CN1124260A - 用磷酸锆或钛配合物涂敷的有机颜料 - Google Patents
用磷酸锆或钛配合物涂敷的有机颜料 Download PDFInfo
- Publication number
- CN1124260A CN1124260A CN94119561A CN94119561A CN1124260A CN 1124260 A CN1124260 A CN 1124260A CN 94119561 A CN94119561 A CN 94119561A CN 94119561 A CN94119561 A CN 94119561A CN 1124260 A CN1124260 A CN 1124260A
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- Prior art keywords
- pigment
- zirconium
- metal
- salt
- weight
- Prior art date
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- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 title claims description 10
- 239000010452 phosphate Substances 0.000 title claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title 1
- 239000000049 pigment Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- -1 phosphate anion Chemical class 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000011368 organic material Substances 0.000 claims description 10
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 241001460678 Napo <wasp> Species 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical class [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002469 indenes Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- UADUAXMDVVGCGW-UHFFFAOYSA-N propanoic acid;zirconium Chemical compound [Zr].CCC(O)=O UADUAXMDVVGCGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical group [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000000976 ink Substances 0.000 abstract 1
- 239000012860 organic pigment Substances 0.000 abstract 1
- 238000000518 rheometry Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- MFFVROSEPLMJAP-UHFFFAOYSA-J zirconium(4+);tetraacetate Chemical class [Zr+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O MFFVROSEPLMJAP-UHFFFAOYSA-J 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 229920001727 cellulose butyrate Polymers 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- VNWKDIUSXQCPGN-UHFFFAOYSA-J dicalcium tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ca+2].[Ca+2] VNWKDIUSXQCPGN-UHFFFAOYSA-J 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
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- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 description 1
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- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
