EP1633819A1 - Photostabilisierte effektpigmente - Google Patents
Photostabilisierte effektpigmenteInfo
- Publication number
- EP1633819A1 EP1633819A1 EP04729647A EP04729647A EP1633819A1 EP 1633819 A1 EP1633819 A1 EP 1633819A1 EP 04729647 A EP04729647 A EP 04729647A EP 04729647 A EP04729647 A EP 04729647A EP 1633819 A1 EP1633819 A1 EP 1633819A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- oxide
- vanadium
- photo
- shaped
- 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.)
- Withdrawn
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 126
- 230000000694 effects Effects 0.000 title claims abstract description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003973 paint Substances 0.000 claims abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 14
- 239000002537 cosmetic Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000004922 lacquer Substances 0.000 claims abstract description 11
- 235000021317 phosphate Nutrition 0.000 claims abstract description 11
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 10
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 9
- 239000000976 ink Substances 0.000 claims abstract description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 9
- 238000010330 laser marking Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 24
- -1 metal oxide hydrates Chemical class 0.000 claims description 21
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 17
- 238000009472 formulation Methods 0.000 claims description 15
- 150000004767 nitrides Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 150000003682 vanadium compounds Chemical class 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
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- 229910052684 Cerium Inorganic materials 0.000 claims description 2
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- 238000003980 solgel method Methods 0.000 claims description 2
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- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- 230000019612 pigmentation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000243 solution Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 9
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- 125000000524 functional group Chemical group 0.000 description 5
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- 238000001556 precipitation Methods 0.000 description 5
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- 239000011787 zinc oxide Substances 0.000 description 5
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- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
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- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 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
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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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- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
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- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- TWWDDFFHABKNMQ-UHFFFAOYSA-N oxosilicon;hydrate Chemical compound O.[Si]=O TWWDDFFHABKNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 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
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DPUZPWAFXJXHBN-UHFFFAOYSA-N tetrasodium dioxidoboranyloxy(dioxido)borane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]B([O-])OB([O-])[O-] DPUZPWAFXJXHBN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-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
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- HLOLETUOZGAKMT-UHFFFAOYSA-N trimethoxysilyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C(C)=C HLOLETUOZGAKMT-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-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
- 125000005287 vanadyl group Chemical group 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 239000001993 wax Substances 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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- 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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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- 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
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- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
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- 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
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- 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
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- 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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-
- 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
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/301—Thickness of the core
-
- 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
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/401—Inorganic protective coating
-
- 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
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- C09C2200/402—Organic protective coating
- C09C2200/407—Organosilicon materials, e.g. silanes, silicones
-
- 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
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- C09C2200/408—Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
Definitions
- the present invention relates to photostabilized effect pigments, one or more calcined and vanadium-containing oxide layers being applied to a substrate, alone or in a mixture with sulfates, borates or phosphates, processes for their preparation and their use in plastics, paints, paints, printing inks, cosmetics , Foils, in security printing, for laser marking, in heat protection or for seed coloring.
- Plastic parts and layers of paint for outdoor applications are often exposed to extreme weather conditions and long-lasting intense light, which leads to an aging of the materials. This manifests itself in discoloration, embrittlement and reduced mechanical and chemical stability.
- the causes for this are oxidative or photolytic decomposition of the binders or decomposition by the action of water in liquid form or water vapor.
- the pigments used in particular pearlescent pigments containing titanium oxide layers, can also impair the resistance of the application media to the effects of light and weather. The reason for this is the special photoactivity of titanium dioxide layers, which accelerates the photolytic decomposition of the organic components of the application medium.
- WO 98/58017 describes a composition containing a polyolefin, an antioxidant and a pearlescent pigment which is said to show a lower tendency to yellowing.
- the antioxidant is an essential component of the mixture, which limits the applicability in application media, since the antioxidant has to be adapted to the other application components in order to avoid destruction of these compounds in the applications.
- DE 2 545 243 describes a method for producing a titanium dioxide pigment with increased photochemical stability by adding water-containing titanium dioxide to metal ions from the group of vanadium, copper and / or manganese and then calcining at 600 to 1100 ° C. This process is limited to pure titanium dioxide pigments, which limits the range of applications for paints, varnishes or plastics.
- photostabilized effect pigments with improved application properties, which can be used without restriction in all common application media and applications, without showing changes in the properties of the effect pigments.
