CN100384946C - 光稳定化效应颜料 - Google Patents
光稳定化效应颜料 Download PDFInfo
- Publication number
- CN100384946C CN100384946C CNB2004800138586A CN200480013858A CN100384946C CN 100384946 C CN100384946 C CN 100384946C CN B2004800138586 A CNB2004800138586 A CN B2004800138586A CN 200480013858 A CN200480013858 A CN 200480013858A CN 100384946 C CN100384946 C CN 100384946C
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- China
- Prior art keywords
- metal
- oxide
- vanadium
- pigment
- effect pigments
- 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.)
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- 239000000049 pigment Substances 0.000 title claims abstract description 130
- 230000000694 effects Effects 0.000 title claims abstract description 53
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 43
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- 239000002537 cosmetic Substances 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 48
- 229910044991 metal oxide Inorganic materials 0.000 claims description 39
- 150000004706 metal oxides Chemical class 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 30
- -1 stupalith Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 150000004767 nitrides Chemical class 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 150000003682 vanadium compounds Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003016 phosphoric acids Chemical class 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
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- 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 description 1
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- 238000005457 optimization Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- TWWDDFFHABKNMQ-UHFFFAOYSA-N oxosilicon;hydrate Chemical compound O.[Si]=O TWWDDFFHABKNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
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- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
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- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
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- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0006—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black containing bismuth and vanadium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
