFFFAOYSA-N 1-(bromomethyl)-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(CBr)C=C1 QZNQSIHCDAGZIA-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 description 1
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical class CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical class OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- LFLCPWCZNJYHRD-UHFFFAOYSA-N C(C)P(=O)(O)OP(=O)O Chemical compound C(C)P(=O)(O)OP(=O)O LFLCPWCZNJYHRD-UHFFFAOYSA-N 0.000 description 1
- PIIWCIWFJKBDDZ-UHFFFAOYSA-N C(CC)C(C(OC)(OC)OC)CCCCCCCC.NC(=O)N Chemical compound C(CC)C(C(OC)(OC)OC)CCCCCCCC.NC(=O)N PIIWCIWFJKBDDZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-L benzyl-dioxido-oxo-$l^{5}-phosphane Chemical class [O-]P([O-])(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-L 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004690 coupled electron pair approximation Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HHCZYYBKCPWBMS-UHFFFAOYSA-N decylurea Chemical class CCCCCCCCCCNC(N)=O HHCZYYBKCPWBMS-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007746 phosphate conversion coating Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 231100000440 toxicity profile Toxicity 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- 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)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本發明係關於用於金屬之不含鉻塗層。更特定言之，本發明係關於用於鋼、鍍鋅鋼、及鋁之表面之可沖洗、無鉻酸鹽、無金屬磷酸鹽之塗層以改良乾燥塗層至該表面之附著並提供增強的防腐蝕作用。
在金屬表面採用鉻酸鹽或磷酸鹽轉化塗層或鈍化塗層以給予裸金屬及經塗佈之金屬之經改良的耐蝕性，改良塗層之附著力，並用於審美目的，此對熟習此項技術者係熟知的。例如，參見Corrosion
,L.L.Sheir,R.A.Jarman,G.T.Burstein,Eds.(第三版，Butterworth－Heinemann Ltd,Oxford,1994)，第二卷，第15.3章。
