JP5872825B2 - Metal oxide / zinc oxide solid solution particle production method, spherical powder production method, coated spherical powder production method, and cosmetic production method - Google Patents
Metal oxide / zinc oxide solid solution particle production method, spherical powder production method, coated spherical powder production method, and cosmetic production method Download PDFInfo
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- JP5872825B2 JP5872825B2 JP2011198551A JP2011198551A JP5872825B2 JP 5872825 B2 JP5872825 B2 JP 5872825B2 JP 2011198551 A JP2011198551 A JP 2011198551A JP 2011198551 A JP2011198551 A JP 2011198551A JP 5872825 B2 JP5872825 B2 JP 5872825B2
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- Prior art keywords
- spherical powder
- zinc oxide
- production method
- particles
- spherical
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 97
- 239000000843 powder Substances 0.000 title claims description 92
- 238000004519 manufacturing process Methods 0.000 title claims description 57
- 239000002245 particle Substances 0.000 title claims description 55
- 239000011787 zinc oxide Substances 0.000 title claims description 46
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 33
- 150000004706 metal oxides Chemical class 0.000 title claims description 33
- 239000006104 solid solution Substances 0.000 title claims description 25
- 239000002537 cosmetic Substances 0.000 title claims description 23
- -1 amine compound Chemical class 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 229910052751 metal Chemical class 0.000 claims description 13
- 239000002184 metal Chemical class 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003752 zinc compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000516 sunscreening agent Substances 0.000 description 7
- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 208000007578 phototoxic dermatitis Diseases 0.000 description 6
- 231100000018 phototoxicity Toxicity 0.000 description 6
- 230000000475 sunscreen effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 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 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 235000019792 magnesium silicate Nutrition 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
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- 208000024891 symptom Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
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Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、金属酸化物・酸化亜鉛固溶体粒子の製造方法と、金属酸化物・酸化亜鉛固溶体粒子を集積する球状粉体の製造方法と、その球状粉体に疎水性の化合物を表面被覆する被覆球状粉体の製造方法と、球状粉体及び／又は被覆球状粉体を配合する化粧料の製造方法に関するものである。 The present invention relates to a method for producing metal oxide / zinc oxide solid solution particles , a method for producing a spherical powder in which metal oxide / zinc oxide solid solution particles are accumulated, and a coating for coating the spherical powder with a hydrophobic compound. and method for producing spherical powder, a process for producing a cosmetic formulation spherical powder and / or coated spherical powder.
近年、酸化亜鉛粉体が、例えば日焼け止め剤やファンデーション、アイシャドウ、口紅などのメイクアップ化粧料において、紫外線遮蔽剤として、あるいはカバー力を付与するためなどに用いられている。また、球状の粒子は、皮膚に塗布した時に感触を向上させることを目的として用いられ、表面に小さな凹凸を付与された粒子は、ソフトフォーカス性を向上させることを目的として用いられている。また、上記酸化亜鉛粉体はフィラーなどの工業用途としても使用され、剛性の付与や制振効果の付与、表面平滑性の付与などを目的として配合されている。 In recent years, zinc oxide powder has been used as an ultraviolet shielding agent or for providing a covering power in makeup cosmetics such as sunscreens, foundations, eye shadows, and lipsticks. In addition, spherical particles are used for the purpose of improving the feel when applied to the skin, and particles having small irregularities on the surface are used for the purpose of improving soft focus properties. Moreover, the said zinc oxide powder is used also for industrial uses, such as a filler, and is mix | blended for the purpose of provision of rigidity, the provision of a damping effect, the provision of surface smoothness, etc.
これら化粧品やフィラーなどに用いられる酸化亜鉛粉体の粒子としては、粒子の形状及び粒子径が均一なもの、表面に小さな凹凸を付与することによって高いソフトフォーカス性が付与されたもの、さらには高い紫外線遮蔽効果をもつものが求められている。 As particles of zinc oxide powder used in these cosmetics and fillers, particles having a uniform shape and particle diameter, those imparted with high soft focus by imparting small irregularities on the surface, and high What has an ultraviolet shielding effect is desired.