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- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical class O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
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- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
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Abstract
包括有机颜料的颜料组合物,颜料的颗粒表面涂有保护涂料,该涂料由金属磷酸盐配合物组成,其中该金属选自锆、钛或它们的混合物,该涂料的用量以颜料为基础的是0.5-100%(重量),优选是0.5-40%(重量),最优选5-40%(重量)。
它们突出表现在各种优异的性质,尤其表现在用它们所获得的着色物的高光泽度,表现在超级分散稳定性,耐热性以及表现在用它所制得的色浆或印刷油墨的非常良好的流变行为。
用该型组合物着色的塑料也突出表现在高耐热性和塑料件基本上无翘曲。
Description
本发明涉及有机颜料类,其颗粒表面有锆或钛磷酸盐配合物的粘滞性涂层,该类颜料的制备及它们的应用。它们突出地表现在各种优异的性能,尤其是用它们所获得的色彩的高光泽度,超级分散稳定性和用它们所制备的色浆或印刷油墨的极其良好的流变性能。
用铝或镁磷酸盐配合物涂覆颜料颗料在US3,946,136中已披露。在这一专利说明书中声称,用该涂料涂覆过的无机和有机颜料具有改进的耐化学药品性能和耐热性能及增强的耐晒性。
现已发现,用锆或钛磷酸盐配合物涂敷颜料颗粒会以惊人、更显著的方式改进颜料的性能,尤其是光泽度、分散稳定性、耐热性和流变行为。
因此,本发明涉及包括有机颜料的颜料组合物,颜料的颗粒表面有保护性涂层,该涂层由金属磷酸盐配合物组成,其中该金属选自锆、钛和它们的混合物,该涂料的用量,以颜料为基础,为0.5—100%(重量),优选不超过40%(重量),最优选5—40%(重量)。该涂料的最理想用量尤其取决于将被涂敷的颜料的特定表面。
锆和/或钛与磷的摩尔比优选为0.25∶0.75,更优选为0.45∶0.55。
氟或BF-离子也可引入该保护涂料,这也在US3,946,134中有披露。
所有的常规颜料,包括:quinophthalones,阴丹酮,黄烷士酮,皮蒽酮,二噁嗪,perinones,硫靛,金属络合物和特别是二酮吡咯并吡咯,喳吖啶二酮、苝、蒽醌、酞菁、偶氮颜料、异二氢[杂]茚和isoindolinone都适合制备该新颖的颜料组合物。喹吖啶二酮是优选的,而二酮吡咯并吡咯是特别优选的。
本发明还涉及将金属磷酸盐配合物的粘滞性涂料施加在有机料的颗粒表面上,其中该金属是锆和/或钛,该方法包括:
a)由普通方法,用Zr和/或Ti的盐或螫合物将颜料分散在水中或低级烷基醇中,或它们的混和物中,和
6)在搅拌下,加入提供磷酸根离子的化合物的水溶液,其加入量使得形成了0.5—100%(重量)(以颜料为基础)的、金属与磷的优选摩尔比为0.25∶0.75的金属磷酸盐配合物,
或
首先用能提供磷酸根离子的化合物分散颜料,然后加入金属配合物或金属螯合物的水溶液,
这样,就地在颜料颗粒表面上形成锆和/或钛磷酸盐配合物并沉淀为保护层。
优选首先用金属盐或金属螯合物分散颜料,然后加入能提供磷酸根离子的化合物的溶液。
合适的锆和/或钛盐或配合物一般是硫酸锆、碳酸锆铵、乙酸锆、丙酸锆、二氯氧化锆、四氯化钛或硫酸氧锆及,较好地,以下结构式的螯合物:其中n是1—3中的数,R1是甲基、乙基、甲氧基或乙氧基,R2是甲基或乙基和R3是卤素或C1—C4烷氧基及其混合物。
卤素取代基可以是溴、碘,优选是氯,C1—C4烷氧基一般是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基或叔丁氧基。
优选使用结构式I、II或III中螯合物的一种,其中:
R1优选是甲基或乙氧基,
R2优选是甲基,
n优选是2,和
R3优选是C1—C4烷氧基,最优选异丙氧基。
特别优选的螯合物是锆和钛的乙酰丙酮化物和三羟乙基胺化钛。
适宜的低级烷基醇一般包括甲基、乙基、正丙基、正丁基、仲丁基、叔丁基或戊基醇。然而,分散是在没有醇的水中进行的。
磷酸根离子优选以正、偏或焦—磷酸或其盐,尤其碱金属盐的形式加进去。
特别适宜的磷酸根离子给体一般是正磷酸,正磷酸盐如MH2PO4,M2HPO4或M3PO4,偏磷酸,克诺尔(Knorre)盐[(NaPO3)3·6H2O],格雷姆(Graham)盐[(NaPO3)6],偏磷酸盐(Calgon)[(NaPO3)12-13·Na2O],M2H2P2O7和M4P2O7,其中M是Na、K或NH4。正磷酸盐尤其优选Na2HPO4和Na3PO4。
该混合物可方便地在20—80℃的温度范围内,优选在室温下搅拌5分钟—2小时。
氟或氟硼酸根离子优选以水溶液或悬浮液的形式加入。现已发现,二氟氢铵(NH4HF2)、氢氟酸和氟化钠是尤其适用于该目的。氟离子可随金属配合体BF4 -离子一道或在它加入后加入到该悬浮液中,如果代替氟离子使用,优选以铵盐的形式加进去。