- the photostabilized effect pigments should be easily and inexpensively accessible, which means that the effort for their production should be low.
- This complex object is achieved according to the present invention by a photostabilized effect pigment, one on a substrate or more calcined and vanadium-containing oxide layers, applied alone or in a mixture with sulfates, borates or phosphates.
- the effect pigments according to the invention are notable for improved photostability, are easily accessible and can be incorporated into all conceivable application media and applications. They are chemically stable and inert and, in combination with the photostability, show the usual features of effect pigments, e.g. Gloss, color strength or variety of colors.
- the pigments according to the invention can be produced in a simple process with a wide selection of substrates, and, depending on the embodiment, the process for producing the pigments according to the invention can be integrated directly into the production process of the effect pigments. This means less expenditure on equipment and allows better control of the desired pigment properties, e.g. Shine, color or opacity.
- the addition of further photostabilizers to formulations or applications can be reduced or even dispensed with entirely, which likewise reduces the production outlay for these formulations and applications.
- the substrate consists of a platelet-shaped, spherical or needle-shaped carrier and / or a layer coated with one or more transparent, semi-transparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials platelet-shaped, spherical or acicular carriers.
- Substrates based on platelet-shaped supports are particularly preferably used.
- platelet-shaped Ti0 2 synthetic or natural mica, glass platelets, metal platelets, platelet-shaped SiO 2 , Al 2 0 3 or platelet-shaped iron oxide.
- the metal platelets can consist of aluminum, titanium, bronze, steel or silver, preferably aluminum and / or titanium.
- the metal platelets can be passivated by appropriate treatment. In a preferred one
- the carrier can be coated with one or more transparent, semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
- Metal nitride, metal oxynitride layers or the mixtures thereof can be low (refractive index ⁇ 1.8) or high refractive index (refractive index> 1.8).
- Suitable metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to the person skilled in the art, such as, for. B. aluminum oxide, aluminum oxide hydrate, silicon oxide, silicon oxide hydrate, iron oxide, tin oxide, cerium oxide, zinc oxide, zirconium oxide, chromium oxide, titanium oxide, in particular titanium dioxide, titanium oxide hydrate and mixtures thereof, such as e.g. Ilmenite or pseudobrookite.
- the titanium suboxides can be used as metal suboxides.
- Suitable metals are e.g. Chromium, aluminum, nickel, silver, gold, titanium, copper or alloys, as
- Metal fluoride is suitable, for example, magnesium fluoride.
- the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used as metal nitrides or metal oxynitrides.
- Metal oxide, metal, metal fluoride and / or metal oxide hydrate layers are preferred and very particularly preferably metal oxide and / or
- Metal oxide hydrate layers applied to the carrier Furthermore, multilayer structures made of high and low refractive metal oxide, metal oxide hydrate, metal or metal fluoride layers can also be present, with high and low refractive layers alternating. Layer packages consisting of a high and a low refractive index layer are particularly preferred, it being possible for one or more of these layer packages to be applied to the support.
- the order of high and low-index layers can be adapted to the carrier in order to include the carrier in the multilayer structure.
- the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers can be mixed or doped with colorants or other elements. As
- Colorants or other elements are suitable, for example, organic or inorganic color pigments such as colored metal oxides, e.g. Magnetite, chromium oxide or color pigments such as Berlin blue, ultramarine, bismuth vanadate, thenards blue, or organic color pigments such as Indigo, azo pigments, phthalocyanines or carmine red or
- organic or inorganic color pigments such as colored metal oxides, e.g. Magnetite, chromium oxide or color pigments such as Berlin blue, ultramarine, bismuth vanadate, thenards blue
- organic color pigments such as Indigo, azo pigments, phthalocyanines or carmine red or
- Elements such as Yttrium or antimony, photostabilized effect pigments containing these layers show, in addition to photostability, a wide range of colors in relation to their body color and can in many cases show an angle-dependent change in color (color flop) due to interference.
- the outer layer on the carrier is a high-index metal oxide.
- This outer layer can additionally be part of a layer package on the above-mentioned layer packages or in the case of high-index supports and, for example, of T1O 2 , titanium suboxides, Fe 2 0 3 , Sn0 2) ZnO, ZrO 2 , Ce 2 0 3 , CoO, Co 3 0 4 , V 2 O 5 , Cr 2 O 3 and / or mixtures thereof, such as, for example, llmenite or pseudobrookite. TiO 2 is particularly preferred.
