JP2591946C - - Google Patents
Info
- Publication number
- JP2591946C JP2591946C JP2591946C JP 2591946 C JP2591946 C JP 2591946C JP 2591946 C JP2591946 C JP 2591946C
- Authority
- JP
- Japan
- Prior art keywords
- metal
- flaky
- metal compound
- fine
- compound
- 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.)
- Expired - Lifetime
Links
- 150000002736 metal compounds Chemical class 0.000 claims description 89
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- 229910001111 Fine metal Inorganic materials 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 239000002537 cosmetic Substances 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- TWXTWZIUMCFMSG-UHFFFAOYSA-N nitride(3-) Chemical compound [N-3] TWXTWZIUMCFMSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 32
- 229910001929 titanium oxide Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- 239000000377 silicon dioxide Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 230000003595 spectral Effects 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- -1 titanium alkoxides Chemical class 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K Aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N Titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001953 sensory Effects 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N Silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 210000003491 Skin Anatomy 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N Titanium isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J Zirconium(IV) chloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- UXRJMLKVSKBDPK-UHFFFAOYSA-N [Mo+6].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [Mo+6].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] UXRJMLKVSKBDPK-UHFFFAOYSA-N 0.000 description 2
- MMLHSHZVZZRNRY-UHFFFAOYSA-J [Ti+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O Chemical compound [Ti+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O MMLHSHZVZZRNRY-UHFFFAOYSA-J 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- MIMCEMSZHORAOF-UHFFFAOYSA-N butan-1-olate;cobalt(2+) Chemical compound [Co+2].CCCC[O-].CCCC[O-] MIMCEMSZHORAOF-UHFFFAOYSA-N 0.000 description 2
- SFVJVIQIWGMENJ-UHFFFAOYSA-N butan-1-olate;iron(3+) Chemical compound [Fe+3].CCCC[O-].CCCC[O-].CCCC[O-] SFVJVIQIWGMENJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052803 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 2
- SBFKENUEAOCRNR-UHFFFAOYSA-K indium(3+);triformate Chemical compound [In+3].[O-]C=O.[O-]C=O.[O-]C=O SBFKENUEAOCRNR-UHFFFAOYSA-K 0.000 description 2
- 229910000460 iron oxide Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- GPMKKHIGAJLBMZ-UHFFFAOYSA-J titanium(4+);tetraacetate Chemical compound [Ti+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GPMKKHIGAJLBMZ-UHFFFAOYSA-J 0.000 description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 2
- WXKZSTUKHWTJCF-UHFFFAOYSA-N zinc;ethanolate Chemical compound [Zn+2].CC[O-].CC[O-] WXKZSTUKHWTJCF-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-Aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 241001279686 Allium moly Species 0.000 description 1
- MJWPFSQVORELDX-UHFFFAOYSA-K Aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N Aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VSOKRFVIDUMWDA-UHFFFAOYSA-N CC(C)O[Ni] Chemical compound CC(C)O[Ni] VSOKRFVIDUMWDA-UHFFFAOYSA-N 0.000 description 1
- YQEVIZPKEOELNL-UHFFFAOYSA-N CCCCO[Zr] Chemical compound CCCCO[Zr] YQEVIZPKEOELNL-UHFFFAOYSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N Chromium(III) oxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L Iron(II) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229940058287 Salicylic acid derivative anticestodals Drugs 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N Silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N Silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 231100000765 Toxin Toxicity 0.000 description 1
- KTCZYCFWUINLCP-UHFFFAOYSA-N [Mo+6].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] Chemical compound [Mo+6].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] KTCZYCFWUINLCP-UHFFFAOYSA-N 0.000 description 1
- ASRYSTKCOQBGBE-UHFFFAOYSA-N [W+6].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [W+6].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ASRYSTKCOQBGBE-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- XHODMTAOVMFHQJ-UHFFFAOYSA-N aluminum;propan-2-ol Chemical compound [Al].CC(C)O XHODMTAOVMFHQJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- PPBAJDRXASKAGH-UHFFFAOYSA-N azane;urea Chemical compound N.NC(N)=O PPBAJDRXASKAGH-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000000903 blocking Effects 0.000 description 1