- C09D5/035—Coloring agents, e.g. pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
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- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/014—Stabilisers against oxidation, heat, light or ozone
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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Abstract
本发明涉及光稳定化效应颜料,其中有一个或多个经煅烧且含钒的氧化物层,单独或与硫酸盐、硼酸盐或磷酸盐混合地施加在基材上,涉及制备该颜料的方法,以及涉及其用于塑料、涂料、油漆、印刷油墨、化妆品、薄膜中,用于安全印刷中,用于激光标记,用于热防护中,或用于将种子着色的用途。
Description
本发明涉及光稳定化效应颜料,其中有一个或多个经煅烧且含钒的氧化物层,单独或与硫酸盐、硼酸盐或磷酸盐混合地施加在基材上,涉及一种制备该颜料的方法,并且涉及该颜料用于塑料、涂料、油漆、印刷油墨、化妆品、薄膜中,用于安全印刷中,用于激光标记,用于热防护中或用于将种子着色的用途。
用于户外应用的塑料部件和涂层经常在长时间内经受极端的气候条件和对光的持久且强烈的暴露,这导致材料的老化。这在变色、变脆和降低的机械和化学稳定性方面表现出来。上述现象的起因是,粘结剂的氧化或光解性分解或由于以液体形式或水蒸气形式的水的作用的分解。另外,采用的颜料,特别是含有氧化钛层的珠光颜料,也可能损坏施用介质对光和大气老化的影响的抵抗力。对此的原因是二氧化钛层的特别的光活性,其加速了施用介质的有机组分的光解性分解。
为了抑制这些老化过程,将稳定剂,例如UV光吸收性物质,添加到用于户外应用的配方中。此外,颜料可以被提供有附加的无机层。例如,WO 98/58017描述了一种包含聚烯烃、抗氧化剂和珠光颜料的组合物,这据说显示较低的黄化倾向。在此,抗氧化剂是混合物的必要组分,这限制了在施用介质中的可使用性,因为抗氧化剂必须与其余施用组分相匹配,以避免这些化合物在应用中的破坏。
二氧化钛颜料的光稳定性通过添加掺杂剂而增加是很长时间以来就已知的。例如,DE 2407429描述了钒化合物沉淀到二氧化钛颜料悬浮液上,在此,颜料必须在任何情况下都不被煅烧,以避免形成着色的化合物或颜料的后变暗。但是,未煅烧的颜料具有较低的稳定性,这在具有长使用寿命的应用,例如涂料或塑料中,是特别不利的。
从DE 2545243中已知一种制备具有提高的光化学稳定性的二氧化钛颜料的方法,其通过将选自钒、铜和/或锰的金属离子掺入含水的二氧化钛中,随后在600-1100℃下煅烧而实现。这种方法受限于纯的二氧化钛颜料,这限制了用于油漆、涂料或塑料的应用范围。
本发明的目的因此是提供光稳定化的效应颜料,其具有改进的应用技术性能,该颜料可以不受限制地在所有通常的施用介质和应用领域中应用,而不会显示在效应颜料的性能方面的改变。另外,该光稳定化的效应颜料应该可以容易地且廉价地获得,即用于制备它们的花费应该很低。
这个复杂的目的根据本发明,通过一种光稳定化的效应颜料而实现,所述光稳定化的效应颜料中有一层或多层经煅烧且含钒的氧化物层,单独或与硫酸盐、硼酸盐或磷酸盐混合地施加在基材上。
根据本发明的效应颜料的突出之处是具有改进的光稳定性,可容易地获得并且可以引入所有可想到的施用介质和应用领域中。它们是化学上稳定的和惰性的并与光稳定性结合地显示出对于效应颜料的常见特征,例如光泽、着色强度或颜色多样性。另外,根据本发明的颜料可以在简单的方法中采用宽泛选择的基材制备,在此取决于实施方案而定,可以将制备根据本发明的颜料的方法直接整合入制备效应颜料的方法中。这意味着较低的设备花费和允许更好地控制所需的颜料性能,例如光泽、颜色或遮盖力。通过使用根据本发明的颜料,可以减少向配方或涂敷剂(Anwendungen)中添加另外的光稳定剂的量或甚至完全不添加,这同样降低了制备这些配方和涂敷剂的复杂性和/或成本。
根据本发明的效应颜料所基于的基材可以具有任何规则或不规则的形状。在一个优选的实施方案中,基材由薄片状、球形或针状载体和/或涂覆有一层或多层透明、半透明和/或不透明的层的薄片状、球形或针状载体,所述层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物。特别优选使用基于薄片状载体的基材。合适的是例如薄片状TiO2、合成或天然云母、玻璃薄片、金属薄片、薄片状SiO2、Al2O3或薄片状氧化铁。金属薄片可以尤其由铝、钛、青铜、钢或银组成,优选铝和/或钛。金属薄片在此可以通过相应的处理而钝化。在一个优选的实施方案中,载体可以涂覆有一层或多层透明、半透明和/或不透明的层,该层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物。所述金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物层或其混合物可以具有低折射率(折射率<1.8)或高折射率(折射率≥1.8)。