しかしながら、現在用いられている酸化亜鉛粉体の粒子は、粒子径の制御が困難であり、粒度分布に幅があるものがほとんどで、形態も不均一である。また、単分散した状態ではなく、粒子が複数重なり合った凝集体を形成しており、酸化亜鉛の特性を十分に発揮できないという問題点がある。また、酸化亜鉛は特に皮膚に塗布した時の感触が悪いなどの問題点がある。このため、粒子径が制御できるとともに、形態を球状に制御でき、皮膚に塗布した時の感触が良く、紫外線遮蔽効果の高い酸化亜鉛粒子を提供することが求められている。 However, most of the particles of zinc oxide powder currently used are difficult to control the particle diameter, have a wide particle size distribution, and have a non-uniform form. In addition, there is a problem that not a monodispersed state but an aggregate in which a plurality of particles overlap each other is formed, and the characteristics of zinc oxide cannot be sufficiently exhibited. In addition, zinc oxide has a problem that it feels bad when applied to the skin. For this reason, while being able to control a particle diameter, a form can be controlled to spherical shape, the touch when it apply | coats to skin is provided, and it is calculated | required to provide a zinc oxide particle with a high ultraviolet-ray shielding effect.
一方、酸化亜鉛粉体の製造方法については、各種の方法が知られている。一般的には、乾式法としてフランス法と呼ばれる製造方法が知られている。この方法は、溶融させた金属亜鉛をレトルトの中で約１０００℃に加熱し、発生する亜鉛蒸気を空気で酸化させ、これを送風機で空冷管に送って冷却し、サイクロン及びバグフィルターで分離、捕集する方法である。一方、湿式法としては、ドイツ法が知られている。この方法は、硫酸亜鉛または塩化亜鉛の水溶液にソーダ灰溶液を加えてできる白色の塩基性炭酸亜鉛の沈殿を水洗乾燥後焼成して製造する方法である。しかし、これらの方法で作製された酸化亜鉛はサイズが不均一であるという問題点がある。また、高温での処理が必要になるため、環境に与える影響があるとともに、反応装置がコスト高になるという問題点がある。 On the other hand, various methods are known for producing zinc oxide powder. In general, a production method called French method is known as a dry method. In this method, molten metal zinc is heated to about 1000 ° C. in a retort, the generated zinc vapor is oxidized with air, this is sent to an air cooling tube with a blower, cooled, and separated with a cyclone and a bag filter. It is a method of collecting. On the other hand, the German method is known as a wet method. In this method, a white basic zinc carbonate precipitate formed by adding a soda ash solution to an aqueous solution of zinc sulfate or zinc chloride is washed with water, dried, and calcined. However, zinc oxide produced by these methods has a problem that the size is non-uniform. In addition, since treatment at a high temperature is required, there are problems in that the environment is affected and the cost of the reaction apparatus is increased.
また、球状の酸化亜鉛を合成する方法としては、ミスト焼成法と呼ばれる方法が知られている。しかしながら、この方法では中空体ができやすく、かつ球状の粒子を得ることが困難である。 As a method for synthesizing spherical zinc oxide, a method called a mist firing method is known. However, this method makes it easy to form a hollow body and it is difficult to obtain spherical particles.
特許文献１においては、低温希薄亜鉛蒸気を酸素と接触させることによって、球状の酸化亜鉛粒子を製造する方法が提案されている。しかしながら、この方法では、高温の亜鉛溶湯に不活性ガスを吹き込むことによって亜鉛蒸気を発生させる必要がある。また、その亜鉛蒸気には毒性があるという問題点もある。 Patent Document 1 proposes a method for producing spherical zinc oxide particles by bringing low temperature dilute zinc vapor into contact with oxygen. However, in this method, it is necessary to generate zinc vapor by blowing an inert gas into a hot zinc melt. There is also a problem that the zinc vapor is toxic.
また、特許文献２においては、有機亜鉛化合物を用いた球状酸化亜鉛の合成方法が提案されている。しかしながら、この方法では焼成時の温度を高く設定する必要がある。また、出発原料に有機亜鉛化合物を使用しているため、焼成過程で有毒ガスが発生する恐れがある。更に、得られる酸化亜鉛の収率が低く、しかも他の形状の酸化亜鉛との混在化でしか得ることができないという問題点がある。 In Patent Document 2, a method for synthesizing spherical zinc oxide using an organic zinc compound is proposed. However, in this method, it is necessary to set a high temperature during firing. Further, since an organic zinc compound is used as a starting material, toxic gas may be generated during the firing process. Furthermore, there is a problem that the yield of the obtained zinc oxide is low and can only be obtained by mixing with zinc oxide of other shapes.