- KYKVJPXYMPRNFK-UHFFFAOYSA-N butan-1-olate;nickel(2+) Chemical compound CCCCO[Ni]OCCCC KYKVJPXYMPRNFK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- VBXHMSMVQZJJLD-UHFFFAOYSA-N cobalt(2+);propan-2-olate Chemical compound [Co+2].CC(C)[O-].CC(C)[O-] VBXHMSMVQZJJLD-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- VSFQMZYFJAOOOG-UHFFFAOYSA-N di(propan-2-yloxy)lead Chemical compound CC(C)O[Pb]OC(C)C VSFQMZYFJAOOOG-UHFFFAOYSA-N 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- CAVJXSIWUWTTQE-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(2+) Chemical compound [O-2].[O-2].[Ti+2].[Fe+2] CAVJXSIWUWTTQE-UHFFFAOYSA-N 0.000 description 1
- QCQJPUZAVFHPMN-UHFFFAOYSA-N iron(2+);propan-2-olate Chemical compound [Fe+2].CC(C)[O-].CC(C)[O-] QCQJPUZAVFHPMN-UHFFFAOYSA-N 0.000 description 1
- 230000036012 kel Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003472 neutralizing Effects 0.000 description 1
- BXWQXMFUEKUGCQ-UHFFFAOYSA-N nickel(2+);propan-2-olate Chemical compound [Ni+2].CC(C)[O-].CC(C)[O-] BXWQXMFUEKUGCQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KREXGRSOTUKPLX-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O KREXGRSOTUKPLX-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000475 sunscreen Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BXILREUWHCQFES-UHFFFAOYSA-J tetrachloroaluminate(1-) Chemical compound Cl[Al-](Cl)(Cl)Cl BXILREUWHCQFES-UHFFFAOYSA-J 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- MCXZOLDSEPCWRB-UHFFFAOYSA-N triethoxyindigane Chemical compound [In+3].CC[O-].CC[O-].CC[O-] MCXZOLDSEPCWRB-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000010333 wet classification Methods 0.000 description 1
- HKIRVJCLEHCVAL-UHFFFAOYSA-N zinc;propan-2-olate Chemical compound CC(C)O[Zn]OC(C)C HKIRVJCLEHCVAL-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、微粒金属化合物を分散含有してな
る薄片状金属化合物に関する。
更に詳細にはマトリクス内部に分散含有した微粒金属化合物とマトリクスであ
る薄片状金属化合物との屈折率差が0.1以上で、その屈折率の違いによる紫外線
の散乱性能に優れた紫外線遮蔽剤として有用な薄片状金属化合物及びそれを配合
してなる化粧料に関するものである。
〈従来の技術〉
紫外線遮蔽剤は、紫外線を散乱或いは吸収して紫外線を遮蔽するもので、サリ
チル酸、パラアミノ安息香酸、けい皮酸及びこれらのエステル類、或いはベンゾ
フェノン類などの有機物、酸化チタン、酸化亜鉛、酸化鉄などの金属酸化物粉末
などが用いられており、金属酸化物粉末による光線の遮蔽能は、粉末の粒径／光
線波長の比が1/2の所が最大であることが知られている。
金属酸化物粉末は、酸化反応用触媒としても用いられ、その製造方法として、
金属の塩化物や硫酸塩にアンモニア水或いは尿素を加えて加
水分解し、得られる水酸化物を焼成する方法、チタンのｉ−プロポキシド、硝酸
亜鉛をそれぞれ加水分解して得られた TiO2・nH2OとZn(OH)2を混練し焼成する方
法等（以上「触媒」Vo1.19,No.5,1997,350〜352頁、触媒学会誌）が知られてい
る。
またケイ素とチタンのアルコキシドの混合物を加水分解し、その加水分解生成
物を焼成する方法及びその生成物を紫外線遮蔽能を有する化粧品用添加剤とする
こと(特開昭59-227813号)も知られている。
この他、微細な粒子のものを得る方法として、チタンの塩化物を昇華させ、酸
素または水蒸気で酸化分解、加水分解を行なわす方法があり、これによると粒径
約0.002μｍ〜0.05μｍのものが得られる。
酸化亜鉛では、金属亜鉛の蒸気を気相酸化させる方法があり、これによると粒
径約0.5μｍ〜１μｍのものが得られる。
〈発明が解決しようとする問題点〉
このような方法で得られた酸化亜鉛、酸化鉄、酸化チタンの粉末は、微粒子を
用いれば良好な紫外線遮蔽能を発揮するが、微粒子の為に凝集しやすく、化粧料
に配合すると、展延性がなく、使用感が悪いとか、ペイント配合時に伸びがない
等の問題点を有する。
また、これら微粒金属酸化物は、表面積が大きく、表面活性が高いので、酸化
反応の触媒能を有し、用途によっては、共存する有機物を変質させる問題点を有
する。
かかる事業下に鑑み、本発明者らは紫外線遮蔽能に優れる事は勿論マトリック
ス等に対する分散能に優れ、化粧料等への配合使用に於いて使用感がよくまた共
存する有機物変質等の問題のない紫外線遮蔽剤を見出すべく鋭意検討した結果、
遂に本発明を完成するに至った。
〈問題点を解決するための手段〉
すなわち、本発明は、薄片状金属化合物に、薄片状金属化合物との屈折率の差
が0.1以上である微粒金属化合物を体積分率で1〜30％分散
含有してなる薄片状金属化合物及びそれを配合してなる化粧料を提供するにある
。
以下、本発明を更に詳細に説明する。
本発明の実施に当り、微粒金属化合物を分散含有するマトリクスとしての薄片
状金属化合物の構成材料としては、２価以上の金属、該金属の金属酸化物、金属
窒化物、金属炭化物、金属水酸化物、金属塩化物または金属アルコキシドや金属
キレート化物や金属有機酸塩のような有機金属化合物の部分加水分解物、または
無機高分子化合物等が用いられる。
具体的には、マグネシウム、亜鉛、アルミニウム、インジウム、ケイ素、スズ
、チタニウム、ジルコニウム、クロム、モリブデン、タングステン、鉄、コバル
ト、ニッケル等の酸化物、窒化物、炭化物、水酸化物、四塩化ケイ素、四塩化チ
タニウム、四塩化ジルコニウム等の金属塩化物の加水分解物、ジエトキシマグネ
シウム、ジイソプロポキシマグネシウム、ジエトキシ亜鉛、ジイソプロポキシ亜
鉛、トリイソプロポキ
シアルミニウム、トリブトキシアルミニウム、トリエトキシインジウム、トリオ
クトキシインジウム、テトラエトキシシラン、テトラブトキシシラン、テトラエ
トキシスズ、テトラオクトキシスズ、テトラエトキシチタニウム、テトライソプ
ロポキシチタニウム、テトラエトキシジルコニウム、テトラペントキシジルコニ
ウム、トリエトキシクロム、トリブトキシクロム、ヘキサエトキシモリブデン、
ヘキサブトキシモリブデン、ヘキサイソプロポキシタングステン、ジイソプロポ
キシ鉄、トリブトキシ鉄、ジブトキシコバルト、ジイソプロポキシコバルト、ジ
イソプロポキシニッケル、ジブトキシニッケル等の金属アルコキシドの部分加水
分解物、マグネシウム、亜鉛、アルミニウム、インジウム、ケイ素、スズ、チタ
ニウム、ジコニウム、クロム、モリブデン、タングステン、鉄、コバルト、ニッ
ケル等のアセチルアセトナートのような金属キレート化物の部分加水分解物、酢
酸アルミニウム、ギ酸インジウム、酢酸ケイ素、酢酸ス
ズ、ギ酸チタニウム、酢酸チタニウム、プロピオン酸ジルコニウム等の金属有機
酸塩の部分加水分解物等の有機金属化合物の部分加水分解物、水ガラス、リン酸
アルミニウム、リン酸ジルコニウム、フォスファゼン等の無機高分子が用いられ
る。
他方、該薄片状金属化合物に分散せしめる微粒金属化合物としては、２価以上
の金属、該金属の金属酸化物、金属窒化物、金属炭化物、金属水酸化物、金属塩
化物または金属アルコキシドや金属キレート化物や金属有機酸塩のような有機金
属化合物の部分加水分解物、金属硫酸塩等が挙げられ、好ましくは２価以上の金
属、該金属の金属酸化物、金属窒化物、金属炭化物、金属水酸化物が、更に好ま
しくは金属酸化物が適している。
具体的には、マグネシウム、亜鉛、アルミニウム、インジウム、ケイ素、スズ
、チタニウム、ジルコニウム、クロム、モリブデン、タングステン、鉄、コバル
ト、ニッケル等の金属、金属
酸化物、金属窒化物、金属炭化物、金属水酸化物、四塩化ケイ素、四塩化チタニ
ウム、四塩化ジルコニウム等の金属塩化物の加水分解物、ジエトキシマグネシウ
