GB2249108A - Phosphating compositions containing zinc ions and a polar or non-polar solvent - Google Patents
Phosphating compositions containing zinc ions and a polar or non-polar solvent Download PDFInfo
- Publication number
- GB2249108A GB2249108A GB9119726A GB9119726A GB2249108A GB 2249108 A GB2249108 A GB 2249108A GB 9119726 A GB9119726 A GB 9119726A GB 9119726 A GB9119726 A GB 9119726A GB 2249108 A GB2249108 A GB 2249108A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- parts
- zinc
- composition
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 67
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims description 21
- 239000012454 non-polar solvent Substances 0.000 title description 2
- 239000002798 polar solvent Substances 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000003495 polar organic solvent Substances 0.000 claims description 11
- 230000003381 solubilizing effect Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- 239000011575 calcium Substances 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 claims 2
- 239000010941 cobalt Substances 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- 235000011007 phosphoric acid Nutrition 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- -1 chlorine ions Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011746 zinc citrate Substances 0.000 description 2
- 235000006076 zinc citrate Nutrition 0.000 description 2
- 229940068475 zinc citrate Drugs 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- SXQXMKMHOFIAHT-UHFFFAOYSA-N 1,1-dichloro-2-(2,2-dichloroethoxy)ethane Chemical compound ClC(Cl)COCC(Cl)Cl SXQXMKMHOFIAHT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- BRFMYUCUGXFMIO-UHFFFAOYSA-N phosphono dihydrogen phosphate phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O BRFMYUCUGXFMIO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 description 1
- ZFQAUDJGELQDAN-UHFFFAOYSA-L zinc;2,2,2-trichloroacetate Chemical compound [Zn+2].[O-]C(=O)C(Cl)(Cl)Cl.[O-]C(=O)C(Cl)(Cl)Cl ZFQAUDJGELQDAN-UHFFFAOYSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 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
- C23C22/02—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 non-aqueous solutions
- C23C22/03—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 non-aqueous solutions containing phosphorus compounds
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
TITLE:
Phosphatizing Compositions
DESCRIPTION
The invention relates to a phosphatizing composition and to metal articles treated therewith.
Japanese Laid-open Patent Application No. 52-107244 discloses a phosphatizing composition containing an aqueous medium. This comprises nitric acid and chlorine ions in an aqueous solution of acidic zinc phosphate so that the ratio of the nitrate ion and the chlorate ion (NO,)-/C103 is 0.2 to 4.5 and the ratio of the phosphate ion, the chlorate ion and the nitrate ion (PO4-3/ClO3-/NO3-) is 1:0.08 to 0.53:0.08 to 0.53.
However, in order to form a zinc phosphate film using a phosphatizing agent containing water as a medium, it is necessary sequentially to carry out a defatting step, a water rinsing step, a pure water rinsing step, a surface regulating step, a chemical treatment step, a water rinsing step, a pure water rinsing step and a drying step in this order, which steps per se are complicated.
Further, since in these steps a large amount of water is needed, the aforementioned method has the disadvantage of necessitating the provision of facilities for waste water, at substantial cost. Further, in the aforementioned phosphatizing composition the nitrate ion is employed as a catalyst and since the pH decreases as the concentration of the nitrate ion increases, the film cannot in practice be formed.
A composition for forming a zine phosphate film without water as a medium is known from Japanese Patent
Publication No. 42-14051, which proposes a phosphatizing composition comprising an oxygen-containing organic solvent, a zinc compound and phosphoric acid. However, in this composition, the zine is hardly dissolved so that sludges and the like are formed in the film obtained so that industrialization is not practicable.
Japanese Patent Publication No. 57-49111 discloses a phosphatizing composition containing a chlorinated hydrocarbon medium. The composition may be used to phosphatize metal surfaces to enhance adhesiveness and moisture proof properties of coatings and so as to form a substantially water insoluble film of iron phosphate. However, while the iron phosphate film exhibits satisfactory performance in certain fields as pre-treatment to painting, it has the disadvantage that corrosion resistance is inferior to that of a zine phosphate film formed with a composition containing water as a medium, as employed in the automobile and electrical household goods industries.
