CN112538281A - 颜料 - Google Patents
颜料 Download PDFInfo
- Publication number
- CN112538281A CN112538281A CN202010989000.4A CN202010989000A CN112538281A CN 112538281 A CN112538281 A CN 112538281A CN 202010989000 A CN202010989000 A CN 202010989000A CN 112538281 A CN112538281 A CN 112538281A
- Authority
- CN
- China
- Prior art keywords
- tio
- graphite layer
- sio
- graphite
- layer substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000049 pigment Substances 0.000 title claims abstract description 170
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 228
- 239000010439 graphite Substances 0.000 claims abstract description 228
- 239000002245 particle Substances 0.000 claims abstract description 74
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002537 cosmetic Substances 0.000 claims abstract description 23
- 238000009472 formulation Methods 0.000 claims abstract description 18
- 239000000976 ink Substances 0.000 claims abstract description 13
- 239000003973 paint Substances 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 8
- 239000006115 industrial coating Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 324
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 224
- 239000000377 silicon dioxide Substances 0.000 claims description 125
- 229910052681 coesite Inorganic materials 0.000 claims description 124
- 229910052906 cristobalite Inorganic materials 0.000 claims description 124
- 229910052682 stishovite Inorganic materials 0.000 claims description 124
- 229910052905 tridymite Inorganic materials 0.000 claims description 124
- 239000000758 substrate Substances 0.000 claims description 120
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 80
- 239000000463 material Substances 0.000 claims description 48
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 38
- 229910052593 corundum Inorganic materials 0.000 claims description 38
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 27
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 26
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004615 ingredient Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910011255 B2O3 Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 235000019198 oils Nutrition 0.000 claims description 9
- 235000000346 sugar Nutrition 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- -1 bleaches Substances 0.000 claims description 6
- 239000007833 carbon precursor Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004904 UV filter Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 4
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000123 paper Substances 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000011782 vitamin Substances 0.000 claims description 4
- 229940088594 vitamin Drugs 0.000 claims description 4
- 229930003231 vitamin Natural products 0.000 claims description 4
- 235000013343 vitamin Nutrition 0.000 claims description 4
- 244000144927 Aloe barbadensis Species 0.000 claims description 3
- 235000002961 Aloe barbadensis Nutrition 0.000 claims description 3
- ACTIUHUUMQJHFO-UHFFFAOYSA-N Coenzym Q10 Natural products COC1=C(OC)C(=O)C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 235000011399 aloe vera Nutrition 0.000 claims description 3
- 235000021302 avocado oil Nutrition 0.000 claims description 3
- 239000008163 avocado oil Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 235000017471 coenzyme Q10 Nutrition 0.000 claims description 3
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 claims description 3
- 229940110767 coenzyme Q10 Drugs 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 235000020688 green tea extract Nutrition 0.000 claims description 3
- 229940094952 green tea extract Drugs 0.000 claims description 3
- 239000000077 insect repellent Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 150000008163 sugars Chemical group 0.000 claims description 3