合适的金属氧化物和金属氧化物水合物是本领域技术人员已知的所有金属氧化物或金属氧化物水合物,例如氧化铝、氧化铝水合物、氧化硅、氧化硅水合物、氧化铁、氧化锡、氧化铈、氧化锌、氧化锆、氧化铬、氧化钛,特别是二氧化钛,氧化钛水合物,和其混合物,例如钛铁矿或铁板钛矿。可以采用的金属低氧化物例如是钛的低氧化物。合适的金属例如是铬、铝、镍、银、金、钛、铜或合金,合适的金属氟化物是例如氟化镁。可以采用的金属氮化物或金属氧氮化物是例如金属钛、锆和/或钽的氮化物或氧氮化物。优选将金属氧化物、金属、金属氟化物和/或金属氧化物水合物层施加到载体上,且非常特别优选将金属氧化物和/或金属氧化物水合物层施加到载体上。另外也可以存在多层结构,其由高和低折射率金属氧化物、金属氧化物水合物、金属或金属氟化物层组成,优选其中高和低折射率层是交替的。特别优选由高和低折射率层组成的层组(Schichtpakete),其中一个或多个这些层组可以施加到载体上。高和低折射率层的序列可以在此与载体相匹配,以将载体引入多层结构中。在另一个实施方案中,所述金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物层可以掺混有或掺杂有着色剂或其它元素。合适的着色剂或其它元素是例如有机或无机彩色颜料,例如有色的金属氧化物,例如磁铁矿,氧化铬,或彩色颜料,例如柏林蓝、群青、钒酸铋、Thenards蓝(钴蓝),或者另选有机彩色颜料,例如靛、偶氮颜料、酞菁,或者胭脂红,或者元素,例如钇或锑。除了光稳定性,包含这些层的光稳定化效应颜料还显示出关于其主色方面的高颜色多样性并且可以在许多情况下由于干涉而显示出取决于角度而定的颜色改变(随角异色)。
在一个优选的实施方案中,在载体上的外层是高折射率金属氧化物。该外层可以附加在上文所述的层组上面,或在高折射率载体的情况下可以是层组的一部分,和可以例如由TiO2、钛的低氧化物、Fe2O3、SnO2、ZnO、ZrO2、Ce2O3、CoO、Co3O4、V2O5、Cr2O3和/或其混合物,例如钛铁矿或铁板钛矿组成。TiO2是特别优选的。
在本发明中特别优选的实施方案中,基材是氧化钛或含氧化钛的基材,所述基材基于涂覆有一个或多个包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物的透明、半透明和/或不透明的层的载体。涂覆有一个或多个包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物的透明、半透明和/或不透明的层的薄片状、球形或针状载体的外层优选包含氧化钛。特别地,这些基材的突出之处是,由所述氧化钛决定的高的光活性,其可能对在围绕颜料的施用介质,例如塑料中的稳定性具有不利的作用。根据本发明,这样的基材可以特别地加以光稳定化,这简化了它们在大量应用领域中的可使用性。
基材的尺寸本身不是关键的并取决于基材的形状和取决于特定的应用领域。基于薄片状载体和/或涂覆有一个或多个金属氧化物、金属或金属氟化物层的薄片状载体的基材一般具有厚度为0.05-5μm,特别是0.1-4.5μm。长度或宽度尺寸通常是1-250μm,优选为2-200μm并特别是2-100μm。由球形载体和/或涂覆有一个或多个金属氧化物、金属或金属氟化物层的球形载体构成的基材一般具有平均直径为10nm-100μm,优选为500nm-50μm,并特别是1-20μm。
所述金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物层或其混合物的厚度通常是3-300nm,并在所述金属氧化物、金属氧化物水合物、金属低氧化物、金属氟化物、金属氮化物、金属氧氮化物层或其混合物的情况下,优选是20-200nm。金属层的厚度优选为4-50nm。
适用于一个或多个施加到基材上的经煅烧且含有钒的氧化物层是Al、Ca、Sr、Zn、Si、Zr、Ce、Ti的氧化物或其混合物,优选采用TiO2、Al2O3、Ce2O3、ZnO、ZrO2和/或SiO2。特别优选使用上述氧化物的混合物,其中ZnO是该一个或多个氧化物层的特别合适的混合物成分。这些氧化物构成的层的突出之处是,具有高透明度,没有或具有低固有颜色和具有高光泽,使得基材的色彩性能不被改变。此外,这些材料在煅烧后得到无水的且化学上惰性的表面。在多次涂覆的载体的情况下,含钒的氧化物层可以整合入多层结构中,这简化了可制备性。例如,多层颜料的外层可以是含钒的氧化钛层,其除了增加了光稳定性,还同时影响颜料的光学性能,例如通过干涉作用。
含钒的氧化物层的钒含量是0.002-0.2重量%,以V2O5形式计算并基于颜料整体计,优选为0.01-0.1重量%。在此,在含钒的氧化物层中的钒浓度可以梯度形式向含钒的氧化物层的表面方向增加或减少。在含钒的氧化物层中的钒浓度优选向含钒的氧化物层的表面方向增加。这使得可以由于将与施用介质接触的颜料表面以特别大的程度降低而进一步增加颜料的光稳定性。另外,所需的钒的数量可以以此方式降低,这防止了在颜料的颜色和光泽性能方面的可能的改变。
在另一个实施方案中,将根据本发明的颜料附加相对于其它大气老化影响而稳定化的有机涂层可以被附加施加到经煅烧的含钒的氧化物层上。这使得根据本发明的颜料可以在例如用于户外应用的涂料中使用,所述户外应用除了光稳定性还要求高的耐湿性。施加的有机涂层可以另外用作向配方或涂敷剂中的周围介质上的偶联剂,并因而改善应用技术性能,例如分散性。
所述有机涂层可以由如下通式的有机硅烷、有机铝酸酯、有机钛酸酯和/或锆酸酯组成:
X4-n-mZ-Rn(-B-Y)m
其中X=OH、卤素、烷氧基、芳氧基,
Z=Si、Al、Ti、Zr,
R=烷基、苯基或氢
B=有机的,至少双官能的基团(亚烷基、亚烷基氧基亚烷基)
Y=烷基、氨基、取代的氨基、羟基、羟烷基、硅氧烷、乙酰氧基、异氰酸酯基、乙烯基、丙烯酰基、环氧基、环氧丙氧基、咪唑基或脲基,
n、m=0、1、2、3,其中n+m≤3。
所述偶联剂由向表面上键合的固着基(X4-n-mZ)、至少一个疏水性基团(R、B)和一个或多个官能基团(Y)组成。偶联剂优选是其中Z=Si的化合物。固着基优选由烷氧基硅烷组成,所述烷氧基硅烷可以通过水解反应条件转化成相应的羟基。后者可以键合至经煅烧的且含钒的金属氧化物表面并通过氧桥而实现固着。另外,也可以采用各种偶联剂的混合物,所述偶联剂可以作为混合物形式或单独施加。
有机涂层可以通过选择合适的官能基团而适应于使用介质。另外,在颜料与介质之间经过偶联剂的附加键合可以通过这些官能基团与在施用介质中相应的官能团反应而产生。在特别的实施方案中,根据本发明的颜料的表面用有机官能团的适应于使用介质的组合而加以改性。对此目的还合适的是,在有机涂层内部使用各种偶联剂的混合物。颜料表面的疏水性可以通过含烷基的偶联剂,例如烷基硅烷的整合入而适应。除了有机硅烷,还优选使用其水解产物和均质和非均质的低聚物和/或聚合物,它们同样可以单独使用或与硅烷、锆酸酯、铝酸酯、锆铝酸酯和/或羧基锆铝酸酯相结合使用作为有机涂层。特别优选具有各种偶联剂形成的混合物的有机涂层,特别是具有彼此不同的官能基团Y的各种偶联剂形成的混合物的有机涂层,其确保特别的应用宽度。
有机硅烷的例子有丙基三甲氧基硅烷、丙基三乙氧基硅烷、异丁基三甲氧基硅烷、正辛基三甲氧基硅烷、异辛基三甲氧基硅烷、正辛基三乙氧基硅烷、正癸基三甲氧基硅烷、十二烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、乙烯基三甲氧基硅烷,优选正辛基三甲氧基硅烷和正辛基三乙氧基硅烷。合适的低聚的无醇的有机硅烷水解产物尤其是由Sivento公司以商品名销售的产品,例如Dynasylan HS 2926、Dynasylan HS 2909、Dynasylan HS 2907、Dynasylan HS 2781、Dynasylan HS 2776、Dynasylan HS 2627。另外,低聚的乙烯基硅烷以及氨基硅烷水解产物适用作有机涂层。官能化的有机硅烷例如是3-氨基丙基三甲氧基硅烷、3-甲基丙烯酰氧基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、β-(3,4-环氧基环己基)乙基三甲氧基硅烷、γ-异氰酸根合丙基三甲氧基硅烷、1,3-双(3-环氧丙氧基丙基)-1,1,3,3-四甲基二硅氧烷、脲基丙基三乙氧基硅烷,优选3-氨基丙基三甲氧基硅烷、3-甲基丙烯酰氧基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、β-(3,4-环氧基环己基)乙基三甲氧基硅烷、γ-异氰酸根合丙基三甲氧基硅烷。聚合的硅烷体系的例子描述于WO 98/13426并例如由Sivento公司以商标销售。
有机涂层对经煅烧的含钒的氧化物层的表面性能具有有利的影响。经用有机涂层后涂覆的基材是比未经处理的氧化物表面更为疏水性和更低极性的,并因而可以更好地被粘结剂和有机溶剂润湿。这导致根据本发明的颜料与在施用中使用的粘结剂体系,特别是涂料的更好的相容性。此外,有机涂层,由于其对颜料表面的空间屏蔽,而抑制了颜料粒子的附聚和因而改善了它们的分散性。
本发明的目的另外通过一种制备光稳定化的效应颜料的方法而实现,在该方法中将一个或多个含钒的氢氧化物、氧化物水合物和/或氧化物层,单独或与硫酸盐、磷酸盐和/或硼酸盐混合地施加到基材上,并将得到的颜料随后进行煅烧。根据本发明的方法可以在一步生产法中进行并因而是廉价和简单的。在多层基材的情况下,根据本发明的方法可以直接并入颜料的生产方法中。
涂覆有一个或多个含钒的氢氧化物、氧化物水合物和/或氧化物层的涂层既可以通过湿法化学方法也可以经过溶胶-凝胶法进行,优选通过湿法化学方法进行沉淀。在通过湿法化学方法施加的情况下,用相应的含钒的氧化物、氢氧化物和/或氧化物水合物进行涂覆。为此目的,将基材悬浮在溶剂或溶剂混合物中,优选水中,并且掺入适用于形成氢氧化物、氧化物水合物和/或氧化物层的金属盐和一种或多种钒化合物的溶液。通过本领域技术人员已知的方法调节和优化对于各自的氢氧化物、氧化物水合物和/或氧化物的沉淀所必需的pH值。
钒化合物可以在任何时间点和以任何形式,例如以一种或多种钒化合物的固体形式或作为溶液形式,引入具有氢氧化物、氧化物水合物和/或氧化物层的涂层。钒化合物优选以溶液形式添加,在此这可以通过适用于形成氢氧化物、氧化物水合物和/或氧化物层的金属盐的溶液和/或通过在涂覆过程中在调节涂覆参数,例如pH值或溶剂的数量方面必要的辅助溶液而进行。钒化合物优选通过对于控制pH值所必要的辅助溶液而添加,其中辅助溶液优选是酸或碱的水溶液,例如盐酸或氢氧化钠溶液。在另一个实施方案中,钒化合物可以一定方式引入氢氧化物、氧化物水合物和/或氧化物层中,使得在层中的钒浓度以梯度形式向含钒的层的表面方向而增加或减少。梯度的形成通过时间点和钒添加速率而控制。如果,例如,钒浓度需要向表面方向增加,则这可以例如通过在将氢氧化物、氧化物水合物和/或氧化物层施加到基材上的过程结束时有目的地添加钒化合物而进行。在此,钒化合物可以引入对于控制pH值所必要的辅助溶液中,用该溶液使氢氧化物、氧化物水合物和/或氧化物层的沉淀完全。所需的梯度大小可以通过控制添加速率加以调节。与本发明相关的所有其它可想到的梯度控制可能性方案都在本领域技术人员的公知常识范围内。