The invention provides a phosphatizing composition comprising
(a) 100 parts by weight of a mixed solvent which contains a polar organic solvent and water, the polar organic solvent having a boiling point of not less than 00C/760 mmHg, and constituting at least 50% by weight of the mixed solvent;
(b) 0.001 to 7 parts by weight of a phosphoric acid;
(c) 0,01 to 5 parts by weight of zinc ions; and
(d) 0.01 to 5 parts by weight of a solubilizing agent.
The invention further provides a phosphatizing composition comprising
(e) 100 parts by weight of a mixed solvent which contains a nonpolar organic solvent having a boiling point of not less than 00C/760 mmHg, not less than 0.5% by weight relative to the nonpolar solvent of a solubilizing solvent and not more than a homogeneous phase forming limit amount of water;
(f) 0.0001 to 7 parts by weight of phosphoric acid;
(g) 0.001 to 3.5 parts by weight of zine ion; and
(h) 0.01 to 5 parts by weight of a solubilizing agent.
The invention also provides a metal article, the surface of which has been phosphatized by treatment with either of the compositions of the invention.
The phosphatizing composition of the invention is used to modify the surfaces of various metallic objects such as various irons, steels, galvanized iron, alloys of iron, aluminium or magnesium or other metallic materials.
A first phosphoric acid type composition according to the invention (hereinafter referred to as "the first composition") contains as essential components (a) a specific first mixed solvent, (b) phosphoric acid, (c) zinc ion and (d) a solubilizing agent in the respective specified amounts.
The first mixed solvent (a) in the first composition contains 100 parts by weight of a polar organic solvent having a boiling point of not less than 00C/760 mmHg and not more than 100 parts by weight of water. The polar organic solvent is preferably substantially water soluble. It may be a proton polar organic solvent such as an alcohol having not more than 14 carbon atoms, for example methanol, ethanol, isopropanol, 2-butoxyethanol, n-propanol, n-butanol, s-butanol, t-butanol or trifluoroethanol.It may alternatively be a non-proton polar organic solvent such as a ketone, for example, acetone, methyl ethyl ketone or diethyl ketone; a polyhydric alcohol ester having not more than 10 carbon atoms, for example diethyleneglycol monoacetal, glycerine monoacetal, glycerine diacetal, glycerine monobutryate, ethylene carbonate, propylene carbonate, ethyleneglycol monoformate ethyleneglycol diformate, ethylyeneglycol monoacetate or ethyleneglycol diacetate; a phosphate, for example trimethyl phosphate; a polyhydric alcohol ether having not more than 10 carbon atoms such as glycol ether, e.g. dimethoxy-ethane, diethoxy-ethane, 2-methoxy-ethanol or 2-ethoxy-ethanol, diethyleneglycol ether, e.g. diethyleneglycolmonomethyl ether, diethyleneglycoldimethyl ether or diethyleneglycolmonoethyl ether, glycerine ether, e.g. glycerinemethyl ether, glycerinetrimethyl ether or glycerinedimethyl ether, propylene ether, e.g. 1-methoxy-2-propanol or 1-ethoxy-2-propanol; a polyhydric alcohol monoester monoether having not more than 10 carbon atoms such as ethyleneglycol monoethylether acetate or ethyleneglycol monomethylether acetate; a cyclic ether, for example tetrahydrofuran or dioxane; a nitrogen compound such as acetonitrile or propionitrile; or diacetone alcohol.
Of these, methanol, ethanol, isopropanol and n-propanol are particularly preferred. The polar organic solvents may be used singly or in combination. The water in the first mixed solvent functions as an accelerator upon forming a film and is contained as water of crystallization. The mixing ratio of the water is not more than 100 parts by weight, preferably 30 to 70 parts by weight relative to 100 parts by weight of the polar organic solvent. If the mixing ratio exceeds 100 parts by weight, the solubility of the film becomes high so that a substantially uniform film is not obtained - The phosphoric acid (b) employed in the first composition of the invention may be any oxyacid or acidic oxide of phosphorus. The phosphoric acid may, for example, be orthophosphoric acid, pyrophosphoric acid, or phosphorus pentoxide. Orthophosphoric acid is most preferred.The mixing ratio of the phosphoric acid is 0.0001 to 7 parts by weight., preferably 0.01 to 2 parts by weight and most preferably 0.03 to 0.5 part by weight relative to 100 parts by weight of the first mixed solvent. If the mixing ratio of the phosphoric acid is less than 0.0001 part by weight, it may possibly be difficult stably and continuously to operate and supply the system for forming a desired phosphoric acid type film, whereas if the mixing ratio exceeds 7 parts by weight, the phosphoric acid may not be homogeneously dissolved in the first mixed solvent resulting in a turbid composition or in precipitation of crystallates.