ム、ジイソプロポキシマグネシウム、ジエトキシ亜鉛、ジイソプロポキシ亜鉛、
トリイソプロポキシアルミニウム、トリブトキシアルミニウム、トリエトキシイ
ンジウム、トリオクトキシインジウム、テトラエトキシシラン、テトラブトキシ
シラン、テトラエトキシスズ、テトラオクトキシスズ、テトラエトキシチタニウ
ム、テトライソプロポキシチタニウム、テトラエトキシジルコニウム、テトラペ
ントキシジルコニウム、トリエトキシクロム、トリブトキシクロム、ヘキサエト
キシモリブデン、ヘキサブトキシモリブデン、ヘキサイソプロポキシタングステ
ン、ジイソプロポキシ鉄、トリブトキシ鉄、ジブトキシコバルト、ジイソプロポ
キシコバルト、ジイソプロポキシニッケル、ジブトキシニッケル等の金属アルコ
キシドの部分加水分解物、マグネシウム、亜鉛、アル
ミニウム、インジウム、ケイ素、スズ、チタニウム、ジコニウム、クロム、モリ
ブデン、タングステン、鉄、コバルト、ニッケル等のアセチルアセトナートのよ
うな金属キレート化物の部分加水分解物、酢酸アルミニウム、ギ酸インジウム、
酢酸ケイ素、酢酸スズ、ギ酸チタニウム、酢酸チタニウム、プロピオン酸ジルコ
ニウム等の金属有機酸塩の部分加水分解物等の有機金属化合物の部分加水分解物
、等が用いられる。
これら微粒金属化合物として、更に具体的には市販のNi,Ag,Cu,Al,Au,Fe等の
金属微粉末（例えば真空冶金(株)、三井金属鉱業(株)製）酸化鉄、シリカ、アル
ミナ、チタニア微粒子（例えば岡村製油(株)、日本アエロジル(株)、住友化学(
株)製）等の金属酸化物、炭化ケイ素（例えば昭和電工(株)製）等の金属炭化物
、窒化ケイ素（例えば宇部興産(株)製）等の金属窒化物等が挙げられる。
金属水酸化物としては、金属塩の水溶液にアルカリを加える等の公知の操作に
より容易に得
られる水酸化マグネシウム、水酸化バリウム、水酸化鉄、水酸化アルミニウム等
の微粒子が挙げられる。
金属硫酸塩は、金属水酸化物または金属塩の水溶液と硫酸の中和反応によって
得られる。
例えば水酸化バリウムの水溶液と硫酸の反応によって得られる硫酸バリウムは
極めて微細な粒子である。
また前述の金属アルコキシドまたは該金属アルコキシドを有機酸で変性したも
のの部分加水分解物も本発明の微粒子として用い得る。
例えばテトラエトキシシランのエタノール溶液に水とアンモニウムを適量加え
る事によって単分散の微粒子が得られるし、アルミニウムイソプロポキシドに適
量のステリアン酸を加えたもののアルコール溶液をノズル等から空気中に吹き出
す事によっても微粒子が得られる。
本発明の実施に際し、マトリクスとしての薄片状金属化合物への微粒金属化合
物の添加混合、分散方法としては、微粒金属化合物がマトリク
スである薄片状金属化合物に均一に分散する方法であれば特にその製造方法を制
限されるものではないが、例えば微粒金属化合物を金属アルコキシド溶液に分散
後、米国特許第2,941,895号明細書、特開昭60-176906号公報等に記載されている
如く平滑面上に塗布し、該塗膜を水または水蒸気によって加水分解を行ない、金
属アルコキシド部分加水分解物をマトリクスとした微粒金属化合物を分散含有す
る薄膜状物質を得た後、これをスクレーパー等で剥離し空気中で焼成する事によ
って、金属酸化物をマトリクスとした微粒金属化合物を分散含有する薄片状金属
化合物を得る事が出来る。
また焼成を炭素存在下等の還元性雰囲気で実施すれば、主として金属炭化物を
マトリクスとした微粒金属化合物を分散含有する薄片状金属化合物が得られる。
更に焼成を炭素の存在下窒素雰囲気で実施すれば主として金属窒化物をマトリ
クスとした微粒金属化合物を分散含有する薄片状金属化合物
が得られる。
また、硫酸チタン水溶液に微粒金属化合物を分散して、米国特許第3,018,186
号明細書等に示されているような薄片状物質の製造方法によって微粒金属化合物
を分散含有する薄片状チタンを得ることもできる。
さらに、これを前述と同様に焼成時の雰囲気を変える事によって微粒金属化合
物を分散含有する薄片状炭化チタンや窒化チタンを得ることもできる。
また、微粒金属化合物を水ガラスや、リン酸アルミニウム溶液のような無機高
分子に分散したのち、特願昭61-82486号に示すような方法で薄片化しても良い。
このとき空気中での安定化を図るために得られた薄片状金属化合物を焼成して
も良い。
このようにして、微粒金属化合物を分散含有する薄片状金属化合物を得ること
ができるが就中、マトリクスを金属酸化物、窒化物、アルコキシド部分加水分解
物、炭化物とする場合には、
微粒金属化合物を金属アルコキシド溶液に分散後、加水分解する上述の方法が最
も品質の均一性、及び生産性の点より推奨される。
このようにして得られた薄片状金属化合物は次いで特定の形状に調整される。
該形状は用途により一義的ではないが通常平均の厚み約0.1μｍ〜約５μｍ、
好ましくは0.2μｍ〜２μｍ、平均の大きさ約１μｍ〜約500μｍ、好ましくは３
μｍ〜100μｍである。
薄片の厚みが約0.1μｍより薄いと、機械的強度が低く、実用に耐えない。
厚みが約５μｍより厚いと肌へのつきや、使用時の感触がわるくなる。
薄片の平均の大きさが約１μｍより小さいと、薄片の形状を保ちにくく、約50
0μｍを越えると、壊れやすくなる。
また、薄片状金属化合物のアスペクト比
｛アスペクト比＝（薄片の平均の大きさ）／（薄片の平均の厚み）｝
は３以上100以下が好ましい。
アスペクト比が３以下の場合には展延性等の改良効果があまりでず、100以上
のときには、機械的に壊れやすくなるので好ましくない。
薄片は一般的に分布を持つため、本発明において大きさは平均の大きさ、即ち
100個の薄片についての（薄片の最長さしわたし径＋最短さしわたし径）/2の値
の平均値で規定し、厚みも平均の厚み、即ち100個の薄片についての平均値で規
定した。
そして、特定の大きさに薄片状金属化合物を調整する方法としては、前記の方
方によって得られた薄片状金属化合物を乾式ボールミル、湿式ボールミル、振動
ミル、ロールミル、ゼットミル等による粉砕及び／またはジャイロシフターやハ
ンマースクリーンのような振動ふるい、スパイラル分級器や水力分級器のような
湿式分級法、動式または遠心式の風力分級器のような乾式分級法、あるいは浮遊
選鉱法等のような分級工程の１つまたは２つ以上を組み合わせる方法等の周知の
方法（例えば粉体工学ハンドブッ
ク、井伊谷鋼一編集、朝倉書店発行）を採用すればよい。
本発明の薄片状金属化合物の用にあたって、マトリクスとこれに混合分散せし
める微粒金属化合物は、その用途によって選択される。
例えば、200℃以上の耐熱性の要求される用途であれば、マトリクスとしては
金属酸化物、窒化物、炭化物、無機高分子等が適している。
一般的には、光線の散乱による紫外線遮蔽はマトリクスと分散微粒子の屈折率
の差が大きいほど効果がある。
この効果を発揮する最低限度としてマトリクスと該マトリクス中に分散せしめ
る微粒金属化合物の屈折率の差は少なくとも0.1以上、好ましくは0.3以上が必要
である。
0.1以下の場合は光線は充分に散乱せず、紫外線の遮蔽効果もあまりない。
例えば、マトリクスとして、屈折率1.4〜1.5のシリカを用いる場合には分散せ
しめる微粒金属化合物としては屈折率1.76のアルミナや、更
に好ましくは2.0 の酸化亜鉛や、2.5の酸化チタンを選択すると効果が大きい。
逆にマトリクスとして酸化亜鉛や、酸化チタン等の屈折率の高い物質を用いる
場合には、分散せしめる微粒金属化合物は屈折率の低いシリカ、アルミナ等を選
択すればよい。
また、微粒金属化合物または薄片状金属化合物として、前述の酸化物、炭化物
、窒化物等を含む混合化合物も、その構成比によって任意に屈折率を変化させる
ことができるために有用である。
例えば、重量比でアルミナ／シリカ＝90/10の混合酸化物の屈折率は約1.7であ
り、80/20であれば約1.65である。
またチタニア／シリカの混合酸化物の屈折率は重量比50/50のとき約1.8であり
、25/75のとき約1.6である。
本発明に於いて用いる微粒金属化合物の平均粒径は、約0.005μｍ〜約0.5μｍ
より好ましくは約0.008μｍ〜約0.1μｍである。
大きさの上限は、これを分散する薄片状金属化合物の厚みによるが、約0.5μ
ｍより大きいと、これを薄片状物質中に均一に分散することが難しく、また紫外
線の波長より大きくなるために、紫外線散乱能が低下する。
他方、約0.005μｍより小さいと、マトリクスと粒子の差が顕著でなくなる。
薄片状金属化合物と微粒金属化合物の組み合わせ方や、その割合はそれぞれの
大きさや使用目的によって異なる。
例えば透明性を重視する紫外線遮蔽の用途には、低屈折率の薄片中に、高屈折
率で且つ約0.1μｍ以下の極微粒の微粒金属化合物をできるだけ少量均一に分散
する方法が好ましいし、透明性を重視しないときは微粒金属化合物の粒径や配合
量の制約はあまりない。
分散粒子の体積分率が50％を越えると、分散粒子を構成する物質がマトリクス
となった薄片の性質となる。
従って、分散粒子構成物質でマトリクスを形
成し、マトリクス構成物質で分散粒子を形成する事が可能であれば、その方が製
造しやすい場合がある。
一般的には必ずしもこの逆転は可能ではなく、製造上の容易さ等を考慮すれば
微粒金属化合物の体積分率は微粒金属化合物を分散せしめる薄片状金属化合物の
約0.1％〜約50％、好ましくは約１％〜約30％の範囲が実用的である。
薄片状物質に対する微粒金属化合物の添加量が多い場合には、微粒金属化合物
を構成する金属化合物よりなる薄片の性質となり、複合効果が顕著でなくまた製
造が困難となり、他方少ない場合には、マトリクスの性質とあまり変わらず、例
えば紫外線の散乱が不十分となり、好ましくない。
更に有色薄片状金属化合物を目的とする場合には、微粒金属化合物及び／また
はマトリクスの薄片状金属化合物、就中、微粒金属化合物として有色微粒金属化
合物を用いればよい。
例えば酸化鉄等の赤色顔料を用いると赤色に、
緑色２号、酸化クロム等では緑色に、酸化モリブデン等では青色に着色可能であ
る。
こうして得られた薄片状金属化合物は、有害紫外線から皮膚を保護する目的で
デイクリームやファンデーション、白粉、リップスティック、アイシャドー等基
礎化粧品からメークアップ化粧品に至る各種の紫外線遮蔽剤が配合されている化
粧料に適用可能で、その配合割合は化粧料の種類によっても異なり、一義的では