また、酸化亜鉛には光触媒活性があることが知られている。酸化亜鉛は太陽光中の紫外線を吸収して、肌に対する太陽光中の紫外線の直接的な影響を除去できる半面、大量に発生する自由電子や正孔に由来する活性酸素・フリーラジカルによって様々な皮膚に対する悪影響、すなわち光毒性が懸念されている。そこで、光触媒活性粉末における主に活性酸素・フリーラジカルによる光毒性に対する防御方法として、光触媒活性粉末の表面改質や表面処理、さらにはラジカルトラップ剤の配合などが提案されているが、いまだ完全ではなく、光触媒活性の低い酸化亜鉛粒子が求められている。 Zinc oxide is known to have photocatalytic activity. Zinc oxide absorbs ultraviolet rays in sunlight and can remove the direct influence of ultraviolet rays in sunlight on the skin. On the other hand, it varies depending on active oxygen and free radicals derived from a large amount of free electrons and holes. There are concerns about adverse effects on the skin, that is, phototoxicity. Thus, surface protection and surface treatment of photocatalytically active powders, and the incorporation of radical trapping agents have been proposed as methods for protecting against phototoxicity caused mainly by active oxygen and free radicals in photocatalytically active powders. There is no need for zinc oxide particles having low photocatalytic activity.
本発明は、前述のような問題点に鑑みてなされたもので、環境に優しく、簡便で低コストな方法にて、形態を球状に制御できると同時に粒子径の制御もでき、粒子表面に小さな凹凸を付与することができ、かつ光触媒活性を低減することのできる金属酸化物・酸化亜鉛固溶体粒子の製造方法を提供し、またその金属酸化物・酸化亜鉛固溶体粒子を集積する球状粉体の製造方法を提供し、さらに、この球状粉体に疎水性の化合物を表面被覆することにより疎水性を付与する被覆球状粉体の製造方法を提供し、併せて球状粉体及び／又は被覆球状粉体を配合することによって、紫外線遮蔽効果が高く、ソフトフォーカス性に優れ、光触媒活性を抑えたことにより活性酸素・フリーラジカルなどに基づく光毒性が抑制され、皮膚老化や皮膚症状の悪化などを未然に防止でき、使用感の優れた化粧料の製造方法を提供することを目的とするものである。 The present invention has been made in view of the above-described problems, and can be controlled in a spherical shape and at the same time with a simple and low-cost method, and at the same time, the particle diameter can be controlled, and the particle surface is small. Provided is a method for producing metal oxide / zinc oxide solid solution particles capable of imparting irregularities and capable of reducing the photocatalytic activity, and also producing spherical powder that accumulates the metal oxide / zinc oxide solid solution particles. It provides a method further provides a method for producing coated spherical powder to impart hydrophobicity by the spherical powder surface coating the hydrophobic compounds, collectively spherical powder and / or coated spherical powder Contains a high UV-shielding effect, excellent soft focus properties, and suppressed photocatalytic activity, which suppresses phototoxicity based on active oxygen and free radicals, resulting in poor skin aging and poor skin symptoms. Etc. can be prevented from occurring, it is an object to provide a manufacturing method excellent cosmetic of feeling.
前記目的を達成するために、本発明者らは鋭意研究した結果、水溶性亜鉛化合物とグリコールとアミン化合物及び電荷が＋４以下の金属イオンの金属塩を用い、ソフト溶液反応にて、粒子を球状に制御することができ、粒子径を均一に制御することができる金属酸化物・酸化亜鉛固溶体粒子の製造方法を見出した。
また、上記製造方法にて得られた金属酸化物・酸化亜鉛固溶体粒子を３００℃から１５００℃にて焼成処理しても良く、この焼成処理を行うことにより、比表面積を制御し、吸油量や結晶性を制御することができる。
さらに、得られた金属酸化物・酸化亜鉛固溶体粒子が集積された球状粉体をポリシロキサン、アルキルシラン化合物、アルキルチタネート化合物、フッ素化合物などの化合物で表面被覆することにより、疎水性を有する被覆球状粉体を得ることができ、また、その被覆球状粉体を化粧料に配合することによって、紫外線遮蔽効果、ソフトフォーカス性や使用感に優れ、更に光毒性が抑制された化粧料を提供することが可能であることを見出し、本発明を完成するに至った。
In order to achieve the above-mentioned object, the present inventors have intensively studied. As a result, the particles were made spherical by a soft solution reaction using a water-soluble zinc compound, a glycol, an amine compound, and a metal salt of a metal ion having a charge of +4 or less. The present inventors have found a method for producing metal oxide / zinc oxide solid solution particles that can be controlled to have a uniform particle size.