The zinc ion (c) may be included in the first composition in the form of zinc oxide; an inorganic salt such as zinc carbonate, zinc nitrate, zinc chloride, zinc sulphate, zinc borate or zinc phosphate; or an organic salt such as zinc formate, zine acetate, zinc citrate, zinc tartrate, zinc oxalate or zinc trichloroacetate. Zinc oxide, zinc carbonate, zinc nitrate, zinc borate, zinc phosphate and zinc citrate are most preferred. A portion of the zinc ion may be replaced by nickel ion, calcium ion, manganese ion, sodium ion, mangnesium ion, copper ion or cobalt ion and the like. The mixing ratio of the zinc ion in the composition is 0.01 to 5 parts by weight, preferably 0.01 to 2.0 parts by weight relative to 100 parts by weight of the first mixed solvent.If the mixing ratio of zinc ion is less than 0.01 part by weight, the desired film is not obtained, whereas in excess of 5 parts by weight an excessive solubilizing agent etches metal so much that a substantially uniform film is not obtained. The mixing ratios of the respective ions replaceable as a portion of the zinc ion are preferably up to 2.5 parts by weight for nickel ion, up to 2.5 parts by weight for manganese ion, up to 2.0 parts by weight for calcium ion, up to 3.0 parts by weight for sodium ion, up to 2.0 parts by weight for magnesium ion, up to 2.0 parts by weight for copper ion and up to 2.0 parts by weight for cobalt ion.
The solubilizing agent (d) employed in the first composition of the invention is a component which can simultaneously dissolve both zinc and phosphoric acid into the solvent in the composition, and can promote etching of the metal surface to dissolve metal ions such as iron ion (Fe ) or zinc ion (Zn ) to form a zinc phosphate type crystalline film on the metal surface. The solubilizing agent may be a hydrogen halide such as hydrogen fluoride or hydrogen chloride; an inorganic acid such as nitric acid, hydrochloric acid, sulphuric acid or nitrous acid; or an organic acid such as trichloroaeetate, trifluoroacetate, picric acid, or nitroaniline. These may be used singly or in combination.The solubilizing agent may be used in an amount more than 2 moles relative to 1 mole of zinc ion in the composition if the solubilizing agent is a monobasic acid. If the solubilizing agent is a dibasic acid, it may be used in an amount more than 1 mole.
Hence, for example if zinc nitrate, zinc chloride and the like are added as the aforementioned zinc ion, a smaller amount of the solubilizing agent may be added.
The mixing ratio of the solubilizing agent in the first composition is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight relative to 100 ptts by weight of the first mixed solvent. If the mixing ratio is less than 0.01 part by weight, the solubilizing agent is not dissolved as zinc is combined with phosphoric acid, whereas if the mixing ratio is more than 5 parts, the pH of the system becomes so excessively low as to etch metal too much.
To prepare the first composition of the invention, the aforementioned components are simply mixed homogeneously at ambient temperature under stirring.
A second phosphatizing composition of the invention (hereinafter referred to as "the second composition") contains as essential components (e) a specific second mixed solvent, (f) phosphoric acid, (g) zinc ion and (h) a solubilizing agent in the respective specified amounts.
The second mixed solvent (e) contains 100 parts by weight of a nonpolar organic solvent having a boiling point of not less than 00C/760 mmHg, not less than 0.5 part by weight of a solubilizing solvent and not more than a homogeneous phase forming limit amount of water.
The nonpolar organic solvent is preferably substantially water insoluble. It may be a hydrocarbon solvent having a molecular weight of not more than 200 such as pentane, hexane, toluene or xylene; a halogenated hydrocarbon solvent such as methylene dichloride, trichloroethane, tetrachloroethylene or tric luorotrifluoroethane; an ether having a molecular weight of not more than 200 such as diethyl ether, diisopropyl ether or bis(2,2 -dichloroethyl)ether; an alcohol having not less than 5 carbon atoms such as n-pentanol or hexanol; an aliphatic ketone having not less than 5 carbon atoms; or an ester such as methyl formate or ethyl acetate. To enable the composition to be non-inflammable, methylene dichloride, trichloroethane and trichlorotrifluoroethane are most preferred. These may be used singly or in combination.