合适的钒化合物原则上是在各种氧化态下的所有钒化合物,它们可溶于溶剂或溶剂混合物中,例如钒(IV)或钒(V)化合物。优选使用氧钒根(IV)盐,例如氯化氧钒或硫酸氧钒,钒酸盐,或钒(V)氧化物的溶液,特别是偏钒酸钠。
合适的用于形成氢氧化物、氧化物水合物和/或氧化物层的金属盐是相应的卤化物、硝酸盐和/或硫酸盐,优选采用相应的卤化物和/或硝酸盐。硫酸盐、磷酸盐和/或硼酸盐可以从合适的金属盐和从相应的硫酸盐、磷酸盐或硼酸盐源,与氧化物、氢氧化物和/或氧化物水合物一起共沉淀。合适的硫酸盐源是硫酸和所有可溶性的硫酸盐,例如硫酸钠、硫酸钾或硫酸锂,合适的磷酸盐源是磷酸或所有可溶性的磷酸盐,例如磷酸钠、磷酸氢二钠或磷酸钾,并且合适的硼酸盐源是所有可溶性的硼酸盐,例如硼酸钠或二硼酸钠。硫酸盐、磷酸盐和/或硼酸盐的数量,和沉淀条件,例如pH值或温度,可以通过本领域技术人员已知的方法加以优化。
以此方式获得的颜料随后进行煅烧。煅烧可以在300-900℃的温度下进行,优选在600-900℃下进行。通过煅烧,沉淀出的氧化物、氢氧化物和/或氧化物水合物被脱水,转化成相应的氧化物并被致密化。
在根据本发明的方法的另一个实施方案中,将根据本发明的颜料附加相对于其它的大气老化影响加以稳定化的有机涂层可以被附加施加到经煅烧的含钒的氧化物层上。该有机涂层以溶液形式在高于60℃,优选高于70℃的温度下施加。合适的溶剂是有机溶剂、水或其混合物,优选使用水。对于该有机涂层的施加必要的反应时间是至少5min,优选在10-90min的时间内进行,但是也可以如需要而延长。将获得的颜料通过本领域技术人员常用的方法,例如通过过滤、干燥和筛分,加以处理和分离。
除了良好的光稳定性,根据本发明的光稳定化的效应颜料的突出之处是具有良好的应用技术性能。通过煅烧,氧化物层被脱水和致密化,这导致颜料表面的孔隙率的降低。较少的水能在致密化的表面上被吸收,并且在界面层中吸附的水的不利作用可以因而在涂层中得到降低。煅烧还除去了以氢氧化物或氧化物水合物形式化学键合的水。这对在塑料中使用颜料具有优点,因为在热塑性聚合物中,例如在聚酯中,存在的水,可能在升高的温度下导致聚合物的水解方式分解。在涂覆有氢氧化物或氧化物水合物的颜料的情况下,可能在塑料加工过程中发生水的释放,这导致引发聚合物链的不期望的降解。在根据本发明的颜料的情况下,通过氧化物层的煅烧,在塑料中的颜料的加工期间也没有水能出现,使得它们特别适用于这种应用领域。
由于改善的应用技术性能,在此描述的光稳定化的效应颜料适用于多种多样的应用。本发明因而进一步提供根据本发明的光稳定化的效应颜料用于将如下物质着色:塑料,涂料,例如水性涂料或粉末涂料,油漆,印刷油墨,化妆品配方,纸,陶瓷材料,玻璃,薄膜;用于安全印刷中,用于农业领域中,例如用于将种子着色方面,用于将例如纸或塑料加以激光标记,用于热防护中和用于制备颜料制剂,例如珠光体(Pearlet)、糊剂和悬浮液,和制备干制剂,例如粒料、颗粒、屑片等的用途,它们优选用于印刷油墨和涂料中。在其中所用材料的毒性需要考虑的应用中,例如在化妆品配方中,优选钒(IV)化合物用于生产含钒的氧化物层。根据本发明的颜料可以在颜色体系中使用的多种多样的已知粘结剂中应用并可以含水和溶剂基体系两种中使用。颜料可以通过本领域技术人员已知的所有方法引入到各自的施用介质中。
在化妆品的情况下,根据本发明的效应颜料特别适用于装饰性化妆品的产品和配方,例如指甲漆、着色粉、唇膏或眼影,皂类、牙膏等。根据本发明的颜料当然也可以在配方中与任何类型的化妆品原料和辅料相结合。这些尤其包括油、脂肪、蜡、成膜剂、防腐剂和一般性决定应用技术性能的辅料,例如增稠剂和流变添加剂,例如膨润土、锂蒙脱石、二氧化硅、硅酸钙、明胶、高分子量碳水化合物和/或表面活性助剂等。包含根据本发明的颜料的配方可以是亲脂性、亲水性或疏水性类型。在具有离散的水相和非水相的非均相配方的情况下,根据本发明的颜料可以在每种情况下存在于所述两相中的仅一相中或分布在两个相中。
含水配方的pH值可以为1-14,优选为2-11和特别优选为5-8。根据本发明的颜料在配方中的浓度不设任何限制。它们可以,取决于应用情况,为0.001%(冲洗掉产品,例如淋浴凝胶)至100%(例如在将效应颜料用作基材的情况下用于特别应用的光泽效果制品)。根据本发明的颜料可以另外还与化妆品活性成分结合。合适的活性成分例如有驱虫剂,UV A/BC防护过滤剂(例如OMC、B3、MBC)、抗老化活性成分、维生素和其衍生物(例如维生素A、C、E等)、自晒黑剂(例如尤其是DHA、赤藓酮糖)和其它化妆品活性成分,例如红没药醇、LPO、依克托因(Ectoin)、Emblica(余甘子)、尿囊素、生物类黄酮和其衍生物。