ないが、通常約0.5重量％〜約70重量％好ましくは約2重量％〜約40重量％の範囲
で添加される。
化粧料中には占める薄片状金属化合物が0.5重量％未満では紫外線遮蔽能が劣
り、他方70重量％を越えるとしっとり感等の使用時の感触が低下する。
また、紫外線遮蔽効果を向上させる目的で、サルチル酸系誘導体、安息香酸系
誘導体、ケイ皮酸系誘導体、ベンゾフェノン誘導体、酸化チタン、酸化亜鉛、カ
リン、酸化アルミニウム、炭酸カルシウム等の公知の紫外線遮蔽剤を添加
し、薄片状金属化合物と併用することもできる。
更に、本発明において薄片状金属化合物よりなる紫外線遮蔽剤を配合する場合
、分散性、使用性を向上させる目的で通常使用される油脂原料による表面被膜処
理、界面活性剤処理或いはステアリン酸亜鉛などの金属石鹸処理等の表面処理を
行ってから配合してもよい。
これらの薄片状金属化合物を化粧料に配合する方法としては、公知の混合方法
、即ちヘンシェルミキサー、リボンミキサー、Ｖ型ブレンダー等を用いることが
できる。
〈発明の効果〉
以上詳述した本発明の薄片状金属化合物は波長400nm以下の紫外線遮蔽能に優
れると伴に微粒金属酸化物に比較し樹脂やビヒクル中への分散性に優れるため、
適用において展延性、のび等の優れた使用感を与え、共存する有機物を変質せし
める事がない為に、化粧料には勿論のこと塗料、農業用フィルム等への添加剤と
しても適用可能でありその工業的価値は頗る大なるも
のである。
〈実施例〉
以下に本発明を実施例により更に詳細に説明するが、本発明はこれにより何ら
制限されるものではない。
実施例１〜３、比較例１〜２
TiCl419g(0.1モル)をメタノール6.4g（0.2モル）と反応させた後に水42gと混
合し、この液中に平均粒径0.012μｍの超微粒子シリカ（日本エアロジル製）を
第１表に示す割合になるように超音波混合した。
この液に洗浄したスライドガラスを浸漬して、75cm/分の速度で引き上げた後
、これをエアーバス中で120℃、30分間乾燥し薄片を得た。
得られた薄片を300℃、５時間、次いで700℃、２時間焼成し平均の大きさ７μ
ｍ、平均の厚み0.8μｍの微粒シリカを分散含有する薄片状酸化チタンを得た。
得られた薄片状酸化チタンの分光透過率の測定結果を第１図に示す。
また超微粒子シリカを加えないで作成した薄片酸化チタンを比較例１として、
更に超微粒子シリカ各単独を比較例２として分光透過率を測定した。
測定結果を第１図に示す。
尚、分光透過率は試料粉末0.03gを低密度ポリエチレン粉末0.47gと混合し、２
本ロール（温度100〜160℃）で混練溶融し厚み約50μｍのフィルムを製作し、対
照フィルムとして試料粉末を含まない低密度ポリエチレンの厚み約50μｍのフィ
ルムを製作した後両フィルムについてJIS K0115に従い分光々度計にて測定した
。（ここで、微粒シリカと薄片状酸化チタンの屈折率は1.46と2.5 であり、屈折
率の差は1.04である。）
比較例３〜５
平均粒子径0.4μｍのルチル形酸化チタン(石原産業社製)、平均粒子径0.3μｍ
のアナタース形酸化チタン（堺化学社製）及び平均粒子径0.03μｍの微粒子酸化
チタン(日本アエロジ
ル)の分光透過率を測定した。
その結果を比較例３〜５として第２図に示す。
実施例４、比較例６
テトラエチルオルトシリケートの40重量％エタノール溶液に、該溶液中のSiの
２倍モルのギ酸を加えて、70℃で３時間攪拌混合した後に、この液中に平均粒径
0.03μｍの超微粒子酸化チタン（日本アエロジル製）を液中のシリカに対して30
重量％になるよう超音波混合した。
次にこの液中に洗浄したスライドガラスを浸漬した。
このガラスを70cm/分で引き上げた後に、エアバス中で90℃、30分間乾燥して
、平均の大きさ100μｍ、平均の厚み1.7μｍの透明且つ表面の平滑な薄片を得た
。
これを450℃で30分間焼成して、平均の大きさ60μｍ、平均の厚み0.9μｍの、
超微粒酸化チタンを分散含有する薄片状シリカを得た。
更に、これを超音波粉砕して平均の大きさ35μｍ、平均の厚み0.9 μｍの、超
微粒酸化チタ
ンを分散含有する薄片状シリカを得た。
得られた超微粒酸化チタンを分散含有する薄片状シリカの分光透過率の測定結
果を第３図に示す。
また、超微粒酸化チタンを加えないで同様に作成した平均の大きさ35μｍ、平
均の厚み0.9μｍの薄片状シリカの分光透過率を比較例６として測定した。
その結果をも第３図に併せて示す。
（尚、超微粒酸化チタンと薄片状シリカの屈折率は2.5と1.46であり屈折率の差
は1.04である。）
実施例５
チタニウムテトラエトキシドの40 重量％エタノール溶液200gに、27gのプロピ
オン酸と液中のチタン量（酸化チタン換算）に対して５重量％のアルミナとなる
如く平均粒径0.1μｍの微粒アルミナ(住友化学製)1.4gを加えて、70℃で３時間
攪拌混合した後、この液中に洗浄したスライドガラスを浸漬した。
このガラスを50cm/分で引き上げた後に、エアバス中で90℃、30分間乾燥後450
℃で30分間焼成して、平均の大きさ20μｍ、平均の厚み0.8μｍの、微粒アルミ
ナを分散含有する薄片状酸化チタンを得た。
これを更に超音波粉砕して水簸し、平均の大きさを10μｍとした。
得られた薄片状酸化チタンの分光透過率の測定結果を第３図に示す。
またアルミナを加えないで同様に作成した薄片状酸化チタンの分光透過率は比
較例１と同じであった。
（尚、微粒アルミナと薄片状チタンの屈折率は1.76と2.5 であり屈折率の差は0.
74である。）
実施例６、比較例７
リンが７重量％、AI/Pのモル比が３の第一リン酸アルミニウム水溶液にリン酸
アルミニウムに対し５重量％となる如く平均粒径0.03μｍの微粒子酸化チタンを
超音波混合した。
次いで洗浄したスライドガラスを溶液中に浸
漬した後このガラスを50cm/分で引き上げた後に、エアバス中で90℃、30分間乾
燥し、スクレーパーで掻き取って薄片化した。
このようにして得られた微粒酸化チタン分散薄片状リン酸アルミニウムは平均
の大きさ 20μ、厚さ２μであった。
得られた薄片状リン酸アルミニウムの300nm及び500nmの分光透過率の測定結果
を第２表に示す。
また、酸化チタンを加えないで同様に作成した薄片状リン酸アルミニウムの30
0nm及び500nmの分光透過率を比較例７として第２表に併せて示す。
実施例７
チタニウムテトラエトキシドの40重量％エタノール溶液200gに、27gのプロピ
オン酸と平均粒径0.03μｍの微粒酸化亜鉛2.8gを加えて、70℃で３時間攪拌混合
した後に、この液中に洗浄したスライドガラスを浸漬した。
このガラスを50cm/分で引き上げた後に、エ
アバス中で90℃、30分間乾燥後450℃で30分間焼成して、平均の大きさ15μｍ、
平均の厚み0.8μｍの微粒酸化亜鉛分散薄片状酸化チタンを得た。これを更に超
音波粉砕して水簸し、平均の大きさを10μｍとした。
この300nm及び500nmの分光透過率を第２表に示す。
実施例８、比較例８、９
チタニウムテトラエトキシドの40重量％エタノール溶液200gに、27gのプロピ
オン酸を加えたものと、テトラエチルオルトシリケートの40重量％エタノール溶
液に該溶液中Siの２倍モルのギ酸を加えたものを、容積比でTiO2/SiO2＝75/25（
実施例８）、TiO2/SiO2＝50/50（比較例８、９）となるように混合し、70℃で３
時間攪拌混合した後に、この液中に平均粒径0.1μｍの微粒アルミナ（住友化学
製）1.4gを表２に示す割合になるように加えて超音波混合した。
次にこの液中に洗浄したスライドガラスを浸漬した。このガラスを75c/分で引
き上げた後に、
エアバス中で90℃、30分間乾燥して、平均の大きさ100μｍ、平均の厚み1.7μｍ
の透明且つ表面の平滑な薄片を得た。
これを450℃で30分間焼成して、平均の大きさ600μｍ、平均の厚み0.9μｍの
、酸化チタン分散薄片状チタニアーシリカを得た。更に、これを超音波粉砕して
平均の大きさ10μｍ、平均の厚み0.9μｍの、酸化チタン分散薄片状チタニア−
シリカを得た。
これらの305nm及び500nmの分光透過率を第２表に示す。
実施例９、10〜12
実施例２で作成した微粒シリカを分散含有する薄片状酸化チタンを用いて、パ
ウダーファンデーションを調整した。
また比較のため比較例１の薄片状酸化チタン、平均粒径0.4μｍの市販ルチル
形粉末状酸化チタン(石原産業社製)、平均粒径0.03μｍの市販微粒酸化チタン（
日本アエロジル社製）を配合したパウダーファンデーションを調整した。
このようにして得られた実施例９及び比較例10〜12の製品について安定性、紫
外線遮蔽効果及び官能評価を実施した。
その結果を第３表に示す。
実施例10、比較例13
実施例２で作成した微粒シリカを含有する薄片状酸化チタンを用いて、プレス
ドパウダーを調整した。
また、比較のため、タルクを主配合としたプレスドパウダーを調整した。
このようにして得られた実施例10及び比較例13の製品について安定性、紫外線
遮蔽効果及び官能効果を実施した。その結果を第４表に示す。
尚、測定法は以下の方法により求めた。
安定性：化粧料を温度調節のない室内に１年間
保存して変質を調べた。
紫外線遮蔽効果：（ＳＰＦ値 日焼け止め指数
化粧料を皮膚へ均一に2mg/cm2また
は２μｌ/cm2塗布した部分、並びに
未塗布部を東光電気（株）製医療用
紫外線照射装置｛Ｍ-DMR-１型；
光源東芝蛍光灯FL20S・Ｅ−30（λ
max305nm）、FL20S・BLB(λ
max352nm)｝で照射、及び東京光学
機械（株）製紫外線強度計（UVR−
305/365・Ｄ型）で、夫々の最小紅
斑生成エネルギーを測定し、塗布部
最小紅斑生成エネルギー／未塗布
部最小紅斑生成エネルギー比で示
した。
官能テスト：女性20名に２週間使用させ、最高
点を５点とする段階法にて評価し
た結果の平均点で評価した。
DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a flaky metal compound containing a fine metal compound dispersed therein. More specifically, a fine metal compound dispersed and contained inside the matrix and the matrix.