本发明的颜料另外还有其它保护层。该另外的保护层可以是金属氧化物保护涂料(例如在US4,880,472中所公开的硅石和/或矾土、或硅酸烷基酯的涂层(例如由Dynamit Nobel销售的DYNA-SYLAN产品),或丙烯酸系树脂涂层。优选的涂料是那些如US4,734,137所公开的含有丙烯酸氨基烷基酯树脂的涂料。
因此,本发明涉及另外涂有丙烯酸氨基烷基酯树脂层的如上所述颜料组合物,该树脂可以通过如下结构式的单体均聚得到:其中R6是氢或甲基,R4和R5各自独立地是其它氢、甲基或乙基,及m是1—6之间的整数,或通过该同样的单体与能与该单体共聚的单体共聚得到。
这种另外的涂料可通过普通方法,如在前面专利说明书中所描述的那样,一般通过将该新颖的颜料组合物在水中制成淤浆并以所需要的常规用量加入所需要的涂料试剂。
这种新颖的颜料组合物非常适合于将高分子量的有机物着色,尤其以油漆体系和印刷油墨的形式。能够用本发明的组合物上色或着色的高分子量有机物是纤维素醚类和酯类,一般包括乙基纤维素、硝基纤维素、醋酸纤维素或丁酸纤维素;天然树脂或合成树脂类,一般是聚合型或缩聚型树脂类如氨基塑料类,优选脲/甲醛和密胺/甲醛树脂类,醇酸树脂类,酚醛塑料类,聚碳酸酯类,聚氨酯类,(聚)硅氧烷和硅氧烷树脂,单独地或以混合物形式。
以溶解形式(如成膜剂)的高分子量有机物,一般是熟炼过的胡麻子油、硝基纤维素、醇酸树脂、密胺树脂、丙烯酸系树脂和脲/甲醛树脂,也是适合的。
取决于最终使用要求,可方便地将该新颖的颜料组合物作为调色剂使用或以制剂的形式使用。该颜料组合物能够以0.01—30%(重量),优选以0.1—10%(重量)的用量使用,以将被着色的高分子量有机物为基础。
用该新颖的组合物将高分子量有机物着色是通过由其本身或以基料中的母料形式使用滚轧机、混合或混炼装置引入这样一种组合物而方便地进行的。然后由本身已知的方法,可方便地通过压延加工、模塑、挤出、涂敷、浇铸或通过注塑将着色过的物质转变为所要求的最终形式。为了制得非脆性模品或降低它们的脆性,在加工前通常需要将增塑剂引入高分子量化合物中。合适的增塑剂一般是磷酸、苯二甲酸或癸二酸的酯类。该增塑剂可在将本发明的组合物混入聚合物之前或之后加入。为获得不同的色调,除了该新型的组合物之外,将填料或其它发色组分如白色、彩色或黑色颜料以任何用量加入到高分子量有机物中。
为了将油漆体系、涂料和印刷油墨着色,高分子量有机物和新型组合物,及选择性可有可无的添加剂如填料、其它颜料、催干剂或增塑剂,被精细地分散或溶解在普通有机溶剂或溶剂混合物中。该操作程序大致是,各组分自己或几种组分一起被分散或溶解在溶剂中,之后,混合所有的组分。
所得着色物突出表现在全面良好的牢度性质如超级透明度,和良好的耐过度喷除性能、耐迁移性、耐热、耐光和耐候。
最特别的方面,本发明的颜料组合物突出表现在优异的流变性质和在油漆和印刷油墨体系中的超级分散稳定性,而且所得涂饰品表现出超级光泽度和优异的DOI(即图像清晰度)。在工业油漆中,该新型产品具有良好的耐热性能。
鉴于新型颜料组合物的良好流变性质,制备高颜料含量的油漆是可能的。
当引入塑料中时,新型产品同样突出表现在超级的耐热性和用它着色过的塑料件基本上无翘曲。
该新型颜料组合物最适合于将水基和/或溶剂基油漆体系,尤其汽车漆上色。最理想的利用是金属效果的涂饰。
本发明通过以下实施例来说明,其中,除非另有指明,百分数按重量计。实施例1
用4.8g锆(IV)乙酰丙酮化物将63.5g31.5%的、以下结构式的二酮吡咯并吡咯(例如根据US4,579,949制备的)含水滤饼分散在132ml水中。边搅拌,将7.05g Na2HPO4·12H2O在70ml水中的溶液经2.5小时用泵抽到该悬浮液中。随后过滤该悬浮液,用水洗涤残余物,在80℃下干燥,并加以粉碎。实施例2
重复实施例1,唯一例外的是用同样量的以下结构式和二酮吡咯并吡咯(例如根据US4,579,949所制得的)代替结构式V的二酮吡咯并吡咯:实施例3
用2.57g以下结构式的三羟乙基胺化钛(IV)(Dynamit Nobel,80%异丙醇溶液)将27.2g36.8%的结构式VI的二酮吡咯并吡咯滤饼分散在70ml水中。在搅拌下,3g Na2HPO4·12H2O在40ml水中的溶液经大约1小时缓慢加进这种悬浮液中。然后,过滤该悬浮液,用水洗涤,在80℃下干燥,并加以粉碎。实施例4
重复实施例3,但是用1.26g Zr(SO4)2·4H2O代替三羟乙基胺化钛,而且不是使用3g,仅使用2.53g Na2HPO4·12H2O。实施例5
将2g根据实施例1获得的产品和48g包括以下各组分:
56g 醇酸树脂ALKYDALF310(Bayer AG;60%
二甲苯溶液)13g 密胺树脂(YMEL327(Cyanamid;90%
丁醇溶液)25g 二甲苯25g 丁醇2.5g 1—甲氧基—2—丙醇和1g 硅油(1%在二甲苯中)的烘漆按普通方法混合。所得色淀在玻璃板上展开成膜。在放入循环空气烘箱中烘烤(在120℃下30分钟)之前,该涂层在25°的倾斜度下风干约30分钟。
根据DIN 67 530,用光泽仪(Zehntner ZGM1020)测定在20°的倾斜度下的光泽度。
如此获得的涂饰层意外地具有比用未涂覆过的颜料所获得的涂饰层更好的光泽。
用实施例2—4的各种产品代替实施例1的产品,得到对比结果,与用未涂覆过的颜料所获得的涂饰层相比,在光泽度上具有非常惊人的改进。实施例6
将128.5g15.56%的以下结构式的2,9—二甲基喹吖啶二酮滤饼和4.8g锆(IV)乙酰丙酮化物分散在366.7g水中。在搅拌下,将7.08g Na2HPO4·12H2O在50ml水中的溶液经50分钟加进去。用稀乙酸将该悬浮液调至pH=5,再搅拌1小时,然后过滤。用水洗涤残留物,在80℃下干燥,并加以粉碎。实施例7:
将27.2g36.8%的二酮吡咯并吡咯颜料(C.I.Pigment Red255)湿滤饼和1.02g锆乙酰丙酮经4小时分散在72g水中。在搅拌下,将1.3g NaH2PO4·2H2O在20ml水中的溶液经40分钟加进去。用水洗涤残余物,干燥和粉化。实施例8:
将27.06g36.96%的isoindolinone C.I.Pigment Yellow110滤饼和2.24g锆(IV)乙酰丙酮化物经4小时分散在71g水中。在搅拌下,将3.3gNa2HPO4·12H2O在40ml水中的溶液经40分钟加进去。用稀乙酸将该悬浮液调至pH=5,进一步搅拌1小时,然后过滤。用水洗涤残留物,干燥和粉化。实施例9:
重复实施例9的操作程序,但从以下金属盐或金属螯合物开始:
实施例 金属盐或金属螯合物
10 三羟乙基胺化钛(IV)
11 Zr(SO4)2
12 Ti(O)SO4
13 乙酸锆(IV)实施例14—21:
重复实施例5的操作程序,但是,不从实施例1的产品;而从实施例6—13的产品开始。如此获得的涂饰层的光泽非常意外地比用来涂覆过的颜料所获得的涂饰层的光泽更好。Ca4B滤饼:
将74.8g2—氨基—5—甲基苯磺酸分散在580ml水中。然后,加入34.9g47%的氢氧化钠水溶液,该混合物在40℃下边搅拌边加热,直到得到完全的溶液为止。通过加入冰将溶液冷至0℃。加入27.6g亚硝酸钠在50ml水中的溶液,随后加入90.0g36%的盐酸。该重氮化淤浆在温度保持在0℃的同时搅拌28分钟。
将75.2g2—羟基—3—萘甲酸在40℃下溶于1300ml水和42.6g47%的氢氧化钠水溶液中。通过加入冰将该偶联剂溶液冷至5℃。
然后将重氮化的淤浆在搅拌下经30分钟加入到偶联剂溶液中。pH最初降至pH10.6—10.8,然后,通过加入稀氢氧化钠溶液继续保持下去。向所获得的悬浮液中加入126.8g固体氯化钙钙并连续搅拌75分钟,同时保持在5—8℃的温度。悬浮液经15分钟加热至70℃,然后过滤。所得Ca4B滤饼用水洗涤,直到无盐为止。实施例22
119.8g20.9%湿Ca4B滤饼在258.2g水中高速分散2小时。然后加入6.88g锆(IV)乙酰丙酮化物,该混合物高速搅拌7小时。在室温下将10.1g Na2HPO4·12H2O在19ml水中的溶液经2.25小时加入。过滤该悬浮液;用水洗涤残余物,在70℃下干燥过度,然后在90℃下烘烤4小时。实施例23
使用球磨机将6.21g根据实施例22所获得的产物和50.0g未着色的甲苯—酚醛树脂凹印油墨(含2.05g树脂)在16小时内进行分散。所得油墨可以通常方式凹印。
如此获得的油墨分散液的质量以及印刷品的透明度和光泽度令人惊奇地比用未涂覆过的颜料所获得的各种相应性质更好。
Claims (16)
1.一种包括有机颜料的颜料组合物,该颜料的颗粒表面有保护涂料层,该涂料由金属磷酸盐配合物组成,其中该金属选自锆、钛和其混合物,该涂料的用量以颜料为基础是0.5—100%(重量),优选是5—40%(重量)。
2.根据权利要求1的颜料组合物,其中该颜料是二酮吡咯并吡咯、喹吖啶二酮、苝、蒽醌、酞菁、偶氮、异二氢氮〔杂〕茚或Isoin-dolinone系颜料。
3.根据权利要求1的颜料组合物,其中该颜料是二酮吡咯并吡咯或喹吖啶二酮系颜料。
5.一种将该金属磷酸盐合物的粘合涂料施加在有机颜料的颗粒表面的方法,其中该金属是锆和/或钛,该方法包括:
a)由普通方法,用Zr和/或Ti的盐或螯合物将颜料分散在水中或低级烷基醇中,或它们的混合物中,和
b)在搅拌下,加入提供磷酸根离子的化合物的水溶液,其加入量使得形成了0.5—100%(重量)(以颜料为基础)的、金属与磷的优选摩尔比为0.25∶0.75的金属磷酸盐配合物,
或
首先用能提供磷酸根离子的化合物分散颜料,然后加入金属配合物或金属螯合物的水溶液,
这样,就地在颜料粒表面上形成锆和/或钛磷酸盐配合物并沉淀为保护层。
6.根据权利要求5的方法,其中获得了5—40%(重量)的金属磷酸盐配合物,以颜料为基础。
7.根据权利要求5的方法,它包括首先用金属盐或金属螯合物分散该颜料,然后加入能提供磷酸根离子的化合物的溶液。
8.根据权利要求5的方法,它包括使用选自硫酸锆、碳酸锆铵、乙酸锆、丙酸锆、二氯氧化锆、四氯化钛(IV)或硫酸氧锆和以下结构式的螯合物的锆或钛盐或配合物,
其中n是1—3中的数,R1是甲基、乙基、甲氧基或乙氧基,R2是甲基或乙基及R3是卤素或C1—C4烷氧基,或它们的混合物。
9.根据权利要求8的方法,它包括使用结构式I、II或III的螯合物,其中R1是甲基或乙氧基,R2是甲基,n是2,以及R3是C1—C4烷氧基。
10.根据权利要求5的方法,其中提供磷酸根离子的化合物是选自磷酸,MN2GPO4,M2HPO4或M3PO4,偏磷酸,克诺尔(Knorre)盐〔(NaPO3)3·6H2O〕,格雷姆(Graham)盐〔(NaPO3)6〕,偏磷酸盐(Calgon)〔(NaPO3)12-13·Na2O〕,M2H2P2O7和M4P2O7的化合物,其中M是Na、K或NH4。
11.根据权利要求10的方法,其中使用正磷酸盐。
12.根据权利要求5的方法,其中分散是在水中进行的。
13.根据权利要求5的方法,其中另外引入氟或氟硼酸根离子。
14.一种含有根据权利要求1所要求的颜料组合物的高分子量有机物。