- 208000001840 Dandruff Diseases 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims description 2
- 230000001166 anti-perspirative effect Effects 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims description 2
- 239000003213 antiperspirant Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 239000003212 astringent agent Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000003398 denaturant Substances 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 239000003974 emollient agent Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000000796 flavoring agent Substances 0.000 claims description 2
- 235000013355 food flavoring agent Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000003906 humectant Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000010330 laser marking Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000004023 plastic welding Methods 0.000 claims description 2
- 239000003380 propellant Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 230000000475 sunscreen effect Effects 0.000 claims description 2
- 239000000516 sunscreening agent Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 1
- 238000005234 chemical deposition Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000011856 silicon-based particle Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 187
- 239000010445 mica Substances 0.000 description 31
- 229910052618 mica group Inorganic materials 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 239000002966 varnish Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005243 fluidization Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
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- 238000001354 calcination Methods 0.000 description 3
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- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 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 3
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 3
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- WTVHAMTYZJGJLJ-UHFFFAOYSA-N (+)-(4S,8R)-8-epi-beta-bisabolol Natural products CC(C)=CCCC(C)C1(O)CCC(C)=CC1 WTVHAMTYZJGJLJ-UHFFFAOYSA-N 0.000 description 2
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- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
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- 239000004677 Nylon Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PNFQFZXRHXDPDK-UHFFFAOYSA-N [O-2].[Fe+2].[Cu+2].[Mn+2].[O-2].[O-2] Chemical compound [O-2].[Fe+2].[Cu+2].[Mn+2].[O-2].[O-2] PNFQFZXRHXDPDK-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229940093797 bioflavonoids Drugs 0.000 description 1
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Classifications
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Abstract
本发明涉及基于颗粒的颜料，所述颗粒涂覆有至少一层由无定形碳(a‑C)和纳米晶石墨(nc‑石墨)的混合物组成的层，并且涉及这些颜料在油漆，塑料，工业涂料，汽车涂料，印刷油墨和化妆品制剂中的用途。
Description
技术领域
本发明涉及颜料，所述颜料基于由至少一层涂覆的颗粒，所述层由无定形碳和纳米晶石墨的混合物组成，并且涉及这些颜料在油漆、塑料、工业涂料、汽车涂料、印刷油墨和化妆品制剂中的用途。
背景技术
目前，深蓝色/深绿色/深灰色至黑色的色调是通过使用无机吸收性颜料实现的，例如：普鲁士蓝(如果是深蓝色色调)，氧化铬(如果是深绿色色调)，尖晶石或赤铁矿型黑色氧化铁或氧化钴，铜锰铁氧化物，铜铬氧化物和锰铁氧化物。此外，石墨或类石墨颜料和炭黑颜料是可商购的，并且也可以以物理共混物/混合物的形式应用以帮助形成深色色调。
深蓝色/深绿色/深灰色至黑色效果的颜料是可商购的，并且通常是通过在片状基材，例如天然或合成云母、玻璃薄片或Al2O3薄片上沉淀深色的铜氧化物或铁氧化物，例如Fe3O4，Co3O4或FeTiO3制备的。可商购的黑色或深灰色颜料是通过沉淀法生产的。
但是，深灰色/深蓝色/深绿色至黑色效果/珠光颜料显示出明显的缺点，这限制了它们在某些应用中的使用：
·由于已知的重金属和钴离子的致敏特性，普鲁士蓝和氧化铬以及含钴的珠光颜料不允许用于化妆品应用；
·黑色氧化铁涂覆的珠光颜料可能会显示出磁效应，这在某些涂料应用中是不利的；
·含钛铁矿的珠光颜料通常会显示出固有的褐色吸收色，因此在以中性灰色调为目标的应用中，需要进行进一步的颜色调整。此外，化妆品制剂中不允许含有钛铁矿的珠光颜料。
当涉及产生黑色珠光效果时，可以使用炭黑或含graphitan的颜料代替重金属氧化物颜料。
含炭黑的颜料是现有技术中，例如DE-AS 11 65 182，DE 25 577 96 A1，DE 41 25134 A1中已知，并且其通过使用表面活性助剂从水溶液施加碳或通过有机化合物的热解来制备。
然而，与纯炭黑或graphitan混合的颗粒或效果颜料显示出不吸引人的光泽。如果要通过炭黑或graphitan来模仿深色珠光效果，则必须将干涉颜料与炭黑颗粒或graphitan颗粒物理共混。但是，这些物理共混物在某些(例如化妆品)应用中可能分离，这可通过添加分散剂和流变添加剂来防止。