關於鉻的毒性概況以及鉻酸鹽、磷酸鹽及藉由該等製程排入河流及水道的其它重金屬之污染影響，吾人擔心日益增加。由於六價鉻離子之高溶解性及強氧化性特徵，習知鉻酸鹽轉化製程需要大量的水處理程序以控制其排出。磷酸鹽製程亦需要在排出之前的廢物處理程序。另外，處理來自該等廢物處理程序之固體污泥為一重要問題。
因此，在此項技術中需要提供基於無鉻酸鹽、無金屬磷酸鹽、或減少的磷酸鹽之有效處理以抑制金屬表面腐蝕並增強可塗覆至該表面之油漆或其它塗層之附著力。
提供酸性水溶液或分散液以與諸如鋼、鍍鋅鋼、及鋁之表面之必要的金屬表面接觸。該等溶液及分散液不含鉻酸鹽並提供金屬表面上經增強之防腐蝕作用及乾燥塗層之黏著性。此等乾燥塗層通常包括油漆、快乾漆、墨水、清漆、樹脂等。
本發明之方法包含將必要的金屬表面與有效量之酸性水性組合物或分散液接觸以增強防腐蝕作用及乾燥塗層之黏著性。不含鉻酸鹽及無機磷酸鹽之組合物或分散液包含(a)包括一IVB族元素之一或多種材料；(b)一氟化物源；及(c)膦酸或膦酸酯。將金屬表面與以上組合物或分散液接觸之後，可沖洗該塗層並在適當位置進行乾燥。隨後該表面便準備好在其上塗覆油漆、快乾漆、清漆、樹脂或其它乾燥塗層。
本發明者已發現可在金屬表面尤其是鋼表面、鍍鋅鋼及鋁表面提供一經改良之無鉻酸鹽轉化塗層或鈍化塗層。此酸性水性組合物或分散液包含(a)包含選自如元素週期表CAS版中所列明之一或多個IVB族元素之一或多種材料。該等元素包含Zr、Ti及Hf。可包括此等元素之混合物。含有Zr及Ti之材料為較佳的。示範性Zr源經調適以於酸性介質中提供Zr陰離子且包括可溶性氟鋯酸鹽、氟化鋯(ZrF4
)、或諸如硝酸鋯或硫酸鋯之水溶性鋯鹽。另外，鋯源可包含銨鹽或鹼性鋯鹽。可使用氧化鋯及Zr金屬本身，只要其於酸性介質中電離為Zr陰離子。最佳地，Zr源包含氟鋯酸H2
ZrF6
。另外，含有機Zr之化合物若能在酸性水性介質中釋放出Zr則可利用含有機Zr之化合物。
IVB族元素亦可包含Ti。較佳的Ti源為H2
TiF6
，但諸如TiF3
及TiF4
之氟化鈦亦可被提及。硝酸鹽、硫酸鹽、銨鹽或鹼性鈦鹽以及Ti金屬本身亦可使用。另外，有機Ti化合物若能在酸性介質中釋放Ti則可使用有機Ti化合物。初步試驗包括使用異丙醇鈦(iv)作為Ti源組分，尤其在其與諸如H2
ZrF6
之酸性溶液反應之情況下。
用作酸性處理液或組合物之組分的氟化物源(b)最佳地可為可用以提供Ti及/或Zr之同樣的氟鋯酸或氟鈦酸。最佳地，該處理液包含H2
ZrF6
與H2
TiF6
，其組合將足以用作Zr、Ti及氟化物之來源。其它適當F源包括氫氟酸及其鹽、鹼金屬二氟化物、H2
SiF6
及HBF4
。此外，該源必須能在介質中釋放F。最佳地，經組合之Zr、Ti及F源在介質中釋放氟鈦酸根及氟鋯酸根，即(TiF6
)－ 2
及(ZrF6
)－ 2
。
所需的氟化物濃度為使該氟化物與Zr及Ti結合以與之形成錯合物之濃度，例如氟鋯酸鹽與氟鈦酸鹽。通常，每存在一莫耳Zr與Ti便提供至少約4莫耳氟化物。鋯及鈦可以高達略大於其溶解限度之量存在於處理介質中。
關於調配物之組分(c)膦酸及膦酸酯，此可敍述為包括為具有下式的任何化合物：
其中X為H或陽離子；R為包括下列基團的任何有機部分：烷基、環烷基、經取代及未經取代之含N及/或P之雜環、芳基、包括經鹵化芳基及烷基取代芳基之經取代芳基，諸如胺基烷基、羧烷基、膦酸基烷基、烷亞胺基、羥烷基、矽烷取代之烷基之經取代之烷基等。
膦酸酯可更特別選自具有按照II、III及IV之式之膦酸及膦酸酯，而膦酸酯(II)具有以下之式：
其中R1
為PO3
X2
或R2
PO3
X2
，其中X2
獨立選自H或陽離子，且R2
為C1
－C5
伸烷基，較佳地為亞甲基。Z為選自H、鹵素、C1
－C5
烷基、NO2
、及COOH中之一員。較佳地，Z處於對位。此群之示範性成員包括4－溴苄膦酸，4－第三丁基苄膦酸，苯基膦酸，4－羥苄基膦酸，4－硝基苄基膦酸，4－甲基苄基膦酸，4－羧基苄基膦酸，及4－溴苄基膦酸乙酯。具有式(III)之膦酸酯亦可被提及
其中X如上文在調配物(I)中所定義且R3
為C1
－C5
烷基、C1
－C5
羧烷基、C1
－C5