15.根据权利要求14的高分子量有机物,它是油漆体系或印刷油墨。
16.根据权利要求15的高分子量有机物,它是汽车漆。
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CH381993 | 1993-12-22 | ||
CH3819/1993 | 1993-12-22 | ||
CH3819/93 | 1993-12-22 |
Publications (2)
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CN1124260A true CN1124260A (zh) | 1996-06-12 |
CN1068362C CN1068362C (zh) | 2001-07-11 |
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CN94119561A Expired - Fee Related CN1068362C (zh) | 1993-12-22 | 1994-12-21 | 用磷酸锆或钛配合物涂敷的有机颜料 |
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US (1) | US5522925A (zh) |
EP (1) | EP0659840B1 (zh) |
JP (1) | JP3630183B2 (zh) |
KR (1) | KR100364950B1 (zh) |
CN (1) | CN1068362C (zh) |
CA (1) | CA2138606A1 (zh) |
DE (1) | DE59409309D1 (zh) |
Cited By (2)
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CN116037935A (zh) * | 2023-02-16 | 2023-05-02 | 华中科技大学 | 一种金属汽车漆用近片状钛合金粉末、其制备方法和应用 |
CN118165585A (zh) * | 2024-05-09 | 2024-06-11 | 陕西帆阳建筑科技有限公司 | 一种耐高温的建筑防腐涂料及其制备方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0717086B1 (de) * | 1994-12-15 | 2000-04-26 | Ciba SC Holding AG | Mit Metallphosphatkomplexen und Aminen beschichtete organische Pigmente |
DE60003508T2 (de) | 1999-11-17 | 2004-04-29 | Ciba Speciality Chemicals Holding Inc. | Diketopyrrolopyrrol |
US20010015154A1 (en) | 2000-01-27 | 2001-08-23 | Roman Lenz | Ternary pigment compositions |
DE10235573A1 (de) | 2002-08-03 | 2004-02-12 | Clariant Gmbh | Pigmentzubereitungen auf Basis von Diketopyrrolopyrrolpigmenten zum verzugsfreien Pigmentieren von teilkristallinen Kunststoffen |
CN100439453C (zh) | 2003-10-23 | 2008-12-03 | 西巴特殊化学品控股有限公司 | 热稳定的二酮基吡咯并吡咯颜料混合物 |
US8092909B2 (en) * | 2006-09-07 | 2012-01-10 | Columbia Insurance Company | Color foundation coat and color top coat paint system |
CN101429053B (zh) * | 2008-12-31 | 2011-12-21 | 广东万兴无机颜料股份有限公司 | 铁锆红色料的制备方法 |
JP4737725B2 (ja) * | 2009-03-26 | 2011-08-03 | ブラザー工業株式会社 | インクジェット記録用水性インク、インクカートリッジおよびインクジェット記録装置 |
CN103569990B (zh) * | 2013-11-20 | 2015-06-24 | 苏州大学 | 一种无机基质的磷酸盐颜料、制备方法及应用 |
CN108239421A (zh) | 2017-12-25 | 2018-07-03 | 先尼科化工(上海)有限公司 | 一种具有高耐候性橙色二酮吡咯并吡咯颜料及其制备方法 |
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FR1226652A (fr) * | 1959-02-26 | 1960-07-15 | Cfmc | Pigments améliorés par incorporation d'un résinate de zirconium |