基于涂覆有包含类石墨和/或石墨烯形式的结晶碳层的层的片状形式的非金属载体的非金属干涉颜料从US 2017/0321057 A1中已知。这些干涉颜料的缺点是它们是导电颜料，并且它们没有非常足够的高化学稳定性和耐候性。另外，现有技术的颜料显示出差的遮盖力并且没有或较少的金属色效应和/或低色的金属闪耀或光泽。
干涉颜料本身显示出较差的遮盖力。为了提高遮盖力，加入吸收颜料例如炭黑以补偿遮盖力。在某些应用，尤其是化妆品制剂(粉饼，口红等)中，颜料和炭黑的共混物可能在压力/剪切应力下分离。结果，光学/化妆品颜色应用可能看起来暗淡无光，甚至黑/脏。
发明内容
本发明的目的是提供颜料，其不显示现有技术颜料的缺点，而是显示具有高光泽度和增加的遮盖力的深灰色至黑色的珠光效果或金属深蓝色/深绿色珠光效果。同时，颜料应至少满足以下要求之一：
·纯中性的深灰色/深蓝色/深绿色/深色金属色调至黑色吸收性色调
·无磁性(由碳层添加)
·无分离/无需添加剂即可防止分离
·颜料的暗度或遮盖力可调
·导电率较低
·没有被认为对化妆品制剂至关重要的成分，例如普鲁士蓝、氧化铬、铝
·流动性提高。
令人惊讶地，现已发现，涂覆有至少一层无定形碳(a-C)和纳米晶石墨(nc-石墨)混合物的颗粒表现出深色金属外观，更好的流动性以及同时的提高的遮盖力和提高的紫外线稳定性。通过改变a-C/nc-石墨层的厚度可以影响涂覆颗粒的光学性能。
本发明涉及基于颗粒的颜料，其包含至少一层，该层由无定形碳(a-C)和纳米晶体石墨(nc-石墨)的混合物组成。
根据本发明的涂覆的颗粒显示出改进的取向，这导致了金属外观、(液态)金属效果和增加的遮盖力。
本发明还涉及本发明的颜料在油漆，涂料，优选在工业涂料和汽车涂料，印刷油墨，安全印刷油墨，塑料，陶瓷材料，玻璃，作为示踪剂，作为填充剂，并且尤其是在化妆品制剂和应用以及汽车涂料中的用途。此外，根据本发明的颜料也适用于颜料制剂的制备和干制剂的制备，例如颗粒，小珠，薄片，小丸，香肠，团块等。干制剂特别是用于印刷油墨和化妆品制剂中。
根据本发明的深色颜料显示深色金属或(液态)金属或有色金属外观，这在最终应用中例如在汽车涂料和化妆品制剂中非常有吸引力。由于通常通过使用黑色氧化铁颜料产生具有足够遮盖力的涂层，因此根据本发明的颜料可以用作有吸引力的替代品，因为这些颜料颗粒固有地具有非磁性并且具有较少的(重)金属特性。
另外，根据本发明的颜料显示出改进的流动性，这对于加工和计量非常有益。此外，颜料显示出优异的分散性并且没有聚集。
优选在颜料表面顶部的共形且均质的a-C和nc-石墨层由无定形碳(a-C)和纳米晶石墨(nc-石墨)的混合物组成，其中a-C：nc-石墨的重量比优选在60:40至80:20的范围内，特别是50:50至95：5，并且最特别是80:20至90:10。在一个优选的实施方案中，相比于在a-C/nc-石墨层中的纳米晶石墨，a-C/nc-石墨层包含更高比例的无定形碳。在另一个优选的实施方案中，a-C/nc-石墨层作为最终层沉淀在颜料上。但是，a-C/nc-石墨层也可以是中间层，即沉积在两层之间，优选沉积在两个金属氧化物层之间。a-C/nc-石墨层的数量没有限制。基材表面上的层排列可包含多于一个的a-C/nc-石墨层，即1、2、3、4、5或甚至更多，但优选仅1或2层。
a-C/nc-石墨层优选通过化学气相沉积(CVD)制备。a-C/nc-石墨层必须光滑，并用均匀和共形的层完全覆盖颗粒。与现有技术相比，a-C/nc-石墨层不由沉积在颗粒表面的单晶碳畴组成，而是由无定形碳和纳米晶石墨的混合物的层组成并且已经以获得无孔且共形和均质的层的方式直接在颗粒上生长。a-C/nc-石墨层是由颗粒表面上的异质生长引起的。
由于在所述相界处的跃迁电阻率增加，因此，a-C和nc-石墨之间的相界导致电导率降低。较高的无定形相导致大量的边界，这降低了电导率。另外，a-C本质上具有较低的电导率。因此，本发明的a-C/nc-石墨层显示出低的导电性能。
在一个优选的实施方案中，各a-C/nc-石墨层的厚度为0.5-10nm，特别是1-5nm，并且特别优选为0.5-3nm。
基于颗粒的纳米晶石墨的含量非常低，这意味着根据本发明的颜料显示出没有或较小的导电性。
所有已知优选具有0.5-500μm的粒度(particle size)或1-150μm的粒径(particle diameter)的颗粒都适合作为本发明颜料的基材。颗粒的形状不是至关重要的。颗粒可以是小板状，针状，球形，不规则形状。在一个优选的实施方案中，颗粒是小板状或球形的。
小板状或薄片状颗粒的大小本身并不重要，可以与各自的应用相匹配。薄片状颗粒的厚度优选为0.05至1μm，特别是0.1至1μm，并且非常特别优选为200至500nm。其他两个(横向)方向的尺寸通常在1至250μm之间，优选在2至200μm之间，并且特别是在5至60μm之间。也可以采用不同粒度的小板状颗粒。特别优选N云母(10-60μm)，F云母(5-20μm)和M云母(<15μm)的云母级分的混合物。此外，优选N和S级分(10-130μm)和F和S级分(5-130μm)。
合适的颗粒优选选自以下基材的组：天然或合成云母，滑石，高岭土，Fe2O3薄片，Fe3O4薄片，Al2O3薄片，BiOCl薄片，玻璃薄片，SiO2薄片，TiO2薄片，BN薄片，Si-/Al-氧氮化物薄片，铝薄片，Si-/Ti-氮化物薄片和石墨薄片，珍珠精华，合成的无载体薄片，玻璃珠，空心玻璃珠，硅颜料，基于基材的颜料，例如填料颜料和效果颜料。合适的填料颜料和效果颜料是例如干涉颜料，多层颜料，随角异色颜料，视角闪色颜料，金属效果颜料，涂覆有一种或多种金属氧化物优选TiO2和/或Fe2O3的SiO2球。
颗粒可以涂覆一层或多层，优选一层，两层或三层，特别是无机层。无机层优选包含吸收性和非吸收性氧化物或氢氧化物或金属。
如果基材涂覆有一层或多层金属氧化物层和/或金属层，则基材表面上所有层的总层厚为50-1000nm，优选100-800nm，并且最优选为100-500nm，包括一个或多个a-C/nc-石墨层。每个a-C/nc-石墨层的层厚优选为0.5-10nm。
合适的颗粒优选选自以下组中的基材：天然或合成云母，滑石，高岭土，Fe2O3薄片，Fe3O4薄片，Al2O3薄片，BiOCl薄片，玻璃薄片，SiO2薄片，TiO2薄片，涂覆或未涂覆的SiO2球，基于小板状基材的干涉颜料和基于小板状基材的多层颜料。
也可以采用不同颗粒的混合物。特别优选的颗粒混合物由以下列举的组组成：
天然云母薄片+SiO2薄片
天然云母薄片+Al2O3薄片
天然云母薄片+玻璃薄片
天然云母薄片+TiO2薄片
天然云母薄片+氮氧化物薄片
天然云母薄片+氮化物薄片
天然云母薄片+珍珠精华
天然云母薄片+石墨薄片
SiO2薄片+Al2O3薄片
玻璃薄片+SiO2薄片
天然云母薄片+SiO2球
合成云母薄片+SiO2球
Al2O3薄片+SiO2球
SiO2薄片+SiO2球
玻璃薄片+SiO2球
天然云母薄片+玻璃球
合成云母薄片+玻璃球
Al2O3薄片+玻璃球
SiO2薄片+玻璃球
玻璃薄片+玻璃球
合成云母薄片+SiO2薄片
合成云母薄片+Al2O3薄片
合成云母薄片+玻璃薄片
合成云母薄片+TiO2薄片
合成云母薄片+Si-氮氧化物薄片
合成云母薄片+Si-/Ti氮化物薄片
合成云母薄片+珍珠精华
合成云母薄片+石墨薄片
合成云母薄片+天然云母薄片
颗粒或颗粒混合物涂覆有一层或多层a-C/nc-石墨层。a-C/nc-石墨层可以在表面上和/或可以是层布置中的中间层。颗粒优选在表面上涂覆有一层a-C/nc-石墨层。
在一个优选的实施方案中，颗粒是基于小板状基材的干涉颜料或单层或多层颜料。优选的干涉颜料是小板状的基材，其涂覆有一层、两层、三层或更多的金属氧化物层。a-C/nc-石墨层沉积在干涉颜料的表面上。
颗粒(＝干涉颜料)优选涂覆有至少一层高折射率层，如金属氧化物层，例如TiO2,ZrO2,SnO2,ZnO,Ce2O3,Fe2O3,Fe3O4,FeTiO5,Cr2O3,CoO,Co3O4,VO2,V2O3,NiO，还有低价钛氧化物(TiO2，部分还原，伴随着氧化态从<4至2，例如低价氧化物Ti3O5,Ti2O3,TiO)，氮氧化钛，FeO(OH)，薄的半透明金属层，例如包含Al，Fe，Cr，Ag，Au，Pt或Pd或其组合。
TiO2层可以是金红石型或锐钛矿型变体。通常，当TiO2为金红石型变体时，可获得最高的质量和光泽度并且同时最稳定的颜料。为了获得金红石型变体，可以使用能够将TiO2引导至金红石型变体的添加剂。可用的金红石型定向剂公开于美国专利4,038,099和5,433,779以及EP 0 271 767中。优选的金红石型定向剂是SnO2。
优选的颗粒是涂覆的小板状基材，其包含一层或多层金属氧化物，优选仅一层金属氧化物，特别是选自TiO2,Fe2O3,Fe3O4,SnO2,ZrO2或Cr2O3。尤其优选的是被TiO2或Fe2O3及其混合物涂覆的天然云母，合成云母，玻璃薄片，SiO2薄片和Al2O3薄片。
在本专利申请中，术语“高折射率”是指折射率n≥1.8。在本专利申请中，术语“低折射率”是指折射率n＜1.8。
每个高折射率层的厚度取决于所需的干涉色。小板状颗粒的表面上的每一层的厚度优选为20-400nm，优选为30-300nm，特别是30-200nm。