- the embodiment is titanium oxide or a substrate containing titanium oxide on the basis of a support coated with one or more transparent, semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
- the outer layer preferably contains one or more transparent, semi-transparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials coated platelet-shaped, spherical or acicular carrier titanium oxide.
- substrates in particular are distinguished by a high photoactivity caused by the titanium oxide, which can have a disadvantageous effect on the stability of the application medium surrounding the pigment, such as, for example, the plastic.
- substrates in particular can be photostabilized, which facilitates their applicability in numerous applications.
- Substrates based on platelet-shaped carriers and / or a platelet-shaped carrier coated with one or more metal oxide, metal or metal fluoride layers generally have a thickness between 0.05 and 5 ⁇ m, in particular between 0.1 and 4.5 ⁇ m.
- the extension in length or width is usually between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m.
- Substrates made of a spherical carrier and / or a spherical carrier coated with one or more metal oxide, metal or metal fluoride layers generally have average diameters of 10 nm to 100 ⁇ m, preferably between 500 nm and 50 ⁇ m and in particular between 1 and 20 ⁇ m on.
- the thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or a mixture thereof is usually 3 to 300 nm and in the case of the metal oxide, metal oxide hydrate, metal suboxide, metal fluoride, metal nitride , Metal oxynitride layers or a mixture thereof, preferably 20 to 200 nm.
- the thickness of the metal layers is preferably 4 to 50 nm.
- the oxides of Al, Ca, Sr, Zn, Si, Zr, Ce, Ti or mixtures thereof are suitable, preferably TiO 2 , Al 2 O. 3 , Ce O 3 , ZnO, ZrO and / or SiO 2 are used. Mixtures of the above are particularly preferred
- Oxides are used, ZnO being a particularly suitable mixture component of the oxide layer or oxide layers. Layers of these oxides are characterized by high transparency, lack of or little inherent color and high gloss, so that the coloristic properties of the substrates are not changed. Furthermore, these materials result in anhydrous and chemically inert surfaces after calcining.
- the oxide layer containing vanadium can be integrated into the multi-layer structure, which makes it easier to manufacture.
- the outer layer of a multilayer pigment can contain a vanadium
- Titanium oxide layer which in addition to increasing the photostability also influences the optical properties of the pigment, e.g. through interference.
- the vanadium content of the vanadium-containing oxide layer is 0.002 to 0.2% by weight, calculated as V 2 O5 and based on the total pigment, preferably 0.01 to 0.1% by weight.
- the vanadium concentration in the vanadium-containing oxide layer can increase or decrease in the form of a gradient in the direction of the surface of the vanadium-containing oxide layer.
- the vanadium concentration in the vanadium-containing oxide layer preferably increases in the direction of the surface of the vanadium-containing oxide layer. This can further increase the photostability of the pigments, since the photoactivity of the surface of the pigment which is in contact with the application medium is reduced particularly strongly.
- the amount of vanadium required can be reduced in this way, which is a possible change in the color and gloss properties of the pigment prevented.
- an organic coating can additionally be applied to the calcined oxide layer containing vanadium, which additionally stabilizes the pigments according to the invention against further weather influences.
- This enables the use of the pigments according to the invention e.g. in paints for outdoor applications that, in addition to photostability, also require high resistance to moisture.
- the applied organic coating can also act as a coupling reagent to the surrounding medium of the formulation or application and thus the application properties such as improve dispersibility.
- the organic coating can consist of organosilanes, aluminates, titanates and / or zirconates of the general formula
- R alkyl, phenyl or hydrogen
- B organic, at least bifunctional group (alkylene, alkyleneoxyalkylene)
- the coupling reagents consist of an anchor group (X4- n -mZ) that binds to the surface, at least one hydrophobic group (R, B) and one or more functional groups (Y).
- the anchor group preferably consists of alkoxysilanes which can be converted into corresponding hydroxyl groups by hydrolytic reaction conditions. The latter can bind to the calcined and vanadium-containing metal oxide surface and cause anchoring via oxygen bridges.
- mixtures of different coupling reagents can be used, which can be applied as a mixture or individually.