膦酸基烷基、C1
－C5
矽烷氧基烷基、C1
－C5
亞胺基烷基及C1
－C5
膦亞胺烷基。此群之示範性成員包括2－羧乙基膦酸、膦酸三羥基矽烷丙基甲酯、1,2－二伸乙基二膦酸、亞胺基雙(甲基膦酸)及第三丁基膦酸。
膦酸酯亦可選自式IV。
較佳地，直鏈EBO與環狀EBO同時以混合溶液之形式存在。基於初步資料，較佳地使用直鏈EBO及環狀EBO之混合物。此等膦酸酯可經由以下製備途徑被製備。
膦酸酯製備：直鏈EBO及環狀EBO之混合物(群IV)向配備有機械攪拌器、溫度計、頂部冷凝器及加料孔之玻璃反應容器饋入70%亞磷酸水溶液(2.00莫耳)及32%鹽酸水溶液(0.33莫耳)。隨後邊攪拌邊向該酸溶液逐滴添加90%活性三聚甲醛(2.00莫耳)。添加後，在氮氣射流下將反應器內容物加熱至85±2℃並保持30分鐘。隨後在維持批料溫度為85±2℃的條件下，將氮氣射流切換為氮氣層並經1至2小時逐滴饋入99%單乙醇胺(1.00莫耳)。添加後，將該批料加熱至93±2℃並保持8小時。保持8小時之後冷卻該批料並藉由添加50%氫氧化鈉水溶液(3.73莫耳)將其pH值調節為9－10。接著將該批料溫度調節至40±2℃並逐滴饋入35%過氧化氫水溶液(1.07莫耳)經大約1小時並同時冷卻以維持該批料溫度在38－52℃之間。添加後，將該批料保持在50±2℃ 2小時。隨後冷卻該批料至室溫並加以收集。在冷卻期間，向該批料饋入50%葡萄糖酸水溶液(0.005莫耳)。
由13P NMR以直鏈EBO與環狀EBO之鈉鹽的標稱莫耳比為1：1來表徵所製得之產物，此產物下文統稱為EBO。此材料亦由痕量之殘餘亞磷酸、氧化副產物磷酸、及副產物亞甲基二膦酸的鈉鹽組成。本發明之一較佳實施例利用所製得的該產物而未經純化。
可如下製備其它示範性膦酸酯：膦酸酯製備：4－溴苄基膦酸(BBPA)(群II)將4－溴苄基溴(4.4 g，0.017 mol)與三乙基膦酸酯(3.5 g，3.5 mL，0.021 mol)結合並在130℃加熱12小時。將反應物冷卻至室溫並儲存於暗處。將中間物溶於20 mL之MeCN中並用固體KI(8.7 g，0.0525 mol)加以處理隨後用Me3
SiCl(5.63 g，6.6 mL，0.105 mol)加以處理。將反應物在60℃攪拌6小時再冷卻至室溫。過濾固體KCl，並將殘餘物蒸發至乾。取出殘餘物置於10 mL蒸餾水中。5分鐘後沉澱出琥珀油。過濾該固體並用冷己烷洗滌。此得到3.02 g(70%)白灰色粉末之產物。
膦酸酯製備：4－第三丁苄基膦酸(TBBPA)(群II)將4－第三丁苄基溴(0.91 g，4.0 mmol)與三乙基膦酸酯(0.798 g，0.836 mL，4.8 mmol)結合並在130℃加熱24小時。將反應物冷卻至室溫並儲存於暗處。隨後將中間物溶於5 mL之MeCN中並用固體KI(1.92 g，11.62 mmol)加以處理隨後用Me3
SiCl(1.27 g，1.47 mL，11.62 mmol)加以處理。將反應物在60℃攪拌12小時再冷卻至室溫。過濾固體KCl，並將殘餘物蒸發至乾。取出殘餘物置於10 mL蒸餾水中。5分鐘後沉澱出琥珀油。過濾該固體並用冷己烷洗滌。此得到0.80 g(90%)淡黃色粉末之產物。
第II類之其它經取代之苄基膦酸酯以類似方式製備。即，使用相應的苄基溴作為初始反應物並隨後與三乙基膦酸反應以形成所要之經取代苄基膦酸酯。該酯可經由習知技術轉化為酸形式或以其此所製得之酯形式使用。
所有其它具體列出的膦酸酯均為可購得的。
另外，該酸性處理組合物中可包括矽烷(d)。代表性矽烷包括但不限於，烷氧基矽烷、胺基矽烷、脲基矽烷、縮水甘油氧基矽烷、或其混合物。美國專利第6,203,854號明示了較佳的烷氧基矽烷及胺基矽烷。目前，最佳為購自GE Silicones－OSI的脲丙基三甲氧基矽烷，名稱為Silquest A 1524。