基材表面上的层数优选为一层或两层，还有为三层，四层，五层，六层或七层。
特别地，由小板状基材的表面上的高和低折射率层组成的干涉层叠导致颜料具有增加的光泽度和进一步增加的干涉色或随角异色。
用于涂层的合适的无色低折射率材料优选金属氧化物或相应的氧化物水合物，例如SiO2,Al2O3,AlO(OH),B2O3,MgO*SiO2,CaO*SiO2,Al2O3*SiO2,B2O3*SiO2化合物，例如MgF2或所述金属氧化物的混合物。
优选的施加在小板状基材表面上的多层体系是TiO2-SiO2-TiO2序列或TiO2-MgO*SiO2-TiO2序列。
小板状颗粒也可以涂覆有一层或多层选自例如铬、镍、银、铋、铜、锡、哈氏合金的金属或金属合金，或涂覆有一层或多层选自例如钨、钼、铈、镧或稀土元素的金属硫化物或硫化物：。
一个或多个a-C/nc-石墨层可以直接沉积在基材表面上，在一个或多个金属或金属氧化物层之间，或沉积在每个金属或金属氧化物层的表面上或颗粒的表面上。在一个优选的实施方案中，至少一个a-C/nc-石墨层被施加在颗粒的表面上，特别是干涉颜料和多层颜料的表面上。
优选的根据本发明的颜料是以下提及的：
基材+a-C/nc-石墨层
基材+a-C/nc-石墨层+TiO2
基材+a-C/nc-石墨层+Fe2O3
基材+a-C/nc-石墨层+Fe3O4
基材+a-C/nc-石墨层+Cr2O3
基材+a-C/nc石墨层+SnO2
基材+a-C/nc-石墨层+SiO2
基材+a-C/nc-石墨层+ZrO2
基材+a-C/nc-石墨层+ZnO
基材+a-C/nc-石墨层+Al
基材+a-C/nc-石墨层+Fe
基材+a-C/nc-石墨层+Cr
基材+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+a-C/nc-石墨层
基材+Fe2O3+a-C/nc-石墨层
基材+Fe3O4+a-C/nc-石墨层
基材+TiO2+Fe2O3+a-C/nc-石墨层
基材+TiO2+Fe3O4+a-C/nc-石墨层
基材+TiO2+SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+Al2O3+TiO2+a-C/nc-石墨层
基材+TiO2+MgO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+Al2O3+TiO2+a-C/nc-石墨层
基材+Fe2O3+MgO*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+Al2O3+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+MgO*SiO2+TiO2+a-C/nc石墨层
基材+TiO2/Fe2O3+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2/Fe2O3+SiO2+TiO2/Fe2O3+a-C/nc石墨层
基材+TiO2/Fe2O3+MgO*SiO2+TiO2/Fe2O3+a-C/nc石墨层
基材+TiO2+Al2O3+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+MgO*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+CaO*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+Al2O3*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+B2O3*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+SiO2+a-C/nc-石墨层
基材+TiO2+SiO2/Al2O3+a-C/nc-石墨层
基材+TiO2+Al2O3+a-C/nc-石墨层
基材+SnO2+a-C/nc-石墨层
基材+SnO2+TiO2+a-C/nc-石墨层
基材+SnO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+a-C/nc-石墨层
基材+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+SiO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Fe3O4+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2/Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2/Al2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Al2O3+a-C/nc-石墨层
基材+a-C/nc-石墨层+TiO2+a-C/nc-石墨层
基材+a-C/nc-石墨层+Fe2O3+a-C/nc-石墨层
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层+TiO2
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层+Fe2O3
在一个特别优选的实施方案中，上述优选的颜料基于小板状的基材，特别是选自天然云母和合成云母。
上述优选实施方案中的一个或多个TiO2层可以是金红石型或锐钛矿型变体。
在上述优选实施方案中的合成基材，例如合成云母，玻璃薄片，SiO2薄片或Al2O3薄片可以掺杂或未掺杂的。基于基材，掺杂剂的量优选在0.005-5wt％的范围内。
通过使用一层或多层a-C/nc石墨层，可以在宽范围内改变或调整颜料的颜色、光泽和遮盖力。
在一个优选的实施方案中，根据本发明的颜料仅包含一个a-C/nc石墨层，其是施加在颗粒表面上的外层。该颗粒也可以是在表面上涂覆有a-C/nc-石墨层的例如云母，钝化的铝薄片，玻璃薄片等的基材。
包含至少一层碳/石墨层的颜料具有出色的遮盖力和深色金属外观。
基于总颜料，根据本发明的颜料优选由90-99wt％的颗粒和10-1wt％的a-C/nc-石墨层组成。
具有至少一层金属氧化物层的基材的涂覆优选通过湿化学涂覆法、通过CVD或PVD法进行。
基材表面上的金属氧化物层优选通过为制备珠光颜料开发的湿化学涂覆法施加。这种类型的方法描述于例如在US 3087828，US 3087829，US 3553001，DE 14 67 468，DE 1959 988，DE 20 09566，DE 2214545，DE 22 15 191，DE 22 44 298，DE 23 13331，DE 25 22572，DE 31 37 808，DE 31 37 809，DE 31 51343，DE 31 51 354，DE 31 51 355，DE 32 11602，DE 32 35 017，DE 196 18 568，EP 0 659 843中，或者也在其他专利文件和本领域技术人员已知的其他出版物中。
在一个优选的实施方案中，共形和均质的a-C/nc-石墨层通过流化床辅助CVD(FBCVD)工艺获得，该工艺在200至＜500℃的温度下操作。碳源选自含碳的有机溶剂，特别是在低于500℃的温度下会分解的溶剂，例如乙醇，异丙醇，2-甲基-3-丁-2-醇或糖化合物，例如糖粉，葡萄糖，果糖，右旋葡萄糖或本领域技术人员已知的任何其他糖。碳前体可以是液态或固态形式。液态碳和固态碳前体的混合物也是可以的。也可以使用不同有机溶剂的混合物或不同糖的混合物或糖和溶剂的混合物作为碳前体。在一个优选的实施方案中，仅使用一种碳源，即溶剂或固态糖。
将颗粒在流化床反应器中加热至所需的200至＜500℃，优选200至480℃，并且特别是250至450℃的温度范围。加热和碳分解反应在惰性气体气氛，例如在N2，氩气，氦气下进行。惰性流化气体优选地以使在整个过程中保持2至6mm/s，优选2至4mm/s的最小流化速度的方式调节。如果达到所需的反应温度，则将碳前体，例如有机溶剂或糖化合物，添加到流化气体中。在化学气相沉积之后，将反应器在惰性气体气氛下冷却直到达到室温。取决于颜料的期望应用，对所得颜料的进一步后处理可能包含筛分。
特别地，与不含a-C/nc-石墨层的颗粒相比，在涂覆或未涂覆的颗粒上沉积至少4nm的薄a-C/nc-石墨层可将遮盖力提高3.5至4.4倍。此外，a-C/nc-石墨层增加了颜料的UV稳定性。
本发明还涉及根据本发明的颜料的制备方法。
在本专利申请中，术语“一个或多个涂层”或“一个或多个层”是指涂覆或未涂覆的基材或颗粒的相应表面的完全覆盖/包封。