- the organic coating can be adapted to the medium used.
- additional bonds between pigment and medium can be generated via the coupling reagent by reaction of the functional groups with corresponding functionalities in the application media.
- the surface of the pigments according to the invention is modified with a combination of organic functionalities adapted to the feed medium.
- the use of mixtures of different coupling agents within the organic coating is also suitable for this.
- the hydrophobicity of the pigment surface can be adjusted by integrating alkyl-containing coupling reagents such as alkyl silanes.
- organosilanes In addition to the organosilanes, the use of their hydrolysates and homogeneous and heterogeneous oligomers and / or polymers is also preferred, which can also be used as an organic coating, either alone or in combination with silanes, zirconates, aluminates, zirconium aluminates and / or carboxyzirconium aluminates.
- An organic coating with mixtures of different coupling reagents, in particular with functional groups Y that differ from one another, is particularly preferred, which ensures a particular range of applications.
- organosilanes are propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, dodecyltrimethoxysilanilysilane As oligomeric, alcohol-free
- Organosilane are, among others, those sold under the trade name "Dynasylan ®" by the company. Sivento products, such. As Dynasylan HS 2926, Dynasylan HS 2909, Dynasylan HS2907, Dynasylan HS 2781, Dynasylan HS 2776, Dynasylan HS 2627. In addition, oligomeric vinylsilane and aminosilane hydrolyzate are suitable as organic coatings. Functionalized organosilanes are, for example, 3-aminopropyltrimethoxysilane, 3-
- Ureidopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanatopropyltrimethoxysilane are preferred.
- Examples of polymeric silane systems are described in WO 98/13426 and are described, for. B. from Sivento under the trademark Hydrosil ® .
- the organic coating has a positive influence on the surface properties of the calcined oxide layers containing vanadium.
- the surfaces coated with the organic coating are more hydrophobic and less polar than the untreated oxide surfaces and are therefore better wettable by binders and organic solvents. This results in better compatibility of the pigments according to the invention with the binder systems used in the application, in particular paints.
- the organic coating also inhibits because of its steric shielding of the pigment surface the agglomeration of the pigment particles and thus improves their dispersibility.
- the object of the present invention is achieved by a method for producing photo-stabilized effect pigments, with a
- One or more hydroxide, oxide hydrate and / or oxide layers containing vanadium are applied alone or in a mixture with sulfates, phosphates and / or borates and the pigment obtained is then calcined.
- the method according to the invention can be carried out in a one-step production process and is therefore inexpensive and simple. In the case of multilayer substrates, the method according to the invention can be directly integrated into the pigment production process.
- Hydroxide, oxide hydrate and / or oxide layers can be carried out both wet-chemically and via sol-gel processes; the precipitation is preferably carried out wet-chemically.
- the corresponding vanadium-containing oxides, hydroxides and / or oxide hydrates are coated.
- the substrates are suspended in a solvent or solvent mixture, preferably water, and solutions with the metal salts suitable for the formation of hydroxide, hydrated oxide and / or oxide layers and one or more vanadium compounds are added.
- the pH value required for the precipitation of the respective hydroxide, oxide hydrate and / or oxide is set and optimized professionally.
- the vanadium compounds can be introduced at any time and in any form into the coating with the hydroxide, hydrated oxide and / or oxide layers, for example in solid form or as a solution of one or more vanadium compounds.
- the vanadium compounds are preferably added in the form of a solution, this being done via the Solutions of the metal salts suitable for the formation of the hydroxide, oxide hydrate and / or oxide layers and / or by means of the auxiliary solutions required in the coating process when setting the coating parameters, such as pH value or amount of solvent.
- the vanadium compounds are preferably added via the auxiliary solutions required for controlling the pH, the auxiliary solutions preferably being aqueous solutions of acids or bases, such as, for example, hydrochloric acid or sodium hydroxide solution.
- the vanadium compound can be introduced into the hydroxide, oxide hydrate and / or oxide layer such that the vanadium concentration in the layer increases or decreases in the form of a gradient in the direction of the surface of the layer containing vanadium.
- the gradient formation is controlled via the time and the speed of the vanadium addition. For example, if the vanadium concentration is to increase toward the surface, this can be done, for example, by adding the vanadium compounds in a targeted manner at the end of the application of the hydroxide, oxide hydrate and / or oxide layer to the substrate.