根据本发明的效应颜料特别适合用于塑料中,例如用于农业用覆膜、红外反射性薄膜和片材、礼品用箔、塑料容器和用于本领域技术人员已知的所有应用的模塑制品中,因为,特别是在塑料中,根据本发明的效应颜料的光稳定性导致由其生产的产品的耐久性的延长。适合于根据本发明的效应颜料的引入过程的塑料是所有通用塑料,例如热固性塑料或热塑性塑料。可能的应用和可以采用的塑料、加工方法和添加剂描述于例如RD 472005,或R.Glausch,M.Kieser,R.Maisch,G.Pfaff,J.Weitzel,Perlglanzpigmente(珠光颜料),Curt R.Vincentz出版社,1996,第83页及后面几页,其公开内容在此并入本发明。所述引入过程可以向所有已知的塑料中进行,并以所有本领域技术人员已知的方式进行,例如通过混合的纯物理方式以及通过可能施加的有机涂层的相应官能基团与塑料的反应的化学方式。特别地,根据本发明的效应颜料适合于具有高剪切能输入的应用中,如,例如在一些塑料应用中所要求的。例如,令人惊奇地发现,根据本发明的光稳定化即使在非常强烈的机械负荷后也仍然存在。这是由于稳定化试剂与决定性的干涉层之间的非常强的相互作用。
在涂料和油墨中使用这些颜料时,所有本领域技术人员已知应用领域都是可能的,例如粉末涂料、水性涂料、汽车油漆,用于凹版、胶版、丝网或柔性版印刷的印刷油墨,和用于在户外应用的涂料中。为了制备印刷油墨,多种多样的粘结剂,特别是水溶性类型,都是合适的,例如基于丙烯酸酯、甲基丙烯酸酯、聚酯、聚氨酯、硝基纤维素、乙基纤维素、聚酰胺、聚丁酸乙烯酯、酚醛树脂、马来酸树脂、淀粉或聚乙烯醇。涂料可以是水基或溶剂基涂料,其中涂料成分的选择遵从于本领域技术人员的公知常识。根据本发明的颜料优选应用于涂料中,例如用于汽车油漆或水基涂料中,它们由于颜料的特别的稳定性而适用于所有户内和户外的应用。在粉末涂料配方中,根据本发明的效应颜料可以甚至不用另外的有机涂层而简单地引入,并在这些应用中显示出具有显著的闪光或放光效果的明亮的金属光泽。在户外应用中使用时,粉化和灰化的发生大大延迟,或在高度大气老化稳定性的配方,所谓的超耐久的粉末涂料中,基本上被避免。在现有技术中已知的硅烷基大气老化稳定化的情况下,经常出现与粉末涂料基体的不相容性,特别是在所谓的干掺混的范围内,这经常在烘烤的粉末涂料层中强的颜料缔合方面表现出来。这种缺陷在根据本发明的效应颜料的情况下几乎不会观察到,因为主要是纯无机的大气老化性层。
由于宽的适用性,本发明同样提供包含一种或多种根据本发明的光稳定化效应颜料的塑料、涂料、油漆、印刷油墨、化妆品配方、纸、陶瓷材料、玻璃、薄膜、种子、颜料制剂和干制剂。
下述实施例意于更详细地解释本发明,而不是对其进行限定。
实施例:
光活性的测定:
将颜料样品引入塑料基体中,并目测Pb2+还原至Pb的程度。灰色着色的评价根据ISO 105第A 02部分(相应于DIN 54 001)进行。测试标度范围为从5(非常好)到1(非常差)。
对比例1:
将100g具有粒子尺寸为10-50μm的云母薄片悬浮在1升水中并在搅拌下加热至75℃。将3.35g SnCl4的10%水溶液在1小时内计量加入到悬浮液中,在此过程中通过添加32%氢氧化钠溶液而将pH值保持在1.8。在随后搅拌30分钟后,将237g TiCl4的30%水溶液在12小时内计量加入,在此过程中通过添加32%氢氧化钠溶液而将pH值保持在1.8。将混合物随后继续搅拌30min,并使用氢氧化钠溶液将pH值调节至4.0。形成的中间产物包含约2%氧化锡和100%二氧化钛,基于云母含量计。将颜料通过过滤与上层清液分离并洗涤。在120℃下干燥后,将颜料在800℃下煅烧45min,并将得到的具有蓝色干涉色的效应颜料通过筛分(目宽为63μm)除去粗级分。该颜料的光活性评价为1。
实施例1:
如在对比例1中所述制备含钒的颜料,其中将64mg钒酸钠*4H2O添加到用于在TiO2层形成过程中保持pH值恒定的氢氧化钠溶液中。该颜料因而包含0.03%氧化钒(V)的掺杂量,基于总重量。该颜料的光活性评价为3。
实施例2:
如在对比例1中所述制备基础颜料悬浮液。随后使用氢氧化钠溶液将pH值调节至6.5。将3.35g氯化锌在60ml水中的溶液在1小时内添加入,在此过程中使用5%氢氧化钠溶液将pH值保持恒定,所述氢氧化钠溶液中溶解有53mg钒酸钠。将颜料如在对比例1中所述进行处理。颜料因而按照计算包含2%氧化锌和0.025%氧化钒,基于总重量计。该颜料的光活性评价为4。
实施例3:
基本上如对比例1中所述制备颜料悬浮液。在涂覆后,将悬浮液的pH值使用氢氧化钠溶液调节至5.0。将9.5g氯化铝*6H2O在100ml水中的溶液在1小时内添加入,在此过程中使用5%氢氧化钠溶液将pH值保持恒定,在所述氢氧化钠溶液中溶解有100mg氧化钒(V)。将颜料如对比例1中所述处理。该颜料因而按计算包含2%氧化铝和0.1%氧化钒,基于总重量计。颜料的主色是泛黄色。该颜料的光活性评价为3-4。
实施例4:
颜料悬浮液基本上如对比例1中所述制备。在第一75%涂覆过程中,将pH值使用32%氢氧化钠溶液保持恒定。将64mg钒酸钠溶解在用于剩余涂覆的氢氧化钠溶液中。将颜料如对比例1中所述加以处理。颜料因而按计算包含0.025%氧化钒,基于总重量计。由于制备条件,掺杂以梯度形式发生并主要在Ti02外层中发生。该颜料的光活性评价为3-4。
实施例5:
将100g新制备的,即仍然未经煅烧的,将用4.0%二氧化锡和62%金红石涂覆的二氧化硅薄片在涂覆后的母液中提供氧化钒和氧化锆的后涂层。在剧烈搅拌下,将5.23g ZrOCl2*8H2O的5%水溶液在1小时内计量加入悬浮液中(体积约为1.5升),该悬浮液使用氢氧化钠溶液调节至pH为3.0并调节温度至75℃下,在此过程中通过添加5%氢氧化钠溶液将pH值保持恒定。32mg NH4VO4预先已经加入氢氧化钠溶液中。在随后搅拌30分钟后,使用氢氧化钠溶液将pH值调节至4.0,并将效应颜料通过过滤与上层清液分离并洗涤。在120℃下干燥后,在800℃下进行煅烧45min,并将具有绿金色干涉色的颜料通过筛分(目宽为63μm)除去粗级分。该颜料的光活性评价为3-4。