为了进一步提高对光，水和气候的稳定性，根据应用领域，经常建议对本发明的颜料进行后涂布或后处理。合适的后涂覆或后处理方法是例如德国专利22 15 191，DE A 3151 354，DE A 32 35 017或DE A 33 34 598中所述的那些方法。这种后涂覆进一步增加了化学和光化学稳定性或特别是掺入各种介质中时，使得颜料混合物的处理变得更容易。为了改进润湿性、分散性和/或与应用介质的相容性，可以将包含Al2O3或ZrO2或其混合物的功能涂层施加到颜料表面上。此外，可以例如用硅烷进行有机后涂覆，例如在EP 0090259，EP0 634 459，WO 99/57204，WO 96/32446，WO 99/57204，US 5,759,255，US 5,571,851，WO01/92425或J.J.Ponjeé,Philips Technical Review,Vol.44,No.3,81ff.和P.H.Harding,J.C.Berg,J.Adhesion Sci.Technol.Vol.11No.4,pp.471-493中所述。
根据本发明的颜料与优选来自油漆、涂料和印刷油墨的多种颜色体系相容。多种粘合剂，特别是水溶性产品，例如由BASF,Marabu,
Sericol,Hartmann,Gebr.Schmidt,Sicpa,Aarberg,Siegwerk,GSB-Wahl,Follmann,Ruco或Coates ScreenGmbH销售的，适用于制备例如用于凹版印刷、柔版印刷、胶版印刷或胶印套印清漆的印刷油墨。印刷油墨可以是水基或溶剂基的。
不言而喻，根据本发明的颜料也可以作为与下列的共混物有利地用于各种应用中：例如与
-金属效果颜料，例如基于铁薄片或铝薄片的；
-基于金属氧化物涂覆的合成云母薄片，天然云母薄片，玻璃薄片，Al2O3薄片，Fe2O3薄片或SiO2薄片的珠光颜料；
-基于金属氧化物涂覆的合成云母薄片，天然云母薄片，玻璃薄片，Al2O3薄片，Fe2O3薄片或SiO2薄片的干涉颜料；
-视角闪色颜料；
-基于金属氧化物涂覆的合成云母薄片，天然云母薄片，玻璃薄片，Al2O3薄片，Fe2O3薄片或SiO2薄片的多层颜料(优选包含2、3、4、5或7层)；
-有机染料；
-有机颜料；
-无机颜料，例如透明和不透明的白色，彩色和黑色颜料；
-薄片状铁氧化物；
-碳黑。
根据本发明的颜料可以以任何比例与可商购获得的颜料和/或其他可商购获得的填充剂混合。
可以提及的可商购获得的填料例如是天然和合成云母，尼龙粉末，纯或填充的三聚氰胺树脂，滑石，玻璃，高岭土，铝、镁、钙、锌的氧化物或氢氧化物，BiOCl，硫酸钡，硫酸钙，碳酸钙，碳酸镁，碳，氮化硼以及这些物质的物理或化学组合。对于填料的颗粒形状没有限制。根据需要，它可以是例如薄片状、球形或针状。
当然，根据本发明的颜料也可以在制剂中与任何类型的化妆品原料和助剂结合。这些尤其包括油，脂肪，蜡，成膜剂，防腐剂和通常确定应用性能的助剂，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。
根据本发明的颜料是简单且易于处理的。可以通过简单搅拌将颜料掺入使用其的体系中。根据本发明的颜料显示出增加的粉末流动性，这对加工非常有利。
根据本发明的颜料可用于涂料，印刷油墨，塑料，农用薄膜，纽扣糊料的着色，用于种子的涂层，用于食品的着色，药物的涂层或化妆品制剂。基于体系的总固体含量，颜料在用其着色的体系中的浓度通常为0.01至50重量％，优选为0.1至5重量％。该浓度通常取决于具体的应用。
含有0.1至50重量％，特别是0.5至7重量％的根据本发明的颜料的塑料经常由于特殊的深色金属和光泽效果而引人注目。
在涂料领域中，特别是在汽车涂料和汽车修补漆中，根据本发明的颜料的用量为0.5至10重量％。用于例如在汽车涂料中，将根据本发明的颜料掺入由树脂(例如聚酯，三聚氰胺和聚氨酯)与用于调节pH值的胺、改进成膜性的共溶剂、至少一种调节流变性能的增稠剂的混合物组成的底涂层制剂中。为了获得可喷涂的粘度，可加入消泡剂，湿润剂，如有必要，还可添加其他添加剂，填料，颜料和/或消光剂以及水。将该底涂层通过喷涂涂覆在所需的基材上。所得的干膜厚度应为10-20μm，最好为12-18μm。预干燥后，在该底涂层上施加清漆，然后烘烤整个涂层。
在涂料中，根据本发明的颜料具有的优点在于，期望的金属(液态)颜色和光泽度通过单层涂布(单涂层体系或在两涂层体系中作为底涂层)获得。在一个优选的实施方案中，根据本发明的颜料用于底涂层中。
在化妆品制剂中，根据本发明的颜料的浓度没有限制。根据应用，它们可以介于0.001(漂洗产品，例如沐浴露)和60％之间。此外，根据本发明的颜料也可以与化妆品活性化合物结合。合适的活性化合物是例如驱虫剂，无机UV过滤剂，例如TiO2，UV A/BC防护过滤剂(例如OMC，B3，MBC)，抗衰老活性化合物，维生素及其衍生物(例如维生素A，C，E等)，自晒黑剂(例如DHA，赤藓酮糖等)和其他化妆品活性化合物，例如红没药醇(bisabolol)，LPO，依克多因(ectoin)，余甘子，尿囊素，生物类黄酮及其衍生物。
基于制剂，有机UV过滤剂的用量通常为0.5-10重量％，优选为1-8重量％；无机UV过滤剂的用量为0.1-30重量％。
另外，所述制剂可以包含其他常规的皮肤保护或护肤活性成分，例如芦荟、鳄梨油、辅酶Q10、绿茶提取物以及活性化合物复合物。
本发明同样涉及制剂，特别是化妆品制剂，其除了根据本发明的颜料外，还包含至少一种选自以下的成分：吸收剂，收敛剂，抗微生物物质，抗氧化剂，止汗剂，消泡剂，去头皮屑活性化合物，抗静电剂，粘合剂，生物添加剂，漂白剂，螯合剂，除臭剂，润肤剂，乳化剂，乳液稳定剂，染料，保湿剂，成膜剂，填充剂，香剂，调味剂，驱虫剂，防腐剂，抗蚀剂，化妆品油，溶剂，水，氧化剂，植物成分，缓冲物质，还原剂，表面活性剂，推进剂气体，遮光剂，UV过滤剂和UV吸收剂，变性剂，芦荟，鳄梨油，辅酶Q10，绿茶提取物，粘度调节剂，香料和维生素。
因此，本发明还涉及根据本发明的颜料在油漆，涂料，汽车涂料，汽车修补漆，工业涂料，油漆，粉末涂料，印刷油墨，安全印刷油墨，塑料，陶瓷材料，化妆品中的用途。根据本发明的颜料还可以用于玻璃，纸张，纸张涂料，电子照相印刷工艺用的调色剂，种子、温室片材和防水油布，用于机器或设备的绝缘的导热、自支撑、电绝缘、柔性片材中，在纸张和塑料的激光打标中用作吸收剂，在塑料的激光焊接中作为吸收剂，在具有水、有机和/或水性溶剂的颜料糊中，在颜料的制剂和干制剂中，例如，工业和汽车领域的清漆中的颗粒，在防晒剂中，作为填料，特别是在汽车涂料和汽车修补漆中以及在化妆品制剂中。
除非另有说明，否则本申请中的所有百分比数据均为重量百分比。
下列实施例旨在更详细地解释本发明，但不限制本发明。
具体实施方式
实施例
实施例1
在搅拌下，将150g粒度为5至15μm的天然云母薄片分散在2000ml去离子水中。然后在持续搅拌下将悬浮液加热至75℃。通过逐滴添加SnCl4溶液(50％)将悬浮液的沉淀pH值设置为1.8。将剩余的SnCl4溶液稳定计量加入到悬浮液中。在该过程中，通过添加氢氧化钠(32％)将pH值保持恒定在1.8。加入溶液完成后，将悬浮液再搅拌10分钟。
在1.4的恒定pH值下，计量加入135g TiCl4溶液(25％)，直到达到色彩终点(蓝银色)，即TiO2为12wt％为止。因此，实现了12nm的TiO2层厚度。在沉淀过程中，通过连续添加32％的氢氧化钠溶液使pH值保持恒定。完成后，将悬浮液再搅拌10分钟，吸滤并用去离子水洗涤直至无盐。颗粒物在120℃下干燥24小时。干燥过程后，接着在800℃下煅烧45分钟。
所获得的颜料具有深蓝色至浅银色的色调。
实施例2
在搅拌下，将150g粒度为5至15μm的天然云母薄片分散在2000ml去离子水中。然后，在持续搅拌下将悬浮液加热至75℃。通过逐滴添加SnCl4溶液(50％)将悬浮液的沉淀pH值设置为1.8。将剩余的SnCl4溶液稳定计量加入到悬浮液中。在该过程中，通过添加氢氧化钠(32％)将pH值保持恒定在1.8。加入溶液完成后，将悬浮液再搅拌10分钟。
在1.4的恒定pH值下，计量加入201g TiCl4溶液(25％)，直到达到色彩终点(蓝银色)，即TiO2为18wt％为止。因此，实现了18nm的TiO2层厚度。在沉淀过程中，通过连续添加32％的氢氧化钠溶液使pH值保持恒定。完成后，将悬浮液再搅拌10分钟，吸滤并用去离子水洗涤直至无盐。颗粒物在120℃下干燥24小时。干燥过程后，接着在800℃下煅烧45分钟。
所获得的颜料具有浅蓝色至深银色的色调。
实施例3
在搅拌下，将150g粒度为5至15μm的天然云母薄片分散在2000ml去离子水中。然后在持续搅拌下将悬浮液加热至75℃。通过逐滴添加SnCl4溶液(50％)将悬浮液的沉淀pH值设置为1.8。将剩余的SnCl4溶液稳定计量加入到悬浮液中。在该过程中，通过添加氢氧化钠(32％)将pH值保持恒定在1.8。加入溶液完成后，将悬浮液再搅拌10分钟。
在1.4的恒定pH值下，计量加入390g TiCl4溶液(25％)，直到达到色彩终点(蓝银色)，即TiO2为35wt％为止。因此，实现了35nm的TiO2层厚度。在沉淀过程中，通过连续添加32％的氢氧化钠溶液使pH值保持恒定。完成后，将悬浮液再搅拌10分钟，吸滤并用去离子水洗涤直至无盐。颗粒物在120℃下干燥24小时。干燥过程后，接着在800℃下煅烧45分钟。