- the vanadium compounds can be introduced in the auxiliary solution necessary for controlling the pH, with which the precipitation of the hydroxide, oxide hydrate and / or oxide layer is completed.
- the desired size of the gradient can be set by controlling the speed of the addition. All other possibilities of gradient control conceivable in connection with this invention are within the knowledge of the person skilled in the art.
- Suitable vanadium compounds are in principle all vanadium compounds of various oxidation levels that are soluble in a solvent or solvent mixture, for example vanadium (IV) or vanadium (V) compounds.
- Vanadyl (IV) salts for example vanadyl chloride or vanadyl sulfate, vanadates or Solutions of vanadium (V) oxide, especially sodium metavanadate, are used.
- the corresponding halides, nitrates and / or sulfates are suitable as metal salts for the formation of the hydroxide, oxide hydrate and / or oxide layers; the corresponding halides and / or nitrates are preferably used.
- the sulfates, phosphates and / or borates can be co-precipitated together with the oxides, hydroxides and / or oxide hydrates from suitable metal salts and from corresponding sulfate, phosphate or borate sources.
- Suitable sulfate sources are sulfuric acid and all soluble sulfates such as.
- sodium sulfate, potassium sulfate or lithium sulfate as phosphate sources phosphoric acid or all soluble phosphates such as. B. sodium phosphate, disodium hydrogen phosphate or potassium phosphate and as borate sources all soluble borates such as. B. sodium borate or sodium diborate.
- the amount of sulfates, phosphates and / or borates and the precipitation conditions, such as. B. pH or temperature can be optimized in a professional manner.
- the pigments obtained in this way are then calcined.
- the calcination can take place at temperatures of 300-900 ° C, preferably at 600-900 ° C.
- the precipitated oxides, hydroxides and / or oxide hydrates are dewatered, converted into the corresponding oxides and compressed.
- an organic coating can additionally be applied to the calcined oxide layer containing vanadium, which additionally stabilizes the pigments according to the invention against further weather influences.
- Coating takes place in solution at temperatures above 60 ° C, preferably above 70 ° C.
- solvents organic solvents, water or mixtures thereof, water is preferably used.
- the reaction time required for applying the organic coating is at least 5 minutes, preferably over a period of 10 to 90 minutes, but can also be extended as desired.
- the pigment obtained is worked up and isolated by methods known to those skilled in the art, e.g. B. by filtration, drying and screening.
- the photostabilized effect pigments according to the invention are notable for good application properties.
- the calcination dehydrates and densifies the oxide layers, which leads to a reduction in the porosity of the pigment surface. Less water can be absorbed on the compacted surface and thus the disadvantageous effects of water adsorbed in the boundary layer in the lacquer can be reduced.
- the calcination also removes water chemically bound in the form of hydroxides or oxide hydrates. This has advantages when using the pigments in plastics, since water present in thermoplastic polymers such as in polyesters, can lead to hydrolytic decomposition of the polymer at higher temperatures.
- the photostabilized effect pigments described here are suitable for one
- the invention thus furthermore relates to the use of the photostabilized agents according to the invention Effect pigments for pigmenting plastics, lacquers, such as hydraulic lacquers or powder lacquers, paints, printing inks, cosmetic formulations, paper, ceramic materials, glasses, foils, in security printing, in the agricultural sector, for example in seed coloring, for laser marking of, for example, paper or plastics, in Thermal protection and for the production of pigment preparations such as pearlets, pastes and pastes as well as dry preparations such as pellets, granules, chips etc, which are preferably used in printing inks and varnishes.
- the toxicity of the materials used plays a role, e.g. in cosmetic
- vanadium (IV) compounds for producing the vanadium-containing oxide layers is preferred.
- the pigments according to the invention can be used in a large number of the known binders used in color systems and can be used both in aqueous and in solvent-based systems.
- the pigments can be incorporated into the respective application media by all methods known to the person skilled in the art.
- the effect pigments according to the invention are particularly suitable for products and formulations of decorative cosmetics, such as, for example, nail polishes, coloring powders, lipsticks or eyeshadows, soaps, toothpastes, etc.
- decorative cosmetics such as, for example, nail polishes, coloring powders, lipsticks or eyeshadows, soaps, toothpastes, etc.