实施例6:
含钒的颜料如对比例1中所述制备,其中将54mg硫酸氧钒(IV)溶解在TiCl4溶液中。颜料因而包含0.03%钒(以V2O5形式计算)的掺杂量,基于总重量计。该颜料的光活性评价为3。
Claims (13)
1.光稳定化效应颜料,其特征在于,有一个或多个经煅烧且含钒的氧化物层,单独或与硫酸盐、硼酸盐或磷酸盐混合地施加在基材上,其中基材是薄片状或针状载体和/或涂覆有一个或多个透明、半透明和/或不透明的层的薄片状或针状载体,所述层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物,并且其中钒含量是0.002-0.2重量%,以V2O5形式计算并基于颜料整体计。
2.根据权利要求1的光稳定化效应颜料,其特征在于,基材是氧化钛或含氧化钛的基材,所述基材基于涂覆有一个或多个透明、半透明和/或不透明的层的薄片状或针状的载体,所述层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物。
3.根据权利要求2的光稳定化效应颜料,其特征在于,涂覆有一个或多个透明、半透明和/或不透明的层的薄片状或针状载体的外层包含氧化钛,所述透明、半透明和/或不透明的层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物。
4.根据权利要求1或2的光稳定化效应颜料,其特征在于,经煅烧且含钒的氧化物层由Al、Ca、Sr、Zn、Si、Zr、Ce、Ti的氧化物或其混合物组成。
5.根据权利要求1或2的光稳定化效应颜料,其特征在于,在含钒的氧化物层中钒的浓度以梯度形式向含钒的氧化物层的表面方向增加或减少。
6.根据权利要求1或2的光稳定化效应颜料,其特征在于,附加将一个有机涂层施加到经煅烧的含钒的氧化物层上。
7.一种制备根据权利要求1的光稳定化效应颜料的方法,其特征在于,将一个或多个含钒的氢氧化物、氧化物水合物和/或氧化物层,单独或与硫酸盐、磷酸盐和/或硼酸盐混合地施加到基材上,并随后进行煅烧,其中基材是薄片状或针状载体和/或涂覆有一个或多个透明、半透明和/或不透明的层的薄片状或针状载体,所述层包含金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物,并且其中钒含量是0.002-0.2重量%,以V2O5形式计算并基于颜料整体计。
8.根据权利要求7的方法,其特征在于,通过湿法化学方法和/或通过溶胶-凝胶法施加所述氢氧化物、氧化物水合物和/或氧化物层。
9.根据权利要求7或8的方法,其特征在于,以一定方式将钒化合物引入所述氢氧化物、氧化物水合物和/或氧化物层,使得在该层中钒的浓度以梯度形式向含钒的层的表面方向增加或减少。
10.根据权利要求7或8的方法,其特征在于,煅烧在300-900℃的温度下进行。
11.根据权利要求7的方法,其特征在于,附加将一个有机涂层施加到经煅烧的含钒的氧化物层上。
12.根据权利要求1的光稳定化效应颜料用于塑料、涂料、油漆、印刷油墨、化妆品配方、纸、陶瓷材料、玻璃、薄膜中,用于安全印刷中,用于激光标记,用于热防护中,或用于将种子着色,和用于干制剂和颜料制剂中的用途。
13.包含一种或多种根据权利要求1的光稳定化效应颜料的塑料、涂料、油漆、印刷油墨、化妆品配方、纸、陶瓷材料、玻璃、薄膜、种子、颜料制剂和干制剂。
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EP (1) | EP1633819A1 (zh) |
JP (1) | JP2007505987A (zh) |
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CN (1) | CN100384946C (zh) |
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DE102004051104A1 (de) * | 2004-10-19 | 2006-04-27 | Merck Patent Gmbh | Opake Kunststoffe |
KR20070086311A (ko) * | 2004-12-15 | 2007-08-27 | 시바 스페셜티 케미칼스 홀딩 인크. | 금속 산화물을 유기 기재에 마이크로파 침착시키는 방법 |
US7842130B2 (en) * | 2005-08-22 | 2010-11-30 | Basf Corporation | Complex inorganic effect materials |
JP5068979B2 (ja) * | 2006-11-07 | 2012-11-07 | 日揮触媒化成株式会社 | 歯科用充填材、その製造方法および歯科用複合材料 |
JP2009078955A (ja) * | 2007-09-27 | 2009-04-16 | Okuno Chem Ind Co Ltd | 無鉛セラミックカラー組成物 |
CN101168624B (zh) * | 2007-11-28 | 2012-02-15 | 四川大学 | 多层结构智能控温功能型云母珠光颜料及其制备 |