根據本發明之較佳酸性水性組合物為無鉻酸鹽並包括：a1)以超過其溶解限度約0.01 wt%至約10 wt%的量存在的鋯源；a2)以超過其溶解限度約0.01 wt%至約10 wt%的量存在的鈦源；b)氟化物源，其中氟化物以相對於所存在Zr與Ti之總莫耳數之過量莫耳數而存在，較佳地以所存在Zr與Ti之總莫耳數至少約4倍之過量莫耳數而存在；c)以約0.01－50 wt%之量存在的膦酸或膦酸酯；及視需要d)矽烷。
組合物之剩餘部份包含水及pH調節劑以調節pH於約0.5－6之範圍內。酸性水性組合物的重量為100 wt%。
本發明之一更具體之態樣中，水性組合物包含：1)0.01－40 wt%之量的H2
ZrF6
；2)0.01－40 wt%之量的H2
TiF6
；3)約0.01－50 wt%之量的膦酸或膦酸酯；4)約0.00－20 wt%之量的矽烷；剩餘部份之水及pH調節劑。組合物總量(包括水)為100 wt%。
較佳組合物包括：1)約0.01－40 wt%之量的H2
ZrF6
；2)約0.01－40 wt%之量的H2
TiF6
；3)選自由(i)直鏈EBO及(ii)環狀EBO及(i)與(ii)之混合物組成之群的膦酸或膦酸酯。此等膦酸酯以約0.01－50 wt%之組合量而存在。組合物之剩餘部份為以約0.00－20 wt%之量視需要之矽烷(4)、水及pH調節劑。
必要的金屬表面可藉由處理液以噴淋、浸沒、或其它應用形式接觸。處理液可加以沖洗並乾燥使得經製備之金屬表面準備好在其上塗覆乾燥塗層。
將根據本發明之酸性水溶液或分散液塗覆至該金屬表面以在經處理之表面產生大於約每平方英尺1毫克的塗層重量，更佳地，重量為每平方英尺約2－500毫克。若用於商業應用中，則可使用包含約3－100 wt%、較佳為10－100 wt%濃度之以上調配物之工作液來接觸所要的金屬表面。
如商業應用之慣例，調配物中可包括添加劑以促進該轉化塗層之形成。可添加諸如硝酸鹽、亞硝酸鹽、氯酸鹽、溴酸鹽及硝基芳族化合物之氧化劑以加快並維持塗層之形成。可添加無機或有機的酸與鹼以維持工作浴液之pH值。
現結合以下比較實例及工作實例對本發明加以說明。工作實例應視為本發明之特定實施例之說明而不應被認為是限制本發明之範疇。
為確立基線效能，在不添加任何額外添加劑的情況下對鈦及鋯組分加以評估。
一般預處理製程：使用ACT Laboratories冷軋鋼板。
用2%Betz Kleen 132(購自GE Water & Process Technologies)在140℉噴淋90秒進行清洗。
沖洗：應用自來水噴淋30秒預處理：在140℉浸沒2分鐘沖洗：去離子水灌沖30秒乾燥：熱風槍調配物：
預處理之後，將板塗佈購自PPG Industries的單塗層聚酯油漆系統White Polycron III(AG452W3223)。根據廠商說明書塗覆油漆並加以固化。塗佈後，根據ASTM B－117使板經受168小時的中性鹽霧試驗(NSS)並根據ASTM D－1654(表1)評價劃線蠕變(creep from the scribe)。
評估以下調配物以檢查向鹼性鈦＋鋯調配物添加膦酸酯的效果。如比較實例1之方式對板加以處理並塗佈。試驗結果包含於表2中。
所使用的縮寫：Ti(ioPr)4
＝異丙醇鈦EBO＝經混合的直鏈與環狀EBO直鏈EBO＝膦酸[[(2－羥乙基)亞胺基]雙(亞甲基)]雙－,N氧化物環狀EBO＝膦酸[(四氫－2－羥基－4H－1,4,2－噁唑膦素－4－基)甲基]－N,P－二氧化物BBPA＝4－溴苄基膦酸CEPA＝2－羧乙基膦酸TEOS＝矽酸四乙酯GPTMS＝縮水甘油氧基丙基三甲氧基矽烷UPTMS＝脲基丙基三甲氧基矽烷TBBPA＝4－第三丁基苯膦酸EDPA＝1,2－伸乙基二膦酸THSPMP＝3－三羥基矽烷基丙基甲基膦酸酯
如比較實例1之方法製備並塗佈以下額外調配物：
所使用的縮寫詞與實例1中相向，另外PPA＝苯基膦酸。
如實例1中所敍述之方法進行根據ASTM B－117及D－1654之中性鹽霧試驗。結果記錄於表3。
如實例1之方法評估額外膦酸酯。按照以下描述製備Ti與Zr組分之鹼性調配物：鹼性調配物：
中性鹽霧結果在表4中給出。