US3946134A (en) * | 1973-07-23 | 1976-03-23 | The Harshaw Chemical Company | Method of encapsulating particles and the resultant product |
GB1506578A (en) * | 1974-09-30 | 1978-04-05 | Ici Ltd | Pigments |
US4110492A (en) * | 1976-11-11 | 1978-08-29 | The Harshaw Chemical Company | Method for encapsulating water-insoluble particles |
US4880472A (en) * | 1987-06-16 | 1989-11-14 | Ciba-Geigy Corporation | Organic pigments coated with metal oxides |
JPS61255964A (ja) * | 1985-05-10 | 1986-11-13 | Toyo Soda Mfg Co Ltd | 有機顔料の製造法 |
US5123965A (en) * | 1989-11-30 | 1992-06-23 | Ciba-Geigy Corporation | Process for stabilizing bismuth vanadate pigments against attack by hydrochloric acid |
EP0466646B1 (de) * | 1990-07-11 | 1996-08-28 | Ciba-Geigy Ag | Verfahren zum verzugsfreien Pigmentieren von Polyolefinen |
GB9117766D0 (en) * | 1991-08-16 | 1991-10-02 | Ciba Geigy Ag | Process for improving storage stability |
-
1994
- 1994-12-13 EP EP94810720A patent/EP0659840B1/de not_active Expired - Lifetime
- 1994-12-13 DE DE59409309T patent/DE59409309D1/de not_active Expired - Lifetime
- 1994-12-20 CA CA002138606A patent/CA2138606A1/en not_active Abandoned
- 1994-12-20 US US08/359,688 patent/US5522925A/en not_active Expired - Lifetime
- 1994-12-21 KR KR1019940035589A patent/KR100364950B1/ko not_active IP Right Cessation
- 1994-12-21 CN CN94119561A patent/CN1068362C/zh not_active Expired - Fee Related
- 1994-12-22 JP JP31895394A patent/JP3630183B2/ja not_active Expired - Fee Related
Cited By (4)
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CN116037935A (zh) * | 2023-02-16 | 2023-05-02 | 华中科技大学 | 一种金属汽车漆用近片状钛合金粉末、其制备方法和应用 |
CN116037935B (zh) * | 2023-02-16 | 2024-04-19 | 华中科技大学 | 一种金属汽车漆用近片状钛合金粉末、其制备方法和应用 |
CN118165585A (zh) * | 2024-05-09 | 2024-06-11 | 陕西帆阳建筑科技有限公司 | 一种耐高温的建筑防腐涂料及其制备方法 |
CN118165585B (zh) * | 2024-05-09 | 2024-07-16 | 陕西帆阳建筑科技有限公司 | 一种耐高温的建筑防腐涂料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0659840A3 (de) | 1996-01-03 |
CA2138606A1 (en) | 1995-06-23 |
EP0659840B1 (de) | 2000-04-26 |
US5522925A (en) | 1996-06-04 |
JPH07216251A (ja) | 1995-08-15 |
DE59409309D1 (de) | 2000-05-31 |
EP0659840A2 (de) | 1995-06-28 |
KR100364950B1 (ko) | 2003-03-19 |
JP3630183B2 (ja) | 2005-03-16 |
KR950018319A (ko) | 1995-07-22 |
CN1068362C (zh) | 2001-07-11 |
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