CN101168625B (zh) * | 2007-11-28 | 2012-02-15 | 四川大学 | 智能控温功能型云母钒珠光颜料及其制备 |
DE102008047572A1 (de) * | 2008-09-16 | 2010-04-15 | Eckart Gmbh | Metalleffektpigmentpräparation in kompaktierter Form, Verfahren zu deren Herstellung und Verwendung derselben |
EP2531563B1 (de) | 2010-02-04 | 2016-11-09 | Merck Patent GmbH | Effektpigmente |
CA2807380A1 (en) * | 2010-08-02 | 2012-02-09 | Oechsler Aktiengesellschaft | Method for producing a coloured fibre-reinforced plastic and chamfering of such fibre-reinforced plastic, as well as forming the part produced therefrom |
CN102029113B (zh) * | 2010-11-09 | 2012-09-26 | 中国海洋石油总公司 | 一种味精工业废水处理膜清洗剂的制备方法 |
DE102012017710A1 (de) * | 2012-09-07 | 2014-03-13 | Polysecure Gmbh | Werkstück oder Werkstoff mit inertem Markersystem |
US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
CN103254664A (zh) * | 2013-05-14 | 2013-08-21 | 四川大学 | 一种二氧化钒包覆云母的智能控温型粉体的制备方法 |
US9881714B2 (en) | 2014-06-19 | 2018-01-30 | Saint-Gobain Performance Plastics Corporation | Laser-markable insulation material for wire or cable assemblies |
US10256009B2 (en) | 2014-06-19 | 2019-04-09 | Saint-Gobain Performance Plastics Corporation | Laser-markable insulation material for wire or cable assemblies |
EP3034562B2 (de) * | 2014-12-19 | 2021-12-08 | Eckart GmbH | Absorbierende Effektpigmente mit hohem Chroma und hoher Brillanz, Verfahren zu ihrer Herstellung und Verwendung derselben |
EP3081601A1 (de) * | 2015-04-15 | 2016-10-19 | Schlenk Metallic Pigments GmbH | Perlglanzpigmente auf der basis von monolithisch aufgebauten substraten |
CN111977686A (zh) * | 2020-08-31 | 2020-11-24 | 攀钢集团重庆钒钛科技有限公司 | 提高耐光性的钛白粉初品制备方法 |
JPWO2022244766A1 (zh) * | 2021-05-17 | 2022-11-24 |
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- 2004-04-27 CN CNB2004800138586A patent/CN100384946C/zh not_active Expired - Fee Related
- 2004-04-27 EP EP04729647A patent/EP1633819A1/de not_active Withdrawn
- 2004-04-27 KR KR1020057022240A patent/KR20060028392A/ko not_active Application Discontinuation
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WO2004104110A1 (de) | 2004-12-02 |
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KR20060028392A (ko) | 2006-03-29 |
EP1633819A1 (de) | 2006-03-15 |
US7455726B2 (en) | 2008-11-25 |
CN1791645A (zh) | 2006-06-21 |
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