The solubilizing solvent employed in the second mixed solvent is a component which dissolved phosphoric acid, zinc, the solubilizing agent and water in the composition. The exemplified compounds described hereinbefore as the polar organic solvent may preferably be enumerated. Methanol, ethanol, isopropanol and n-propanol are most preferred. The solubilizing solvent may be used singly or in combination. The solubilizing solvent is present in an amount of not less than 0.5 part by weight, but preferably 5 to 50 parts by weight and most preferably 10 to 40 parts by weight, relative to 100 parts by weight of the nonpolar organic solvent.
If the solubilizing solvent is present in an amount of less than 0.5 part by weight, phoshoric acid, zinc, the solubilizing agent and water are not dissolved.
The water used in the second mixed solvent functions as a promoter for forming a film and is contained in the film as water of crystallization. The mixing ratio of water is not more than a homogeneous phase forming limit amount, preferably 1.0 part by weight to not more than the homogeneous phase forming limit amount. The homogeneous phase forming limit amount means an amount which forms non-turbid state in the composition itself upon mixing the essential components. If the mixing ratio of water exceeds the homogeneous phase forming limit amount, the solubilizing reaction is too strong to obtain a substantially uniform film.
Phosphoric acid (f) and the solubilizing agent (h) in the second composition may be enumerated by phosphoric acid (b) and the solubilizing agent (d) in the first composition. The mixing ratios of the phosphoric acid (f) and the solubilizing agent (h) in the second composition are the same as those in the first composition.
The zinc ion (g) employed in the second composition may be enumerated by the same aforementioned compounds in the first composition. The zinc ion may similarly be replaced by the other metal ions as set forth above.
The mixing ratio of the zine ion is 0.001 to 3.5 parts by weight, preferably 0.01 to 2.0 parts by weight relative to 100 parts by weight of the second mixed solvent. If the mixing ratio is less than 0.001 part by weight, a desired film is not obtained, whereas in excess of 3.5 parts by weight, it is not dissolved into the second mixed solvent.
To prepare the second composition, the respective components may be mixed homogeneously at ambient temperature under stirring.
To form a film employing the first and second compositions of the invention, immersing treatment, spraying or flow coating methods may be utilized.
For example, the known defatting and phosphatizing chemical treatment system commercially available under the tradename "COOLPHOSB' from NIPPON DACRO SHAMROCK
CO., LTD. or a mono- or multi-bath type solvent defatting and rinsing device may be used. The composition of the invention is charged into the device and heated to a temperature between room temperature and the boiling point, preferably between a temperature of 10 C lower than the boiling point and the boiling point, to generate solvent vapour. The metal article to be treated is maintained in the solvent vapour zone preferably for 10 seconds to 1 minute, more preferably for 15 to 30 seconds, to preform defatting treatment.
The metal article is then immersed in the heated composition and maintained therein, preferably for 10 seconds to 30 minutes, more preferably for 1 to 20 minutes, to effect the chemical treatment. The chemically treated article is then washed in the boiling solvents to remove the unreacted materials followed by drying. The conditions for the chemical treatment are not particularly limited and may be freely decided depending on weight and thickness of the films formed by the phosphatizing composition and the concentration of each component.
The phosphatizing composition of the invention enables the formation of a durable zinc phosphate film of excellent corrosion resistance and adhesiveness. In addition, the phosphatizing composition according to the invention is a substantially non-aqueous system so that the zinc phosphate film is easily formed in a short time period on the article to be treated.
The following Examples illustrate the invention.
Example 1 89.7 parts by weight of ethanol, 10.3 parts by weight of water, 0.48 part by weight of zinc borate equivalent to 0.11 part by weight of Zn2+, 0.17 part by weight of pyrophosphoric acid and 1.1 parts by weight of 61 wt% nitric acid were mixed under stirring in a glass beaker at ambient temperature to prepare a homogeneous phosphatizing composition. The composition was then applied to a SPCC-SD steel test piece (0.8 x 70 x 150 mm) using the apparatus described with reference to the accompanying drawing.