所获得的颜料具有带浅蓝色高光的强银色的色调。
实施例4–化学气相沉积
在恒定的惰性气体气氛(N2)下，在流化床反应器(DI：63mm)中将150g根据实施例1的蓝-银色颗粒加热至490℃。调整体积流量以达到2mm/s的最小流化速度，因此可确保出色的混合以及传热和传质性能。一旦达到反应温度，就向流化体积流中计量入C前体丙酮。由于升高的反应温度，C前体将以引发蓝-银色颜料表面上的C层生长的方式分解。CVD法运行60分钟，以使C层厚度达到4nm。在惰性气体气氛下的冷却阶段后，将最终颜料从反应器中除去并过筛。
深色颜料显示出具有高光泽和高遮盖力的金属效果。
沉积的C层由重量比为90:10的a-C和nc-石墨的混合物组成。该比率是结合了根据Ferrari等人的拉曼光谱研究和根据Müller[Müller,J-O；Su,Dang Sheng；Jentoft,RolfE.；
Jutta；Jentoft,Friederike C.；
Robert；Morphology-controlled reactivity of carbonaceous materials towards oxidation,in:Catalysis Today,102,2005,S.259–265.]等人和Trigueiro等人[Trigueiro,
PauloC.；Silva,Glaura G.；Lavall,Rodrigo L.；Furtado,Clascídia A.；Oliveira,Sérgio；Ferlauto,Andre S.；Lacerda,Rodrigo G.；Ladeira,Luiz O.；Liu,Jiang-Wen；Frost,RayL.；Purity evaluation of carbon nanotube materials by thermogravimetric,TEM,and SEM methods,in:Journal of nanoscience and nanotechnology,7,2007,S.3477–3486.]的热重分析确定的。
实施例5–化学气相沉积
在恒定的惰性气体气氛(N2)下，在流化床反应器(DI：63mm)中将150g根据实施例2的蓝-银色颗粒加热至490℃。调整体积流量以达到2mm/s的最小流化速度，因此可确保出色的混合以及传热和传质性能。一旦达到反应温度，就向流化体积流中计量入C前体2-甲基-3-丁-2-醇。由于升高的反应温度，C前体将以引发在颗粒表面上的C层生长的方式分解。CVD法运行60分钟，以使C层厚度达到4nm。在惰性气体气氛下的冷却阶段后，将最终颜料从反应器中除去并过筛。
深色颜料显示出具有高光泽和高遮盖力的深色金属效果。
沉积的C层由重量比为90:10的a-C和nc-石墨的混合物组成。该比率是结合了根据Ferrari等人的拉曼光谱研究和根据Müller等人的热重分析确定的。
实施例6–化学气相沉积
在恒定的惰性气体气氛(N2)下，在流化床反应器(DI：63mm)中将150g根据实施例3的蓝-银色颗粒加热至490℃。调整体积流量以达到2mm/s的最小流化速度，因此可确保出色的混合以及传热和传质性能。一旦达到490℃的反应温度，就向流化体积流中计量入C前体丙酮。由于升高的反应温度，C前体将以引发在颗粒表面上的C层生长的方式分解。CVD法运行60分钟，以使C层厚度达到4nm。在惰性气体气氛(N2)下的冷却阶段后，将最终颜料从反应器中除去并过筛。
深色颜料显示出具有高光泽和高遮盖力的深色金属效果。
沉积的C层由重量比为90:10的a-C和nc-石墨的混合物组成。该比率是结合了根据Ferrari等人的拉曼光谱研究和根据Müller等人的热重分析确定的。
实施例7-在可商购获得的蓝色干涉颜料上的a-C/nc-石墨涂层
1kg下列可商购获得的蓝色干涉颜料
实施例7a)：
7225Ultra Blue(Merck KGaA；涂覆有TiO2的天然云母，粒度为10-60μm)
实施例7b)：
Splendid Blue(Merck KGaA；基于涂覆有TiO2和SiO2的天然云母的多层颜料，粒度为10-60μm)
实施例7c)：
Colour Space Blue(Merck KGaA；涂覆有TiO2和SnO2的天然云母，粒度为5-35μm)
实施例7d)：
Caribbean Blue(Merck KGaA，基于涂覆有TiO2，SiO2和SnO2的天然云母的多层颜料，粒度为10-60μm)
实施例7e)：
Royal Exterior Blue(BASF，涂覆有TiO2，SiO2和SnO2的天然云母，d10＝10μm，d50＝19μm，d90＝34μm)
实施例7f)：Mirage Bright Blue(Eckart，涂覆有TiO2和SnO2的硼硅酸盐玻璃薄片，粒度为10-70μm)
实施例7g)：SynCrystal Blue(Eckart，涂覆有TiO2和SnO2的合成云母(氟金云母)，粒度为10-50μm)
实施例7h)：XillaMay(Kuncai，涂覆有TiO2和SnO2，SiO2和Ce2O3的合成云母，粒度为6-30μm)
在流化床反应器(DI：100mm)中被加热到所需的480℃的反应温度。加热和C沉积反应在惰性气体气氛(N2)中进行。以使在整个过程中均保持2mm/s的最小流化速度的方式调节惰性流化气体。如果达到480℃的反应温度，则将C前体丙酮或2-甲基-3-丁-2-醇加入到流化气体中。在惰性气体气氛(N2)下的冷却阶段后，将最终颜料从反应器中除去并过筛。
沉积的C层由a-C nc-石墨的混合物组成：
实施例7a)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例7b)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例7c)：a-C/nc-石墨比率：95：5，层厚度：1-2nm
实施例7d)：a-C/nc-石墨比率：90：10，层厚度：1-2nm
实施例7e)：a-C/nc-石墨比率：95：5，层厚度：1-2nm
实施例7f)：a-C/nc-石墨比率：95：5，层厚度：1-2nm
实施例7g)：a-C/nc-石墨比率：90：10，层厚度：1-2nm
实施例7h)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例7a)至7h)的涂覆的颜料显示出(深色)的天然(masstone)蓝色色调。同时，与未涂覆的颜料相比，遮盖力得到了显著改进。此外，与原始(＝未涂覆)颜料相比，a-C/nc-石墨涂覆的颜料显得更具金属感。
在实施例7d)的情况下，a-C/nc-石墨层增强了色彩迁移效果，即，从蓝色到紫色到绿色的非常强烈的色彩迁移(＝至少三种颜色的多色随角异色)。这种效果以由于增强了色彩迁移而因此可以看到所谓的全息效果的方式，非常适合化妆品应用，例如眼影、唇彩、口红和指甲油。
实施例8-可商购获得的绿色干涉颜料上的碳/石墨涂层
1kg的下列可商购获得的绿色干涉颜料
实施例8a)：
Colour Space Turquoise(Merck KGaA；涂覆有TiO2的天然云母，粒度为5-35μm)
实施例8b)：
Splendid Green(Merck KGaA；基于涂覆有TiO2和SiO2的天然云母的多层颜料，粒度为10-60μm)
实施例8c)：
Nordic Sunset(Merck KGaA，涂覆有SnO2和TiO2的SiO2薄片，粒度为5-50μm)
实施例8d)：Mirage Dazzling Green(Eckart，涂覆有TiO2和SnO2的硼硅酸盐玻璃薄片，粒度为150-200μm)
实施例8e)：
AE-791K-OP Splendor Green(CQV，涂覆有TiO2和SnO2的Al2O3薄片，d10＝5μm，d50＝15-19μm，d90＝30μm)
在流化床反应器(DI：100mm)中被加热到所需的450℃反应温度。加热和C沉积反应在惰性气体气氛中进行。以使在整个过程中均保持2mm/s的最小流化速度的方式调节惰性流化气体。如果达到反应温度，例如450℃，将C前体丙酮或2-甲基-3-丁-2-醇添加到流化气体中。在惰性气体气氛(例如：N2)下的冷却阶段后，将最终颜料从反应器中除去并过筛。
沉积的C层由a-C/nc-石墨的混合物组成：
实施例8a)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例8b)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例8c)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
实施例8d)：a-C/nc-石墨比率：95：5，层厚度：1-2nm
实施例8e)：a-C/nc-石墨比率：85：15，层厚度：1-2nm