為進一步評估本發明之效能，製備並試驗以下調配物。製備並使用各組合物之多份浴液以便可製成多個複製品。NSS結果為穿過各組合物之二十塊板的平均值。如實例1之方法處理鋼板。
為說明氧化劑及pH調節劑之用途，製備以下實例。
藉由以下製程順序製備購自ACT Laboratories之CRS板：在140℉下、在鹼性清洗劑(Kleen 132)中清洗60秒用水沖洗15秒處理一在120℉及10 psi噴淋塗覆30秒用去離子水沖洗10秒熱空氣乾燥
將板塗佈Polycron油漆並於240小時中性鹽霧暴露評估效能。
儘管本發明已關於特定實施例進行描述，但是顯然本發明之諸多其它形式及修改對於熟習此項技術者顯而易見。所附申請專利範圍及本發明通常被理解為涵蓋在本發明之真正精神及範疇內的所有該等各種形式及修改。
Claims (13)
- 一種塗佈一金屬或金屬合金表面之方法，其包含將該表面與一有效量之無鉻酸鹽水性處理溶液或分散液接觸，該處理溶液或分散液包含(a)包含一或多個選自IV B族元素的一或多種材料；(b)氟化物，(c)膦酸或膦酸酯；其中該膦酸或膦酸酯(c)係選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群，且其中該膦酸或膦酸酯(c)以約0.01-50 wt%之量存在。
- 如請求項1之方法，其中(a)包含H2 ZrF6 及H2 TiF6 。
- 如請求項1之方法，其中該溶液或分散液進一步包含至少再一膦酸或膦酸酯。
- 如請求項3之方法，其中該至少再一膦酸或膦酸酯係選自由式II、III或IV組成之群，其中式II具有結構：
- 如請求項4之方法，其中該至少再一膦酸或膦酸酯係選自式(II)。
- 如請求項5之方法，其中該至少再一膦酸或膦酸酯係選 自以下各物組成之群之一或多個成員：4-溴苄基膦酸，4-第三丁基苄基膦酸，苯基膦酸，4-羥苄基膦酸，4-硝基苄基膦酸，4-甲基苄基膦酸，4-羧基苄基膦酸及4-溴苄基膦酸乙酯。
- 一種用於在金屬表面上形成一轉化或鈍化塗層之酸性、水性組合物或分散液，該組合物不含鉻酸鹽並包含(a)包含一或多個選自IV B族元素的一或多種材料；(b)氟化物；及(c)膦酸或膦酸酯；其中該膦酸或膦酸酯(c)係選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群，且其中該膦酸或膦酸酯以約0.01-50 wt%之量存在。
- 如請求項7之組合物，其中(a)包含H2 ZrF6 及H2 TiF6 。
- 如請求項7之組合物，其中該組合物進一步包含至少再一膦酸或膦酸酯。
- 如請求項9之組合物，其中該至少再一膦酸或膦酸酯係選自由式II、III或IV組成之群，其中式II具有結構：
- 如請求項10之組合物，其中該至少再一膦酸或磷酸酯係 選自式II。
- 如請求項11之組合物，其中該至少再一膦酸或膦酸酯係選自由以下各物組成之群：4-溴苄基膦酸、4-第三丁基苄基膦酸、苯基膦酸，4-羥基苄基膦酸，4-硝基苄基膦酸，4-甲基苄基膦酸，4-羧基苄基膦酸及4-溴苄基膦酸乙酯。
- 一種在金屬表面上形成一轉化或鈍化塗層之組合物，該組合物包含以下物質之酸性水溶液或分散液：1)0.01-40 wt%之量的H2 ZrF6 ；2)0.01-40 wt%之量的H2 TiF6 ；3)選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群之膦酸或膦酸酯；該膦酸或膦酸酯3)以約0.01-50 wt%之量存在，pH調節劑4)，約0.00-20 wt%之量的矽烷5)，剩餘部份之水，以等於100 wt%。
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| US11/034,416 US20060151070A1 (en) | 2005-01-12 | 2005-01-12 | Rinsable metal pretreatment methods and compositions |