The refractive index difference from the flaky metal compound is 0.1 or more.
Flaky metal compound useful as an ultraviolet ray shielding agent with excellent scattering performance and its compounding
The present invention relates to cosmetics. <Conventional technology> An ultraviolet shielding agent scatters or absorbs ultraviolet rays to shield ultraviolet rays.
Tylic acid, para-aminobenzoic acid, cinnamic acid and their esters or benzoic acid
Organic substances such as phenones, and metal oxide powders such as titanium oxide, zinc oxide and iron oxide
And the like, and the shielding ability of the light beam by the metal oxide powder is expressed by the particle size of the powder / light
It is known that the ratio where the line wavelength is 1/2 is maximum. Metal oxide powder is also used as an oxidation reaction catalyst, as a production method thereof,
A method in which ammonia water or urea is added to metal chlorides or sulfates to hydrolyze them, and the resulting hydroxides are calcined, i-propoxide of titanium, nitric acid
TiO obtained by hydrolysis of zinc Two ・ NH Two O and Zn (OH) Two For kneading and firing
Method (above "catalyst" Vo1.19, No. 5, 1997, pp. 350-352, Journal of the Society of Catalysts)
You. It also hydrolyzes a mixture of silicon and titanium alkoxides,
For baking products and using the products as cosmetic additives with ultraviolet shielding ability
(JP-A-59-227813) is also known. In addition, as a method of obtaining fine particles, titanium chloride is sublimated and acid is added.
There is a method of performing oxidative decomposition and hydrolysis with elemental or steam,
A thickness of about 0.002 μm to 0.05 μm is obtained. In the case of zinc oxide, there is a method in which vapor of metallic zinc is vapor-phase oxidized.
Those having a diameter of about 0.5 μm to 1 μm are obtained. <Problems to be Solved by the Invention> The powders of zinc oxide, iron oxide and titanium oxide obtained by such a method reduce fine particles.
When used, it exhibits good ultraviolet shielding ability, but it is easy to aggregate due to its fine particles,
When blended, there is no extensibility, poor usability, and no stretch when blending paint
And the like. In addition, these fine metal oxides have a large surface area and a high surface activity,
It has the ability to catalyze the reaction and, depending on the application, has the problem of altering coexisting organic substances.
I do. In view of this business, the present inventors have not only excellent
It has excellent dispersing ability for cosmetics, etc.
As a result of intensive studies to find an ultraviolet shielding agent that does not have problems such as alteration of existing organic substances,
Finally, the present invention has been completed. <Means for Solving the Problems> That is, the present invention provides For flaky metal compounds, Difference in refractive index from flaky metal compound
Is 0.1 or more 1-30% by volume fraction DISCLOSURE OF THE INVENTION An object of the present invention is to provide a flaky metal compound which is dispersed and contained and a cosmetic which comprises the compound.
. Hereinafter, the present invention will be described in more detail. In the practice of the present invention, flakes as a matrix containing dispersed fine metal compounds
As the constituent material of the metallic compound, a divalent or higher valent metal, a metal oxide of the metal, a metal
Nitride, metal carbide, metal hydroxide, metal chloride or metal alkoxide or metal
Partial hydrolysates of organometallic compounds such as chelates and metal organic acid salts, or
An inorganic polymer compound or the like is used. Specifically, magnesium, zinc, aluminum, indium, silicon, tin
, Titanium, zirconium, chromium, molybdenum, tungsten, iron, koval
Oxides, nitrides, carbides, hydroxides, silicon tetrachloride, titanium tetrachloride
Hydrolysis products of metal chlorides such as titanium and zirconium tetrachloride, and diethoxymagne
Cium, diisopropoxy magnesium, diethoxy zinc, diisopropoxy
Lead, triisopropoxy aluminum, tributoxy aluminum, triethoxy indium, trio
Ctoxyindium, tetraethoxysilane, tetrabutoxysilane, tetraethyl
Toxin, tetraoctoxytin, tetraethoxytitanium, tetraisop
Ropoxytitanium, tetraethoxyzirconium, tetrapentoxyzirconi
, Triethoxychrome, tributoxychrome, hexaethoxymolybdenum,
Hexabutoxymolybdenum, hexaisopropoxytungsten, diisopropo
Iron xylate, tributoxy iron, dibutoxy cobalt, diisopropoxy cobalt, di
Partial hydrolysis of metal alkoxides such as isopropoxy nickel and dibutoxy nickel
Decomposed products, magnesium, zinc, aluminum, indium, silicon, tin, titanium
, Zirconium, chromium, molybdenum, tungsten, iron, cobalt, nickel
Partial hydrolyzate of metal chelates such as acetylacetonate such as Kel, vinegar
Metal organic such as aluminum formate, indium formate, silicon acetate, tin acetate, titanium formate, titanium acetate, zirconium propionate
Partial hydrolysates of organometallic compounds such as partial hydrolysates of acid salts, water glass, phosphoric acid
Inorganic polymers such as aluminum, zirconium phosphate and phosphazene are used
You. On the other hand, as the fine metal compound dispersed in the flaky metal compound,
Metal, metal oxide, metal nitride, metal carbide, metal hydroxide, metal salt of the metal
Or organic gold such as metal alkoxides, metal chelates and metal organic acid salts
Partial hydrolysates of the genus compounds, metal sulfates, etc., and preferably divalent or higher valent gold.
Metals, metal oxides, metal nitrides, metal carbides, and metal hydroxides of the metals are more preferred.
Alternatively, a metal oxide is suitable. Specifically, magnesium, zinc, aluminum, indium, silicon, tin
, Titanium, zirconium, chromium, molybdenum, tungsten, iron, koval
Metal, metal oxides, metal nitrides, metal carbides, metal hydroxides, silicon tetrachloride, titanium tetrachloride
Hydrolyzate of metal chlorides such as aluminum and zirconium tetrachloride, diethoxymagnesium
System, diisopropoxy magnesium, diethoxy zinc, diisopropoxy zinc,
Aluminum triisopropoxy, aluminum tributoxy, triethoxyi
Indium, trioctoxyindium, tetraethoxysilane, tetrabutoxy
Silane, tetraethoxytin, tetraoctoxytin, tetraethoxytitanium
System, tetraisopropoxytitanium, tetraethoxyzirconium, tetrape
Butoxyzirconium, triethoxychrome, tributoxychrome, hexaeth
Xymolybdenum, hexabutoxymolybdenum, hexaisopropoxytantange
Iron, diisopropoxy iron, tributoxy iron, dibutoxy cobalt, diisopropoxy
Metallic alcohols such as xycobalt, diisopropoxynickel and dibutoxynickel
Partial hydrolyzate of oxide, magnesium, zinc, aluminum, indium, silicon, tin, titanium, zirconium, chromium, moly
Acetylacetonate such as butene, tungsten, iron, cobalt, nickel, etc.
Metal chelate partial hydrolyzate, aluminum acetate, indium formate,
Silicon acetate, tin acetate, titanium formate, titanium acetate, zirconium propionate
Partial hydrolysates of organometallic compounds such as partial hydrolysates of metal organic acid salts such asium
, Etc. are used. As these fine metal compounds, more specifically, commercially available Ni, Ag, Cu, Al, Au, Fe, etc.