- the pigments according to the invention can also be used in the formulations with any type of cosmetic raw and auxiliary materials can be combined. These include oils, fats, waxes, film formers, preservatives and auxiliary substances that determine general application properties, such as thickeners and rheological additives such as bentonites, hectorites, silicon dioxide, calcium silicates, gelatin, high-molecular carbohydrates and / or surface-active additives, etc.
- Formulations containing pigments according to the invention can be of the lipophilic, hydrophilic or hydrophobic type.
- the pigments according to the invention can each contain only one of the two phases or can be distributed over both phases.
- the pH values of the aqueous formulations can be between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8. There are no limits to the concentrations of the pigments according to the invention in the formulation. Depending on the application, they can be between 0.001 (rinse-off products, e.g. shower gels) - 100% (e.g. gloss effect articles for special applications when using effect pigments as a substrate).
- the pigments according to the invention can also be combined with cosmetic active ingredients. Suitable active ingredients are e.g. Insect repellents, UV A / BC protective filters (e.g. OMC, B3, MBC), anti-aging ingredients, vitamins and their derivatives (e.g.
- vitamins A, C, E etc. vitamins A, C, E etc.
- self-tanners e.g. DHA, erytrolosis etc.
- others cosmetic active ingredients such as Bisaboloi, LPO, ectoin, emblica, allantoin, bioflavanoids and their derivatives.
- the effect pigments according to the invention are particularly suitable for use in plastics, for example in agricultural foils, infrared-reflecting foils and disks, gift foils, plastic containers and moldings, for all applications known to the person skilled in the art, since the photostability of the effect pigments according to the invention, in particular in plastics, in order to extend the shelf life of them Leads products.
- All common plastics are suitable as plastics for incorporating the effect pigments according to the invention, for example duromers or thermoplastic plastics.
- the description of the possible uses and the plastics, processing methods and additives that can be used can be found, for example, in RD 472005 or in R. Glausch, M. Kieser, R. Maisch, G. Pfaff, J.
- binders in particular water-soluble types, are suitable for the production of the printing inks, e.g. based on acrylates, methacrylates, polyesters, polyurethanes, nitrocellulose, ethyl cellulose, polyamide, polyvinyl butyrate, phenolic resins, maleic resins, starch or polyvinyl alcohol.
- the lacquers can be water- or solvent-based lacquers, the selection of the lacquer components being subject to the general knowledge of the person skilled in the art.
- the pigments of the invention are preferably used in paints such as in car paints or water-based paints that are suitable for all indoor and outdoor applications due to the special stability of the pigments.
- Powder coating formulations allow the effect pigments according to the invention to be easily incorporated even without further organic coating and, in these applications, have a bright, metallic luster with a pronounced sparkle or glitter effect.
- the so-called superdurable powder coatings When used in outdoor applications, the occurrence of chalking and graying is greatly delayed or largely avoided with highly weather-stable formulations, the so-called superdurable powder coatings.
- silane-based weather stabilizations known from the prior art, there are often incompatibilities with the powder coating matrix, in particular in the area of so-called dry blending, which is often expressed in strong pigment associations in the baked powder coating layer. This disorder is in the invention
- plastics, lacquers, paints, printing inks, cosmetic formulations, paper, ceramic materials, glasses, foils, seeds, pigment preparations and dry preparations containing one or more of the photostabilized effect pigments according to the invention are also an object of the present invention.
- the pigment samples were worked into a plastic matrix and the extent of the reduction from Pb 2+ to Pb was determined visually.
- the gray color is assessed according to ISO 105-Part A 02 (corresponds to DIN 54 001).
- the test scale ranges from 5 (very good) to 1 (very bad).
- the pigment is washed off from the supernatant by filtration. After drying at 120 ° C, the pigment is calcined at 800 ° C for 45 min and the effect pigment obtained is freed from coarse fractions by sieving (mesh size 63 ⁇ m) with blue interference color.
- Example 1 The vanadium-containing pigment is produced as in
- Example 2 The base pigment suspension is prepared as in
- Comparative Example 1 described. The pH is then adjusted to 6.5 with sodium hydroxide solution. A solution of 3.35 g of zinc chloride in 60 ml of water is added within one hour, the pH being kept constant with 5% sodium hydroxide solution in which 53 mg of sodium vanadate has been dissolved. The pigment is worked up as described in Comparative Example 1. The pigment therefore contains 2% zinc oxide and 0.025%
- Vanadium oxide based on the total weight.