The apparatus 1 comprises a glass reactor 2 which includes a solvent defatting zone A, a chemical treatment zone B and a drying zone C. The reactor 2 is provided with a heater 14 around the chemical treatment zone B. The heater 4 is controlled by a heat controller 5. A water jacket 6 is provided around the drying zone
C. To avoid the colling of solvent vapour in the defatting zone A glass wool 3 surrounds the reactor 2 between the heater 4 and the cooling jacket 6. The phosphatizing composition was placed in the chemical treatment zone B and heated by the heater 4 to 14140C (boiling point).A test piece 7, movable upwards and downwards by a stainless steel wire attached to it, was placed in the solvent defatting zone A and solvent defatting treatment was performed for 20 seconds. The vapour evaporating from the composition was cooled by contact with the test piece 7 and the cooling jacket 6.
The solvent defatted test piece 7 was then immersed in the phosphatizing composition, heated to 1140C for 10 minutes. The test piece 7 was then taken out of the reactor 2 and washed using a solvent having solvent components similar to those of the composition.
Afterwards the test piece 7 was placed in the drying zone C and dried for 15 seconds to form a film of zine phosphate on the surface of the test piece.
A second test piece 7 was treated similarly.
On to the film formed onthe surface of the first test piece 7, "MELAMINE No.1, WHITE EXTERIOR USE" (manufactured by NIPPON OIL AND FATS CO., LTD. melamine alkyd type solvent synthetic resin paint, hereinafter abbreviated as "MELAMI NO.1") was baked at 1300C for 20 minutes to form a film thickness of 20 Sm. Likewise onto the film formed on the surface of the second test piece 7, "BELCOAT NO.1 1100 WHITE" (manufactured by
NIPPON OIL AND FATS CO., LTD., acrylic solvent synthetic resin paint, hereinafter abbreviated "BELCOAT") was baked at 1500C for 20 minutes to form a film thickness of 20 to 30 Sm.
Saline spraying tests were conducted on each of the baked test pieces. In the test, firstly each baked test piece was diagonally crosscut with an NT cutter "A-300" so that the cutter reached the metal surface through the coating. Then, with respect to each coating on each of the baked test pieces, the test was conducted in accordance with JIS Z2371 for a predetermined time period. Afterwards, the test pieces were washed with water and left for 214 hours. An adhesive tape sold under the tradename "CELLOTAPE" (manufactured by
NICHIBAN CO., LTD.) having a width of 18 mm was contacted and attached along the cross-cut lines on each test piece. The tape was peeled at 145 degrees and the maximum width at one side peeled from the cross cut portions of the coating was measured. The measured values are shown in Table 2.Saline spraying time periods in the tests were 48 hours for MELAMI No. 1 and 240 hours for BELCOAT.
Table 1 summarizes the nature of the composition and summarizes the test treatment conditions and results.
Examples 2 to 4 Example 1 was repeated, but using the phosphatizing compositions detailed in Table 1 and the test conditions shown in Table 2. The results of the saline spraying tests are also shown in Table 2.
Comparative Example 1
Using a phosphatizing composition containing 72.6 parts by weight of methylene dichloride, 25.5 parts by weight of methanol, 1.9 parts by weight of water, 0.5 part by weight of phosphoric acid, 3.1 parts by weight of
N,N-dimethylformamide and 0.07 part by weight of dinitrotoluene, chemical treatment was carried out under the conditions shown in Table 2 and the test pieces were baked as described in Example 1. The baked test pieces were subjected to the saline spraying test, and the results are shown in Table 2.
Comparative Example 2
Test pieces were prepared without chemical treating and baked. The baked test pieces were subjected to the saline spraying test, with the results shown in Table 2.
Comparative Example 3 72.6 parts by weight of methylene dichloride, 25.5 parts by weight of methanol, 1.9 parts by weight of water, 0.5 part by weight of phosphoric acid, 0.1 part by weight of zinc oxide, 3.1 parts by weight of
N,N-dimethylformamide and 0.07 part by weight of dinitrotoluene were mixed and stirred in a glass beaker at ambient temperature. However, the solubilizing agent was not included in the composition, so that zinc phosphate was formed and a homogeneous solution was not obtained. The composition was thus not suitable for chemically treating a metal test piece.