Fine metal powder (for example, manufactured by Vacuum Metallurgy Co., Ltd., Mitsui Mining & Smelting Co., Ltd.) iron oxide, silica, aluminum
Mina, titania fine particles (for example, Okamura Oil Co., Ltd., Nippon Aerosil Co., Ltd., Sumitomo Chemical (
Co., Ltd.) and metal carbides such as silicon carbide (eg, Showa Denko KK)
And metal nitrides such as silicon nitride (for example, manufactured by Ube Industries, Ltd.). As a metal hydroxide, a known operation such as adding an alkali to an aqueous solution of a metal salt can be used.
More easily obtainable magnesium hydroxide, barium hydroxide, iron hydroxide, aluminum hydroxide, etc.
Fine particles. Metal sulfates are obtained by neutralizing sulfuric acid with an aqueous solution of a metal hydroxide or metal salt.
can get. For example, barium sulfate obtained by the reaction of an aqueous solution of barium hydroxide with sulfuric acid is
Very fine particles. Further, the metal alkoxide or the metal alkoxide is modified with an organic acid.
The partial hydrolyzate of the above can also be used as the fine particles of the present invention. For example, add an appropriate amount of water and ammonium to an ethanol solution of tetraethoxysilane.
Monodispersed fine particles can be obtained and suitable for aluminum isopropoxide.
An alcohol solution containing a certain amount of steric acid is blown out into the air from a nozzle, etc.
By doing so, fine particles can be obtained. In the practice of the present invention, the fine metal compound into a flaky metal compound as a matrix
The method for adding, mixing and dispersing the substances is particularly limited as long as the fine metal compound is uniformly dispersed in the flaky metal compound serving as the matrix.
Although not limited, for example, a fine metal compound is dispersed in a metal alkoxide solution.
Later, U.S. Pat.No. 2,941,895, described in JP-A-60-176906, etc.
On a smooth surface, hydrolyze the coating with water or steam,
Dispersion-containing fine-grained metal compounds with genus alkoxide partial hydrolyzate as matrix
After obtaining a thin film-like substance, this is peeled off with a scraper or the like and fired in air.
Thus, a flaky metal dispersedly containing a fine metal compound having a metal oxide matrix.
Getting a compound But I can do it. Also, if the firing is performed in a reducing atmosphere such as in the presence of carbon, mainly the metal carbide
A flaky metal compound containing the fine metal compound dispersed therein as a matrix is obtained. Furthermore, if calcination is performed in a nitrogen atmosphere in the presence of carbon, metal nitrides are mainly
Thus, a flaky metal compound containing dispersed fine metal compounds is obtained. Further, a fine metal compound is dispersed in an aqueous solution of titanium sulfate, and US Pat. No. 3,018,186
Fine metal compounds by a method for producing a flaky material as shown in
Can be obtained. Furthermore, by changing the atmosphere during firing in the same manner as described above, fine metal compound
Flaky titanium carbide or titanium nitride containing a dispersed material. In addition, fine metal compounds may be used in inorganic glass such as water glass or aluminum phosphate solution.
After dispersing in the molecule, it may be sliced by a method shown in Japanese Patent Application No. 61-82486. At this time, the flaky metal compound obtained for stabilization in air is fired.
Is also good. Thus, obtaining a flaky metal compound containing a fine metal compound dispersed therein
In particular, the matrix is partially hydrolyzed with metal oxides, nitrides and alkoxides.
In the case of a metal or carbide, the above-described method of dispersing a fine metal compound in a metal alkoxide solution and then hydrolyzing the metal compound is the most preferable.
It is also recommended in terms of quality uniformity and productivity. The flaky metal compound thus obtained is then adjusted to a specific shape. The shape is not unique depending on the application, but usually an average thickness of about 0.1 μm to about 5 μm,
Preferably from 0.2 μm to 2 μm, average size from about 1 μm to about 500 μm, preferably 3 μm
μm to 100 μm. If the thickness of the flakes is less than about 0.1 μm, the mechanical strength is low, and it is not practical. If the thickness is more than about 5 μm, it will be sticky to the skin and the feel during use will be poor. If the average size of the flakes is smaller than about 1 μm, it is difficult to maintain the shape of the flakes,
If it exceeds 0 μm, it will be easily broken. The aspect ratio of the flaky metal compound {Aspect ratio = (average size of flake) / (average thickness of flake)} is preferably 3 or more and 100 or less. When the aspect ratio is 3 or less, the effect of improving ductility and the like is not so high, and is 100 or more.
In this case, it is not preferable because it is easily broken mechanically. Since flakes generally have a distribution, in the present invention, the size is the average size, that is,
The value of (the maximum length of the slice and the minimum diameter of the slice + the minimum length of the slice) / 2 for 100 slices
The thickness is also defined as the average thickness, that is, the average value of 100 slices.
Specified. As a method for adjusting the flaky metal compound to a specific size, the above-described method is used.
Flaky metal compound obtained by dry ball mill, wet ball mill, vibration
Grinding with a mill, roll mill, zet mill, etc. and / or gyro shifter or
Vibrating sieves like hammer screens, spiral classifiers and hydraulic classifiers
Wet classification, dry classification such as a dynamic or centrifugal air classifier, or floating
Well-known methods such as a method of combining one or more of the classification steps such as a beneficiation method
A method (for example, Handbook of Powder Engineering, edited by Koichi Iitani, published by Asakura Shoten) may be adopted. In using the flaky metal compound of the present invention, a matrix is mixed and dispersed in the matrix.
The fine metal compound is selected according to its use. For example, if the application requires heat resistance of 200 ° C or higher, the matrix
Metal oxides, nitrides, carbides, inorganic polymers and the like are suitable. In general, UV shielding by light scattering is based on the refractive index of the matrix and dispersed fine particles.
The greater the difference, the more effective. The minimum to achieve this effect is to disperse the matrix and the matrix.
The difference in the refractive index of the fine metal compound must be at least 0.1 or more, preferably 0.3 or more
It is. When the ratio is less than 0.1, the light beam is not sufficiently scattered and the effect of blocking ultraviolet rays is not so much. For example, when silica having a refractive index of 1.4 to 1.5 is used as a matrix,
Alumina having a refractive index of 1.76, more preferably zinc oxide having a refractive index of 2.0, or titanium oxide having a refractive index of 2.5 can be effectively used as the fine metal compound to be compacted. Conversely, a substance having a high refractive index such as zinc oxide or titanium oxide is used as a matrix.
In this case, select a silica or alumina with a low refractive index as the fine metal compound to be dispersed.
You can choose. In addition, as the fine metal compound or flaky metal compound, the oxides and carbides described above.
, Nitrides, etc., also change the refractive index arbitrarily according to the composition ratio.
Useful for being able. For example, a mixed oxide having a weight ratio of alumina / silica = 90/10 has a refractive index of about 1.7.
In the case of 80/20, it is about 1.65. The refractive index of the titania / silica mixed oxide is about 1.8 when the weight ratio is 50/50.
, 25/75, about 1.6. The average particle size of the fine metal compound used in the present invention is from about 0.005 μm to about 0.5 μm.
More preferably, it is about 0.008 μm to about 0.1 μm. The upper limit of the size depends on the thickness of the flaky metal compound in which it is dispersed, but is approximately 0.5 μm.
If it is larger than m, it is difficult to disperse it uniformly in the flaky material,
Since the wavelength is larger than the wavelength of the line, the ultraviolet scattering ability is reduced. On the other hand, if it is smaller than about 0.005 μm, the difference between the matrix and the particles will not be significant. The combination of the flaky metal compound and the fine metal compound and the ratio
Depends on size and purpose of use. For example, for applications of ultraviolet shielding that emphasize transparency, high refractive index
As small as possible and uniformly disperse ultra-fine metal compounds of about 0.1μm or less
Is preferred, and when transparency is not important, the particle size and compounding of the fine metal compound
There is not much restriction on quantity. If the volume fraction of the dispersed particles exceeds 50%, the substances that make up the dispersed particles
And the properties of the flake. Therefore, if it is possible to form a matrix with the dispersed particle constituent material and to form the dispersed particles with the matrix constituent material, that method is preferred.
May be easy to build. Generally, this reversal is not always possible, and considering the ease of manufacturing, etc.
The volume fraction of the fine metal compound is determined by the flaky metal compound that disperses the fine metal compound.
A range from about 0.1% to about 50%, preferably about 1% to about 30%, is practical. If the amount of the fine metal compound added to the flaky material is large,
Flakes made of a metal compound that constitutes
If it is difficult to construct, on the other hand, if there are few
For example, the scattering of ultraviolet rays becomes insufficient, which is not preferable. Further, when a colored flaky metal compound is intended, a fine metal compound and / or
Is a flaky metal compound of a matrix, especially a fine metal compound
A compound may be used. For example, if a red pigment such as iron oxide is used, it can be colored red, green No. 2, chrome oxide and the like can be colored green, and molybdenum oxide and the like can be colored blue.