- the pigment suspension is generally prepared as described in Comparative Example 1. Following the assignment, the pH of the suspension is adjusted to 5.0 with sodium hydroxide solution. A solution of 9.5 g of aluminum chloride * 6 H 2 O in 100 ml of water is added over the course of an hour, the pH being kept constant with 5% sodium hydroxide solution in which 100 mg of vanadium (V) oxide has been dissolved.
- the pigment is worked up as described in Comparative Example 1. The pigment therefore contains 2% aluminum oxide and 0.1% vanadium oxide, based on the total weight. The body color of the pigment is yellowish. The photoactivity of this pigment is rated 3-4.
- the pigment suspension is generally prepared as described in Comparative Example 1. During the first 75% of the occupancy, the pH is kept constant with 32% sodium hydroxide solution. 64 mg of sodium vanadate are dissolved in the sodium hydroxide solution, which is used for the remaining coating. The pigment is worked up as described in Comparative Example 1.
- the pigment therefore contains a calculated 0.025% vanadium oxide based on the total weight. Due to the manufacturing conditions, the doping takes place in the form of a gradient and primarily in the outer TiO 2 layer.
- the photoactivity of this pigment is rated 3-4.
- Example 6 The vanadium-containing pigment is produced as in
- Vanadyl (IV) sulfate can be dissolved.
- the pigment therefore contains a doping of 0.03% vanadium (calculated as V 2 O 5 ) based on the total weight.
- the photoactivity of this pigment is rated 3.
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Applications Claiming Priority (2)
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US47213803P | 2003-05-21 | 2003-05-21 | |
PCT/EP2004/004418 WO2004104110A1 (de) | 2003-05-21 | 2004-04-27 | Photostabilisierte effektpigmente |
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US (1) | US7455726B2 (ru) |
EP (1) | EP1633819A1 (ru) |
JP (1) | JP2007505987A (ru) |
KR (1) | KR20060028392A (ru) |
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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 (ru) * | 2021-05-17 | 2022-11-24 |
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US3087829A (en) * | 1961-06-28 | 1963-04-30 | Du Pont | Micaceous pigment composition |
US3087828A (en) | 1961-06-28 | 1963-04-30 | Du Pont | Nacreous pigment compositions |
NL135722C (ru) | 1961-06-28 | |||
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JP2565716B2 (ja) * | 1987-09-18 | 1996-12-18 | テイカ株式会社 | 二酸化チタン被覆酸化鉄顔料 |
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JP2585128B2 (ja) * | 1989-06-02 | 1997-02-26 | テイカ株式会社 | 有色微粒子無機顔料 |
JP3044949B2 (ja) * | 1992-09-11 | 2000-05-22 | トピー工業株式会社 | 装飾用顔料 |
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EP0803549B1 (de) * | 1996-04-25 | 2001-09-19 | Ciba Specialty Chemicals Holding Inc. | Farbige Glanzpigmente |
US5958125A (en) * | 1996-07-05 | 1999-09-28 | Schmid; Raimund | Goniochromatic luster pigments based on transparent, nonmetallic, platelet-shaped substrates |
DE59809174D1 (de) * | 1997-04-22 | 2003-09-11 | Ciba Sc Holding Ag | Verfahren zur Herstellung farbiger Effektpigmente |
DE10151844A1 (de) * | 2001-10-24 | 2003-05-08 | Merck Patent Gmbh | Farbige Interferenzpigmente |
-
2004
- 2004-04-27 JP JP2006529713A patent/JP2007505987A/ja active Pending
- 2004-04-27 US US10/557,476 patent/US7455726B2/en not_active Expired - Fee Related
- 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
- 2004-04-27 WO PCT/EP2004/004418 patent/WO2004104110A1/de active Application Filing
Non-Patent Citations (1)
Title |
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See references of WO2004104110A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2007505987A (ja) | 2007-03-15 |
WO2004104110A1 (de) | 2004-12-02 |
US20070060668A1 (en) | 2007-03-15 |
CN100384946C (zh) | 2008-04-30 |
KR20060028392A (ko) | 2006-03-29 |
US7455726B2 (en) | 2008-11-25 |
CN1791645A (zh) | 2006-06-21 |
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