Examples 5 to 13
Phosphatizing compositions were prepared according to the formulations shown in Table 3. Using these compositions, test pieces were chemically treated under the conditions shown in Table 4 and baked to obtain baked test pieces as described in Example 1. The saline spraying test was carried out on each baked test piece.
The chemical treatment conditions, weight of films and measured results of the saline spraying tests are shown in Table 14.
T a b l e 1
Composition Ex.1 Ex.2 Ex.3 Ex.4 Methanol - 42.1 - Ethanol 89.7 - - Isopropanol - 52.6 - 68.6 t-Butanol - - 76.5 Ethylene Carbonate - - 21.9 Acetonitrile - - - 24.5 Water 10.3 5.3 1.6 6.9 Zinc Borate Zinc Nitrate Zinc Oxide Zinc Nitrate Zn2+ Compound 0.48 1.05 0.1 0.3 (0.11) (0.23) (0.01) (0.064) Nickel Carbonate Nickel Nitrate Ni2+ Compound - - 0.03 0.098 (0.015) (0.02) Sodium Dihydrogen Sodium Carbonate Na+ Compound - - Phosphate 0.098 0.01 (0.0016) (0.02) Orthophosphoric Acid Pyrophosphoric Acid 85% Phosphoric Acid Pyrophosphoric Acid 85% Phosphoric Acid 0.17 0.32 0.05 0.49 Solubilizing Agent 61% Acetic Acid 36% Chloric Acid Trichloroacetic 61% Nitric Acid 1.1 0.53 Acid 0.77 0.98 . The numerals are parts by weight.
. The numerals in the parentheses indicate quantities of ions.
T a b l e 2
Time for Temperature Weight of Film Saline Spraying Test Treatment under Treatment g/m MELAMI NO.1 BELCOAT Ex.1 10 Min. Boiling Point of 44 C 2.5 2mm or less 1mm or less Ex.2 18 Min. Boiling Point of 59 C 3.7 0mm 0mm Ex.3 20 Min. 43 ~ 48 C 1.5 3mm or less 2mm or less Ex.4 5 Min. Boiling Point of 42 C 2.3 1mm or less 1mm or less Comp.Ex.1 2 Min. Boiling Point of 39 C 0.2 8mm 8mm Comp.Ex.2 - - - 8mm or more 8mm or more * The temperature under treatment measured under atmospheric pressure.
* The time for treatment indicates duration of time for contacting with chemical treatment liquid, excluding the time period required before or after the treatment process.
T a b l e 3
Composition Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 Ex.12 Ex.13 Methylene 100 - - 100 100 100 100 100 Chloride Ethyl Ether - - - - - - - - 74.2 Trichloroethane - 100 - - - - - - FURON 13 - - 100 - - - - - Methanol - 31.25 - 46 - - 7.8 - 21.1 Ethanol 23.3 - - - - - - 83 Ethylene - - - - 25 - - - Carbonate Acetonitrile - - - - - 54 - - t-Butanol - - 23.2 - - - - - Water 2.2 1.5 0.21 8 1.6 2.3 0.45 6.7 4.7 Zn2+ Compound Zinc Carbonate Zinc Oxide Zinc Oxide Zinc Carbonate Zinc Chloride Zinc Nitrate Zinc Oxide Zinc Carbonate Zinc Oxide 0.13 0.063 0.026 0.7 0.1 0.7 0.056 1.7 1.0 (0.076) (0.05) (0.02) (0.4) (0.05) (0.15) (0.044) (0.95) (0.1) Ni2+ Compound Nickel Carbonate - - - - Nickel Nitrate Nickel Carbonate Nickel Nickel Carbonate Carbonate 0.13 0.046 0.11 2 0.2 (0.062) (0.009) (0.05) (0.93) (0.11) Ca2+ Compound - Calcium Carbonate - - - - - - 0.03 (0.01) Mn2+ Compound - - Manganese - - - - - Carbonate 0.01 (0.048) Na+ Compound - - - Sodium Carbonate - Sodium Carbonate Sodium Nitrate Sodium Nitrate 0.15 0.3 0.44 4.8 (0.07) (0.14) (0.12) (1.3) Phosphoric Acid 0.11 0.38 0.03 1.5 0.21 0.6 0.28 0.42 0.3 Nitric Acid 0.39 0.38 1.2 2.5 - 0.77 0.11 1.7 0.9 Chloric Acid - - - - 0.53 - - - Others - - - - - - *1 *2 *1 Galvanized sheet ion was treated.