You. The flaky metal compound thus obtained is used to protect the skin from harmful ultraviolet rays.
Day cream, foundation, white powder, lipstick, eye shadow, etc.
Various UV shielding agents from basic cosmetics to makeup cosmetics are compounded
It can be applied to cosmetics, and the compounding ratio varies depending on the type of cosmetics.
But usually in the range of about 0.5% to about 70% by weight, preferably about 2% to about 40% by weight
Is added. If the amount of the flaky metal compound in the cosmetic is less than 0.5% by weight, the ultraviolet shielding ability is poor.
On the other hand, when the content exceeds 70% by weight, the feeling at the time of use, such as a moist feeling, is reduced. In addition, salicylic acid derivatives, benzoic acid derivatives
Derivatives, cinnamic acid derivatives, benzophenone derivatives, titanium oxide, zinc oxide,
A known ultraviolet shielding agent such as phosphorus, aluminum oxide, calcium carbonate or the like may be added and used together with the flaky metal compound. Further, in the case of blending an ultraviolet shielding agent comprising a flaky metal compound in the present invention
Surface coating with oils and fats usually used to improve dispersibility and usability
Surface treatment such as surface treatment, surfactant treatment or metal soap such as zinc stearate.
You may mix after performing. As a method of blending these flaky metal compounds into cosmetics, a known mixing method is used.
That is, using a Henschel mixer, a ribbon mixer, a V-type blender, etc.
it can. <Effect of the Invention> The flaky metal compound of the present invention described in detail above has an excellent ability to block ultraviolet rays having a wavelength of 400 nm or less.
As compared to fine metal oxides, it has better dispersibility in resin and vehicle.
Provides excellent usability such as spreadability and spreadability in application, and alters coexisting organic substances.
As it is not used in cosmetics, it can be used not only in cosmetics but also in additives for paints, agricultural films, etc.
However, it is applicable and its industrial value is extremely large. <Examples> Hereinafter, the present invention will be described in more detail with reference to examples.
There is no restriction. Examples 1-3, Comparative Examples 1-2 TiCl Four After reacting 19 g (0.1 mol) with 6.4 g (0.2 mol) of methanol, it is mixed with 42 g of water.
Ultrafine silica (average particle size 0.012 μm) (Nippon Aerosil)
Ultrasonic mixing was performed so that the ratios shown in Table 1 were obtained. After immersing the washed slide glass in this solution and pulling it up at a speed of 75 cm / min,
This was dried in an air bath at 120 ° C. for 30 minutes to obtain a flake. The obtained flakes are baked at 300 ° C. for 5 hours, then at 700 ° C. for 2 hours, and the average size is 7 μm.
m, a flaky titanium oxide containing dispersed fine silica having an average thickness of 0.8 μm was obtained. FIG. 1 shows the measurement results of the spectral transmittance of the obtained flaky titanium oxide. In addition, flaky titanium oxide prepared without adding ultrafine silica was used as Comparative Example 1,
Further, each of the ultrafine silica particles was used as Comparative Example 2 to measure the spectral transmittance. FIG. 1 shows the measurement results. The spectral transmittance was 0.02 g of sample powder mixed with 0.47 g of low-density polyethylene powder,
Knead and melted with this roll (temperature: 100-160 ° C) to produce a film with a thickness of about 50 µm.
As a reference film, a low-density polyethylene
After producing the film, both films were measured with a spectrophotometer according to JIS K0115.
. (Here, the refractive index of fine silica and flaky titanium oxide is 1.46 and 2.5.
The difference in rates is 1.04. Comparative Examples 3 to 5 Rutile-type titanium oxide having an average particle diameter of 0.4 μm (manufactured by Ishihara Sangyo Co., Ltd.), average particle diameter of 0.3 μm
Anatase-type titanium oxide (made by Sakai Chemical Co., Ltd.) and oxidation of fine particles with an average particle diameter of 0.03 μm
The spectral transmittance of titanium (Nippon Aerosil) was measured. The results are shown in FIG. 2 as Comparative Examples 3 to 5. Example 4, Comparative Example 6 A solution of Si in the solution was added to a 40% by weight ethanol solution of tetraethylorthosilicate.
After adding 2 times mol of formic acid and stirring and mixing at 70 ° C for 3 hours, the average particle size
0.03 μm ultrafine titanium oxide (Nippon Aerosil)
The mixture was ultrasonically mixed so as to obtain a weight%. Next, the washed slide glass was immersed in this solution. After raising this glass at 70 cm / min, it is dried at 90 ° C for 30 minutes in an air bath.
A transparent and smooth surface flake having an average size of 100 μm and an average thickness of 1.7 μm was obtained.
. This is baked at 450 ° C. for 30 minutes, and has an average size of 60 μm and an average thickness of 0.9 μm.
Flaky silica containing ultrafine titanium oxide dispersed therein was obtained. Furthermore, this is ultrasonically pulverized to obtain an average size of 35 μm and an average thickness of 0.9 μm.
Flaky silica containing finely divided titanium oxide was obtained. Measurement of spectral transmittance of flaky silica containing ultrafine titanium oxide dispersed
The results are shown in FIG. An average size of 35 μm, similarly prepared without adding ultra-fine titanium oxide,
The spectral transmittance of flaky silica having an average thickness of 0.9 μm was measured as Comparative Example 6. The results are also shown in FIG. (Note that the refractive index of ultrafine titanium oxide and flaky silica is 2.5 and 1.46.
Is 1.04. Example 5 27 g of propylene was added to 200 g of a 40% by weight ethanol solution of titanium tetraethoxide.
5% by weight alumina based on the amount of on-acid and titanium in the liquid (in terms of titanium oxide)
Add 1.4 g of fine alumina (Sumitomo Chemical Co., Ltd.) with an average particle size of 0.1 μm as above, and at 70 ° C for 3 hours
After stirring and mixing, the washed slide glass was immersed in this liquid. After raising this glass at 50 cm / min, it is dried in an air bath at 90 ° C. for 30 minutes and then 450
Fine aluminum with average size of 20μm and average thickness of 0.8μm
Thus, a flaky titanium oxide containing Na in a dispersed manner was obtained. This was further ultrasonically crushed and elutriated to make the average size 10 μm. FIG. 3 shows the measurement results of the spectral transmittance of the obtained flaky titanium oxide. The spectral transmittance of the flaky titanium oxide prepared similarly without adding alumina was
It was the same as Comparative Example 1. (The refractive index of fine-grained alumina and flaky titanium is 1.76 and 2.5, and the difference between the refractive indices is 0.
74. Example 6, Comparative Example 7 Phosphoric acid was added to an aqueous solution of monobasic aluminum phosphate having a phosphorus content of 7% by weight and a molar ratio of AI / P of 3.
Fine particle titanium oxide having an average particle size of 0.03 μm to be 5% by weight with respect to aluminum
Ultrasonic mixing. Then, after immersing the washed slide glass in the solution, the glass is pulled up at 50 cm / min, and then dried in an air bath at 90 ° C. for 30 minutes.
It was dried, scraped off with a scraper, and thinned. The fine-grained titanium oxide-dispersed flaky aluminum phosphate thus obtained is averaged.
Was 20μ in size and 2μ in thickness. Measurement results of spectral transmittance at 300 nm and 500 nm of the obtained flaky aluminum phosphate
Are shown in Table 2. In addition, 30% of flaky aluminum phosphate prepared in the same manner without adding titanium oxide
The spectral transmittances at 0 nm and 500 nm are shown in Table 2 as Comparative Example 7. Example 7 To 200 g of a 40% by weight ethanol solution of titanium tetraethoxide was added 27 g of propylene.
Add onic acid and 2.8 g of fine zinc oxide with an average particle size of 0.03 μm, and stir and mix at 70 ° C for 3 hours
After that, the washed slide glass was immersed in this solution. After pulling up this glass at 50 cm / min, it is dried in an air bath at 90 ° C. for 30 minutes and baked at 450 ° C. for 30 minutes to give an average size of 15 μm.
A fine zinc oxide dispersed flaky titanium oxide having an average thickness of 0.8 μm was obtained. More than this
The particles were sonicated and elutriated to make the average size 10 μm. Table 2 shows the spectral transmittances at 300 nm and 500 nm. Example 8, Comparative Examples 8, 9 To 200 g of a 40% by weight ethanol solution of titanium tetraethoxide, 27 g of propylene was added.