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| CN103668158A (zh) * | 2013-12-09 | 2014-03-26 | 常熟市大康汽车座垫有限责任公司 | 钝化金属表面的方法 |
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| CN105779984A (zh) * | 2016-04-20 | 2016-07-20 | 南京科润工业介质股份有限公司 | 一种适用于铝合金的无铬钝化剂 |
| CA3042087C (en) | 2016-12-22 | 2024-02-13 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
| JP7221868B2 (ja) * | 2016-12-22 | 2023-02-14 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | ベア金属表面の酸化を減らすためのカテコール化合物および官能化共反応化合物の予め形成された反応生成物の使用 |
| JP7182547B2 (ja) | 2016-12-22 | 2022-12-02 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | カテコール化合物および官能化共反応化合物の予め形成された反応生成物による化成コートされた金属基板の処理 |
| FI3663435T3 (fi) * | 2018-12-05 | 2024-05-24 | Henkel Ag & Co Kgaa | Fosfori- ja fosfonihappojen seoksiin perustuva passivointikoostumus |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1841898A1 (en) | 2007-10-10 |
| EP1841898B1 (en) | 2016-04-13 |
| CN104195537A (zh) | 2014-12-10 |
| CA2594732C (en) | 2014-02-18 |
| US20060151070A1 (en) | 2006-07-13 |
| AU2006205215A1 (en) | 2006-07-20 |
| BRPI0606235A2 (pt) | 2009-06-09 |
| TW200643222A (en) | 2006-12-16 |
| RU2007130697A (ru) | 2009-02-20 |
| US8585834B2 (en) | 2013-11-19 |
| EP2949781B1 (en) | 2017-11-22 |
| US20080245444A1 (en) | 2008-10-09 |
| RU2400562C2 (ru) | 2010-09-27 |
| MX2007008510A (es) | 2007-11-12 |
| WO2006076197A1 (en) | 2006-07-20 |
| EP2949781A1 (en) | 2015-12-02 |
| AU2006205215C1 (en) | 2012-01-19 |
| NZ556408A (en) | 2010-11-26 |
| EP2942422A1 (en) | 2015-11-11 |
| AU2006205215B2 (en) | 2011-08-18 |
| AR092124A2 (es) | 2015-03-25 |
| CA2594732A1 (en) | 2006-07-20 |
| CN101137767A (zh) | 2008-03-05 |
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