*2 Sodium nitrite was dissolved immediately before the iron plate was immersed in the treating liquid.
Numerals are parts by weight.
The numerals in the parenthese indicate quantities of ions.
T a b l e 4
Time for Temperature Weght of Film Saline Spraying Test Treatment under Treatment g/m MELAMI NO.1 BELCOAT Ex.5 15 Min. 55 ~ 60 C 4.5 1mm or less 1mm or less Ex.6 10 Min. Boiling Point of 73 C 3.0 3mm or less 1mm or less Ex.7 20 Min. 65 ~ 70 C 1.2 5mm or less 2mm or less Ex.8 8 Min. Boiling Point of 77 C 1.5 5mm or less 2mm or less Ex.9 5 Min. Boiling Point of 49 C 0.8 3mm or less 2mm or less Ex.10 3.5 Min. Boiling Point of 56 C 0.6 5mm or less 3mm or less Ex.11 2 Min. Boiling Point of 42 C 4.5 2mm or less 1mm or less Ex.12 8 Min. 15 ~ 25 C 1.2 2mm or less 2mm or less * The temperature under treatment measured under atmospheric pressure.
* The time for treatment indicates duration of time for contacting with chemical treatment liquid, excluding the time period required or after the treatment process.
* In Example 11, galvanized sheet ion was treatment.
Claims (6)
1. A phosphatizing composition comprising
(a) 100 parts by weight of a mixed solvent which contains a polar organic solvent and water, the polar organic solvent having a boiling point of not less than 0 C/760 mmHg and constituting at least 50% by weight of the mixed solvent;
(b) 0.0001 to 7 parts by weight of a phosphoric acid;
(c) 0.01 to 5 parts by weight of zinc ions; and
(d) 0.01 to 5 parts by weight of a solubilizing agent.
2. A composition according to claim 1 further comprising ions of one or more of nickel, manganese, calcium, sodium, magnesium, copper and cobalt, and in which the total of the zinc ions and the said further ions is from 0.01 to 5 parts by weight per 100 parts by weight of the mixed solvent.
3. A metal article, the surface of which has been phosphatized by treatment with a composition according to claim 1 or claim 2.
14. A phosphatizing composition comprising
(e) 100 parts by weight of a mixed solvent which contains a nonpolar organic solvent having a boiling point of not less than 00C/760 mmHg, not less than 0.5% by weight relative to the nonpolar organic solvent of a solubilizing solvent and not more than a homogeneous phase forming limit amount of water;
(f) 0.0001 to 7 parts by weight of phosphoric acid;
(g) 0.001 to 3.5 parts by weight of zinc ion; and
(h) 0.01 to 5 parts by weight of a solubilizing agent.
5. A composition according to claim 4 further comprising ions of one or more of nickel, manganese, calcium, sodium, magnesium, copper and cobalt, and in which the total of the zinc ions and the said further ions is from 0.001 to 3.5 parts by weight per 100 parts by weight of the mixed solvent.