根据实施例8a)至8e)的涂覆的颜料显示出(深色)的天然绿色色调和显著改进的遮盖力。此外，与原始(＝未涂覆)颜料相比，a-C/nc-石墨涂覆的颜料显得更具金属感。
在实施例8c)的情况下，a-C/nc-石墨层增强了色彩迁移效果，并且显示出从银-绿色到银-红色到绿-金色的非常强烈的色彩迁移。这种效果以由于增强了色彩迁移而使得可以看到所谓的全息效果的方式在化妆品应用，例如眼影、唇彩、口红和指甲油中被特别利用。
实施例9-15-在可商购获得的干涉颜料上的a-C/nc-石墨涂层
1kg的选自下表的可商购获得的干涉颜料
在流化床反应器(DI：100mm)中被加热到所需的反应温度。加热和C沉积反应在惰性N2气体气氛中进行。以使在整个过程中均保持2mm/s的最小流化速度的方式调节N2惰性流化气体。如果达到反应温度，将C前体添加到流化气体中。在惰性气体(N2)气氛下的冷却阶段后，将最终颜料从反应器中除去并过筛。
实施例9b)和9c)的C涂层导致液态金属效果，尤其是在化妆品应用中，例如口红，唇彩，指甲油。这三种C涂覆的颜料的液态金属指数为8.58(Fop(flop)指数＝18.09，颗粒性＝2.11)。迄今为止，只能通过使用铝薄片达到这种效果，而由于法规限制，不允许在唇彩口、红和眼影中使用铝薄片。
应用实施例
应用实施例A1-涂料
通过搅拌将根据实施例4的a-C/nc-石墨涂覆的颜料掺入底涂料MIPA WBC 000(MIPA SE，德国)中。根据所需的色调，必须使用一定浓度的颜料。为了获得实施例4的颜料的完全色调，在制剂上使用1重量％的颜料。如有必要，可通过用去离子水稀释将涂料调整为在1000s-1时喷涂粘度为70-75mPa·s。通过喷涂将着色的底涂料施加在黑-白金属面板(Metopac T21G，从Leneta公司购买)上。对于自动喷涂应用，使用带有喷枪DeVilbissAGMD2616的Oerter APL 4.6(喷嘴1,4mm，盖767c)。喷涂压力为4200mbar，进料速度为约110ml/min，喷枪与基材之间的距离为约30cm。喷枪以0.45m/s的速度移动，施加三层，每层之间的中间闪蒸时间为30s。所得的干膜厚度为10-20μm，优选11-15μm。如果颜料的碳含量足够高，也可以施加仅一层干膜厚度为1-3μm的层。在室温下通过空气循环将着色层预干燥后，在该底涂层的顶部施加一层清漆层，然后烘烤整个涂层。
应用实施例A2-涂料
通过搅拌将根据实施例5的a-C/nc-石墨涂覆的颜料掺入底涂料MIPA WBC 000(MIPA SE，德国)中。根据所需的色调，必须使用一定浓度的颜料。为了获得实施例5的颜料的完全色调，在制剂上使用1重量％的颜料。如有必要，可通过用去离子水稀释将涂料调整为在1000s-1时喷涂粘度为70-75mPa·s。通过喷涂将着色的底涂层施加在黑-白金属面板(Metopac T21G，从Leneta公司购买)上。对于自动喷涂应用，使用带有喷枪DeVilbissAGMD2616的Oerter APL 4.6(喷嘴1,4mm，盖767c)。喷涂压力为4200mbar，进料速度为约110ml/min，喷枪与基材之间的距离为约30cm。喷枪以0.45m/s的速度移动，施加三层，每层之间的中间闪蒸时间为30s。所得的干膜厚度为10-20μm，优选11-15μm。如果颜料的碳含量足够高，也可以施加仅一层干膜厚度为1-3μm的层。在室温下通过空气循环将着色层预干燥后，在该底涂层的顶部施加一层清漆层，然后烘烤整个涂层。
应用实施例A3-口红
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入预热至55℃的口红模具中。将模具存放在冰箱中约1小时后，将棒取出并将其插入口红机械中。小心地灼烧口红。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
应用实施例A4-口红
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入预热至55℃的口红模具中。将模具存放在冰箱中约1小时后，将棒取出并将其插入口红机械中。小心地灼烧口红。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
应用实施例A5-口红
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入预热至55℃的口红模具中。将模具存放在冰箱中约1小时后，将棒取出并将其插入口红机械中。小心地灼烧口红。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
应用实施例A6-口红
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入预热至55℃的口红模具中。将模具存放在冰箱中约1小时后，将棒取出并将其插入口红机械中。小心地灼烧口红。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
应用实施例A7-眼影
程序:
将B相加热至80℃，直到所有成分融化。冷却至65℃，并在搅拌的同时添加A相的成分。在65℃下大量填充到所需的包装中。冷却至室温。
供应商:
(2)Croda
(3)IOI Oleo GmbH (4)Ashland
(5)Gustav Heess GmbH (6)Schülke&Mayr GmbH
应用实施例A8-润唇膏
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入模具中。将模具存放在冰箱中约1小时后，将口红基质倒入眼影盘中。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
应用实施例A9-润唇膏
程序:
将B相的成分加热至75℃，并搅拌直至完全融化。加入A相并搅拌直至所有成分均匀分散。冷却至65℃，搅拌直至相中无空气，添加C相并倒入模具中。将模具存放在冰箱中约1小时后，将口红基质倒入眼影盘中。
供应商:
(2)Schülke&Mayr GmbH
(3)Henry Lamotte Oils (4)Azelis Germany GmbH
GmbH
(5)BASF AG (6)Cosnaderm GmbH
Claims (16)
1.基于颗粒的颜料，其特征在于所述颗粒涂覆有至少一层，所述层由无定形碳(a-C)和纳米晶石墨(nc-石墨)的混合物组成。
2.根据权利要求1的颜料，其特征在于a-C/nc-石墨的比例在60:40至80:20的范围内。
3.根据权利要求1或2的颜料，其特征在于a-C/nc-石墨层的厚度为1-10nm。
4.根据权利要求1至3中一项或多项的颜料，其特征在于所述颗粒选自以下基材的组：天然或合成云母，滑石，高岭土，Fe2O3薄片，Fe3O4薄片，Al2O3薄片，BiOCl薄片，玻璃薄片，SiO2薄片，TiO2薄片，BN薄片，铝薄片，Si-氧氮化物薄片，Si-/Ti-氮化物薄片和石墨薄片，珍珠精华，合成的无载体薄片，玻璃珠，填料颜料，干涉颜料，多层颜料，随角异色颜料，视角闪色颜料，金属效果颜料，硅颗粒或其混合物。
5.根据权利要求1至4中一项或多项的颜料，其特征在于所述基材是球形或小板状的。
6.根据权利要求1至5中一项或多项的颜料，其特征在于所述基材涂覆有至少一种金属氧化物和/或金属。
7.根据权利要求1至6中一项或多项的颜料，其特征在于所述颗粒选自以下的组：
基材+a-C/nc-石墨层
基材+a-C/nc-石墨层+TiO2
基材+a-C/nc-石墨层+Fe2O3
基材+a-C/nc-石墨层+Fe3O4
基材+a-C/nc-石墨层+Cr2O3
基材+a-C/nc-石墨层+SiO2
基材+a-C/nc-石墨层+ZrO2
基材+a-C/nc石墨层+SnO2
基材+a-C/nc-石墨层+ZnO
基材+a-C/nc-石墨层+Al
基材+a-C/nc-石墨层+Fe
基材+a-C/nc-石墨层+Cr
基材+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+a-C/nc-石墨层
基材+Fe2O3+a-C/nc-石墨层
基材+Fe3O4+a-C/nc-石墨层
基材+TiO2+Fe2O3+a-C/nc-石墨层
基材+TiO2+Fe3O4+a-C/nc-石墨层
基材+TiO2+SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+Al2O3+TiO2+a-C/nc-石墨层
基材+TiO2+MgO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+Al2O3+TiO2+a-C/nc-石墨层
基材+Fe2O3+MgO*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+Fe2O3+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+Al2O3+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+MgO*SiO2+TiO2+a-C/nc石墨层