Addition of on-acid and 40% by weight ethanol solution of tetraethyl orthosilicate
A solution obtained by adding formic acid twice as much as Si in the solution to the solution is mixed with TiO 2 by volume ratio. Two / SiO Two = 75/25 (
Example 8 ), TiO Two / SiO Two = 50/50 (Comparative example 8 , 9 ) And mix at 70 ° C
After stirring and mixing for a period of time, fine alumina particles with an average particle size of 0.1 μm (Sumitomo Chemical Co., Ltd.)
(1.4 g) was added so that the ratio shown in Table 2 was obtained, followed by ultrasonic mixing. Next, the washed slide glass was immersed in this solution. Draw this glass at 75c / min
After cleaning, dried in air bath at 90 ℃ for 30 minutes, average size 100μm, average thickness 1.7μm
Was obtained. This is baked at 450 ° C. for 30 minutes, and has an average size of 600 μm and an average thickness of 0.9 μm.
Thus, flaky titania-silica dispersed with titanium oxide was obtained. Furthermore, this is ultrasonically crushed
Titanium oxide dispersed flaky titania having an average size of 10 μm and an average thickness of 0.9 μm
Silica was obtained. Table 2 shows the spectral transmittance at 305 nm and 500 nm. Examples 9, 10 to 12 Using the flaky titanium oxide dispersion-containing fine silica prepared in Example 2,
Adjusted the powder foundation. For comparison, flaky titanium oxide of Comparative Example 1, commercially available rutile having an average particle size of 0.4 μm
Powdered titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.), commercially available fine titanium oxide with an average particle size of 0.03 μm (
A powder foundation containing Nippon Aerosil Co., Ltd.) was prepared. With respect to the products of Example 9 and Comparative Examples 10 to 12 thus obtained, the stability, purple
An outside line shielding effect and a sensory evaluation were performed. Table 3 shows the results. Example 10 and Comparative Example 13 Using the flaky titanium oxide containing fine silica prepared in Example 2, pressing was performed.
Adjusted powder. For comparison, a pressed powder mainly containing talc was prepared. Stability, ultraviolet light of the products of Example 10 and Comparative Example 13 thus obtained
The shielding effect and the sensory effect were implemented. Table 4 shows the results. In addition, the measuring method was calculated | required by the following methods. Stability: The cosmetics were stored in a room without temperature control for one year and examined for deterioration. Ultraviolet ray shielding effect: (SPF value sunscreen index 2mg / cm Two Or 2μl / cm Two The coated part and the uncoated part are medical ultraviolet light irradiation equipment manufactured by Toko Electric Co., Ltd. {M-DMR-1 type; The minimum erythema generation energy of each part was measured using an ultraviolet intensity meter (UVR-305 / 365 / D type) manufactured by Tokyo Kogaku Kikai Co., Ltd. It is shown as an energy ratio. Sensory test: Twenty women were used for two weeks, and the average score of the results was evaluated according to a scale of 5 to 5 points.
【図面の簡単な説明】
第１図〜第３図は本発明の薄片状物質及び市販の金属酸化物粉末等の300nm〜6
00nmにおける分光透過率を示したものである。BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 to 3 show 300 nm to 6 nm of a flaky material of the present invention and a commercially available metal oxide powder.
It shows the spectral transmittance at 00 nm.
Claims (1)
粒金属化合物を体積分率で1〜30％分散含有してなる薄片状金属化合物。(2) 微粒金属化合物の平均粒子径が0.005μｍ〜0.5 μｍであることを特徴とす
る特許請求の範囲第１項記載の薄片状金属化合物。 (3) マトリクスを構成する薄片状金属物質の平均の厚みが0.1μｍ〜５μｍ、平
均の大きさが１μｍ〜500μｍであることを特徴とする特許請求の範囲第１項記
載の薄片状金属化合物。 (4) 微粒金属化合物が微粒金属酸化物であることを特徴とする特許請求の範囲
第１項記載の薄片状金属化合物。 (5) 微粒金属酸化物の粒径が0.005μｍ〜0.5μｍであることを特徴とする特許
請求の範囲第４項記載 の薄片状金属化合物。 (6) 薄片状金属化合物が２価以上の金属、該金属の金属酸化物、金属窒化物、
金属炭化物、金属水酸化物、金属塩化物、金属アルコキシド、金属キレート化合
物、有機金属化合物の部分加水分解物または無機高分子化合物よりなるグループ
より選ばれた少なくとも１種の薄片状金属化合物であることを特徴とする特許請
求の範囲第１項記載の薄片状金属化合物。 (7) 薄片状金属化合物が薄片状金属酸化物であることを特徴とする特許請求の
範囲第１項記載の薄片状金属化合物。 (8) 薄片状金属化合物に、薄片状金属化合物との屈折率の差が0.1以上である微
粒金属化合物を体積分率で1〜30％分散含有してなる薄片状金属化合物を配合し
てなる化粧料。 (9) 微粒金属化合物の平均粒子径が0.005μｍ〜0.5μｍであることを特徴とす
る特許請求の範囲第８項記載の化粧料。 (10) マトリクスを構成する薄片状金属化合物の平均の厚みが0.1μｍ〜５μｍ
、平均の大きさが１μｍ 〜500μｍであることを特徴とする特許請求の範囲第８項記載の化粧料。 (11) 微粒金属化合物が微粒金属酸化物であることを特徴とする特許請求の範囲
第８項記載の化粧料。 (12) 微粒金属酸化物の粒径が0.005μｍ〜0.5μｍであることを特徴とする特許
請求の範囲第１１項記載の化粧料。 (13) 薄片状金属化合物が２価以上の金属、該金属の金属酸化物、金属窒化物、
金属炭化物、金属水酸化物、金属塩化物、金属アルコキシド、金属キレート化合
物、有機金属化合物の部分加水分解物または無機高分子化合物よりなるグループ
より選ばれた少なくとも１種の薄片状金属化合物であることを特徴とする特許請
求の範囲第８項記載の化粧料。 (14) 薄片状金属化合物が薄片状金属酸化物であることを特徴とする特許請求の
範囲第８項記載の化粧料。 Claims: (1) A flaky metal compound comprising a flaky metal compound containing 1 to 30% by volume fraction of a fine metal compound having a difference in refractive index from the flaky metal compound of 0.1 or more. Compound. (2) The fine metal compound has an average particle diameter of 0.005 μm to 0.5 μm.
The flaky metal compound according to claim 1. (3) The average thickness of the flaky metal material constituting the matrix is 0.1 μm to 5 μm,
2. The method according to claim 1, wherein the average size is 1 μm to 500 μm.
The flaky metal compound shown. (4) Claims, wherein the fine metal compound is a fine metal oxide.
2. The flaky metal compound according to claim 1. (5) Patents characterized in that the particle diameter of the fine metal oxide is 0.005 μm to 0.5 μm
The flaky metal compound according to claim 4 . (6) the flaky metal compound is a divalent or higher-valent metal, a metal oxide, a metal nitride of the metal,
Metal carbide, metal hydroxide, metal chloride, metal alkoxide, metal chelate compound
Group consisting of products, partial hydrolysates of organometallic compounds or inorganic high molecular compounds
Patent at least one flaky metal compound selected from the group consisting of:
2. The flaky metal compound according to claim 1. (7) The flaky metal compound is a flaky metal oxide.
2. The flaky metal compound according to claim 1. (8) The flaky metal compound has a refractive index difference of 0.1 or more from the flaky metal compound.
A flaky metal compound containing 1-30% dispersed by volume fraction of a granular metal compound
Makeup cosmetics. (9) The fine metal compound has an average particle diameter of 0.005 μm to 0.5 μm.
The cosmetic according to claim 8, wherein (10) The average thickness of the flaky metal compound constituting the matrix is 0.1 μm to 5 μm
9. The cosmetic according to claim 8 , wherein the average size is 1 μm to 500 μm . (11) The claim, wherein the fine metal compound is a fine metal oxide.
Item 9. The cosmetic according to item 8, (12) Patents characterized in that the particle size of the fine metal oxide is 0.005 μm to 0.5 μm
The cosmetic according to claim 11. (13) The flaky metal compound is a divalent or higher-valent metal, a metal oxide, a metal nitride of the metal,
Metal carbide, metal hydroxide, metal chloride, metal alkoxide, metal chelate compound
Group consisting of products, partial hydrolysates of organometallic compounds or inorganic high molecular compounds
Patent at least one flaky metal compound selected from the group consisting of:
9. The cosmetic according to claim 8, wherein the cosmetic is a cosmetic. (14) The flaky metal compound is a flaky metal oxide,
Item 9. The cosmetic according to item 8, wherein
Family
ID=
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