6. A metal article, the surface of which has been phosphatized by treatment with a composition according to claim 4 or claim 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246189A JP3062763B2 (en) | 1990-09-18 | 1990-09-18 | Phosphate-based treatment composition and treated product |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9119726D0 GB9119726D0 (en) | 1991-10-30 |
| GB2249108A true GB2249108A (en) | 1992-04-29 |
| GB2249108B GB2249108B (en) | 1995-01-11 |
Family
ID=17144841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9119726A Expired - Fee Related GB2249108B (en) | 1990-09-18 | 1991-09-16 | Phosphatizing compositions |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3062763B2 (en) |
| FR (1) | FR2666822B1 (en) |
| GB (1) | GB2249108B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2876186B1 (en) * | 2013-11-21 | 2018-07-18 | Samsung Electronics Co., Ltd | Composition for forming film of metal object, film formed using the same, and method of forming film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342575A (en) | 2000-05-31 | 2001-12-14 | Nippon Dacro Shamrock Co Ltd | Aqueous metal surface treatment agent |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB934313A (en) * | 1961-01-12 | 1963-08-14 | Du Pont | Stabilization of chlorohydrocarbon solvents in phosphatizing baths |
| GB974188A (en) * | 1962-06-11 | 1964-11-04 | Nikex Nehezipari Kulkere | Process for manufacturing profiled pieces especially gears from steel bars by means of cold drawing |
| GB986044A (en) * | 1963-07-18 | 1965-03-17 | Hooker Chemical Corp | Process and composition for phosphatizing metals |
| GB990446A (en) * | 1962-07-26 | 1965-04-28 | Du Pont | Improvements in and relating to the treatment of metals |
| JPS52107244A (en) * | 1976-03-06 | 1977-09-08 | Nippon Paint Co Ltd | Chemical treatment of zinc phosphate coating |
| US4102710A (en) * | 1976-12-22 | 1978-07-25 | Diamond Shamrock Corporation | Adjuvant composition for solvent phosphatizing solution |
| GB1548731A (en) * | 1975-03-20 | 1979-07-18 | Diamond Shamrock Corp | Phosphatizing compositions |
| US4334936A (en) * | 1980-02-14 | 1982-06-15 | Akzo N.V. | Liquid composition for phosphating metal surfaces |
| DE3644887A1 (en) * | 1986-04-02 | 1987-10-15 | Werner Dreisoerner Gmbh | Degreasing and anti-corrosive agent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306785A (en) * | 1963-06-04 | 1967-02-28 | Du Pont | Phosphatizing compositions and processes |
| US4029523A (en) * | 1975-03-20 | 1977-06-14 | Diamond Shamrock Corporation | Solvent phosphatizing compositions yielding non water soluble coatings |
| DE3708909A1 (en) * | 1986-04-02 | 1987-10-15 | Werner Dreisoerner Gmbh | Degreasing and corrosion-prevention agent |
| US4931109A (en) * | 1987-09-11 | 1990-06-05 | Finishing Equipment, Inc. | Method and apparatus for depositing an inorganic phosphate coating |
-
1990
- 1990-09-18 JP JP2246189A patent/JP3062763B2/en not_active Expired - Lifetime
-
1991
- 1991-09-16 GB GB9119726A patent/GB2249108B/en not_active Expired - Fee Related
- 1991-09-18 FR FR9111516A patent/FR2666822B1/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB934313A (en) * | 1961-01-12 | 1963-08-14 | Du Pont | Stabilization of chlorohydrocarbon solvents in phosphatizing baths |
| GB974188A (en) * | 1962-06-11 | 1964-11-04 | Nikex Nehezipari Kulkere | Process for manufacturing profiled pieces especially gears from steel bars by means of cold drawing |
| GB990446A (en) * | 1962-07-26 | 1965-04-28 | Du Pont | Improvements in and relating to the treatment of metals |
| GB986044A (en) * | 1963-07-18 | 1965-03-17 | Hooker Chemical Corp | Process and composition for phosphatizing metals |
| GB1548731A (en) * | 1975-03-20 | 1979-07-18 | Diamond Shamrock Corp | Phosphatizing compositions |
| JPS52107244A (en) * | 1976-03-06 | 1977-09-08 | Nippon Paint Co Ltd | Chemical treatment of zinc phosphate coating |
| US4102710A (en) * | 1976-12-22 | 1978-07-25 | Diamond Shamrock Corporation | Adjuvant composition for solvent phosphatizing solution |
| US4334936A (en) * | 1980-02-14 | 1982-06-15 | Akzo N.V. | Liquid composition for phosphating metal surfaces |
| DE3644887A1 (en) * | 1986-04-02 | 1987-10-15 | Werner Dreisoerner Gmbh | Degreasing and anti-corrosive agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2876186B1 (en) * | 2013-11-21 | 2018-07-18 | Samsung Electronics Co., Ltd | Composition for forming film of metal object, film formed using the same, and method of forming film |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2666822B1 (en) | 1995-08-11 |
| JPH04128383A (en) | 1992-04-28 |
| GB2249108B (en) | 1995-01-11 |
| JP3062763B2 (en) | 2000-07-12 |
| FR2666822A1 (en) | 1992-03-20 |
| GB9119726D0 (en) | 1991-10-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990916 |