基材+TiO2/Fe2O3+CaO*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+Al2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2/Fe2O3+B2O3*SiO2+TiO2+a-C/nc-石墨层
基材+TiO2+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2/Fe2O3+SiO2+TiO2/Fe2O3+a-C/nc石墨层
基材+TiO2/Fe2O3+MgO*SiO2+TiO2/Fe2O3+a-C/nc石墨层
基材+TiO2+Al2O3+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+MgO*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+CaO*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+Al2O3*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+B2O3*SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+TiO2+SiO2+a-C/nc-石墨层
基材+TiO2+SiO2/Al2O3+a-C/nc-石墨层
基材+TiO2+Al2O3+a-C/nc-石墨层
基材+SnO2+a-C/nc-石墨层
基材+SnO2+TiO2+a-C/nc-石墨层
基材+SnO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+a-C/nc-石墨层
基材+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+SiO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Fe3O4+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2/Fe2O3+SiO2+TiO2+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+TiO2/Fe2O3+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2+a-C/nc-石墨层
基材+SiO2+TiO2+SiO2/Al2O3+a-C/nc-石墨层
基材+SiO2+TiO2+Al2O3+a-C/nc-石墨层
基材+a-C/nc-石墨层+TiO2+a-C/nc-石墨层
基材+a-C/nc-石墨层+Fe2O3+a-C/nc-石墨层
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层+TiO2
基材+a-C/nc-石墨层+SiO2+SnO2+TiO2+a-C/nc-石墨层+Fe2O3。
8.根据权利要求1至7中一项或多项的颜料，其特征在于，基于总颜料，所述颜料由90-99wt％的颗粒和1-10wt％的一个或多个a-C/nc-石墨层组成。
9.根据权利要求1至8中一项或多项的颜料的制备方法，其特征在于，将颗粒在惰性气体气氛中在流化床反应器中加热至所需温度，并且在达到所需的反应温度时将碳前体添加到流化气体中，并且在化学沉积之后，在惰性气体气氛下冷却流化床反应直到达到室温。
10.根据权利要求9的方法，其特征在于所述碳前体选自糖和有机溶剂。
11.根据权利要求9和10的方法，其特征在于，所述前体为乙醇，异丙醇，丙酮，2-甲基-3-丁-2-醇，糖粉，葡萄糖，果糖，右旋葡萄糖。
12.根据权利要求9至11中一项或多项的方法，其特征在于，所述反应温度为200至＜500℃。
13.根据权利要求9至12中一项或多项的方法，其特征在于，所述流化床反应器是流化床辅助的CVD反应器(FBCVD)。
14.根据权利要求1至8中一项或多项的颜料在油漆，涂料，汽车涂料，汽车修补漆，工业涂料，油漆，粉末涂料，印刷油墨，安全印刷油墨，塑料，陶瓷材料，化妆品，玻璃，纸张，纸张涂料，电子照相印刷工艺的调色剂，种子，温室片材和防水油布，用于机器或设备的绝缘的导热、自支撑、电绝缘、柔性片材，在纸张和塑料的激光打标中用作吸收剂，在塑料的激光焊接中作为吸收剂，具有水、有机和/或水性溶剂的颜料糊，在颜料制剂和干制剂中的用途。
15.制剂，其以0.01-95重量％的量包含根据权利要求1至8中一项或多项的颜料，基于制剂的整体计。
16.根据权利要求15的制剂，其特征在于，另外包含至少一种选自吸收剂，收敛剂，抗微生物物质，抗氧化剂，止汗剂，消泡剂，去头皮屑活性化合物，抗静电剂，粘合剂，生物添加剂，漂白剂，螯合剂，除臭剂，润肤剂，乳化剂，乳液稳定剂，染料，保湿剂，成膜剂，填充剂，香剂，调味剂，驱虫剂，防腐剂，抗蚀剂，化妆品油，溶剂，水，氧化剂，植物成分，缓冲物质，还原剂，表面活性剂，推进剂气体，遮光剂，UV过滤剂和UV吸收剂，变性剂，芦荟，鳄梨油，辅酶Q10，绿茶提取物，粘度调节剂，香料和维生素的组分。
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| KR20230074789A (ko) | 2020-09-28 | 2023-05-31 | 메르크 파텐트 게엠베하 | 기재 상의 금속 효과 안료-무함유 레이더-호환성 코팅 |
| US20240199896A1 (en) | 2021-04-26 | 2024-06-20 | Merck Patent Gmbh | Radar-Compatible Plastic Part |
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- 2020-09-01 TW TW109129863A patent/TW202124596A/zh unknown
- 2020-09-01 US US17/009,305 patent/US20210087403A1/en active Pending
- 2020-09-07 EP EP20194758.7A patent/EP3795645B1/en active Active
- 2020-09-17 KR KR1020200119555A patent/KR20210034515A/ko unknown
- 2020-09-18 CN CN202010989000.4A patent/CN112538281B/zh active Active
- 2020-09-18 JP JP2020156985A patent/JP2021050333A/ja active Pending
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| CN1761725A (zh) * | 2003-01-17 | 2006-04-19 | 密苏里大学学监 | 含碳颜料的抗腐蚀涂层 |
| US20070207099A1 (en) * | 2003-12-10 | 2007-09-06 | Christian Erker | Cosmetic Preparations for the Generation of a Cosmetic Covering with a Metallic and Multi-Coloured Shimmering Appearance and Artifical Fingernail |
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| CN104870571A (zh) * | 2012-12-20 | 2015-08-26 | 默克专利股份有限公司 | 颜料 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3795645B1 (en) | 2024-02-14 |
| CN112538281B (zh) | 2024-05-14 |
| JP2021050333A (ja) | 2021-04-01 |
| KR20210034515A (ko) | 2021-03-30 |
| EP3795645A1 (en) | 2021-03-24 |
| TW202124596A (zh) | 2021-07-01 |
| US20210087403A1 (en) | 2021-03-25 |
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