In addition, the metal oxide / zinc oxide solid solution particles obtained by the above production method may be subjected to a firing treatment at 300 ° C. to 1500 ° C., and by performing this firing treatment, the specific surface area is controlled, Crystallinity can be controlled.
Furthermore, the spherical powder in which the obtained metal oxide / zinc oxide solid solution particles are collected is surface-coated with a compound such as polysiloxane, an alkylsilane compound, an alkyl titanate compound, or a fluorine compound, so that the coated spherical powder has hydrophobicity. It is possible to obtain a powder, and by providing the coated spherical powder in a cosmetic, it is possible to provide a cosmetic that is excellent in ultraviolet shielding effect, soft focus property and feeling of use, and further has reduced phototoxicity. As a result, the present invention has been completed.
要するに、第１発明による金属酸化物・酸化亜鉛固溶体粒子の製造方法は、酸化亜鉛に電荷が＋４以下の金属イオンをドープした球状粒子よりなる金属酸化物・酸化亜鉛固溶体粒子の製造方法であって、水溶性亜鉛化合物とグリコールとアミン化合物と、電荷が＋４以下の金属塩とを混合し、５０℃〜１００℃でのソフト溶液反応を行うことにより合成し、該ソフト溶液反応にて、粒子を球状に制御するとともに、粒子径を均一に制御し、その後４００℃〜１５００℃で焼成することを特徴とするものである。ここで、ドープとは、何らかの形で酸化亜鉛粉体に金属酸化物を付加することを意味し、その付加状態を問うものではなく、酸化亜鉛に金属酸化物の一部が入り込んでいる状態も、酸化亜鉛粉体に金属酸化物が被覆されている状態も、このドープの概念に包括される。
上記金属酸化物・酸化亜鉛固溶体粒子の製造に際しては、水溶性亜鉛化合物、グリコール、アミン化合物及びドープする金属塩以外に、ｐＨを調整するために、水酸化ナトリウムなどを加えても構わない。
In short , the method for producing metal oxide / zinc oxide solid solution particles according to the first invention is a method for producing metal oxide / zinc oxide solid solution particles comprising spherical particles doped with metal ions having a charge of +4 or less. , a water-soluble zinc compound with a glycol and an amine compound, charges are mixed with +4 following metal salts were synthesized by performing a soft solution reaction at 50 ° C. to 100 ° C., at the software solution reaction, the particles controls spherically, uniformly control the particle size, it is characterized in that the calcining thereafter 4 00 ℃ ~1500 ℃. Here, the dope means that a metal oxide is added to the zinc oxide powder in some form, and the addition state is not questioned, and a state where a part of the metal oxide enters the zinc oxide is also included. The state where zinc oxide powder is coated with a metal oxide is also included in the concept of this dope.
In the production of the metal oxide / zinc oxide solid solution particles, sodium hydroxide or the like may be added to adjust the pH in addition to the water-soluble zinc compound, glycol, amine compound, and metal salt to be doped.
第２発明による球状粉体の製造方法は、第１発明の金属酸化物・酸化亜鉛固溶体粒子の製造方法によって一次粒子の粒子径が２〜２００ｎｍの金属酸化物・酸化亜鉛固溶体粒子を製造し、それらを集積して、２０〜５０００ｎｍの球状に形成することを特徴とするものである。 The method for producing a spherical powder according to the second invention produces metal oxide / zinc oxide solid solution particles having a primary particle diameter of 2 to 200 nm by the method for producing metal oxide / zinc oxide solid solution particles of the first invention , These are accumulated and formed into a spherical shape of 20 to 5000 nm .
第３発明による被覆球状粉体の製造方法は、第２発明の球状粉体の製造方法によって製造された球状粉体の表面を、下記一般式（１）にて示されるポリシロキサン、下記一般式（２）にて示されるアルキルアルコキシシラン化合物、下記一般式（３）にて示されるアルキルチタネート化合物、下記一般式（４）、下記一般式（５）又は下記一般式（６）で示されるフッ素化合物から選ばれる１種又は２種以上の化合物で被覆処理することを特徴とするものである。
（式中、ｍは１以上の整数であり、ｎは０以上の整数である。また、Ｒ１〜Ｒ３は水素、アルキル基、アルコキシル基又はフェニル基であり、同一であっても異なっていても良い。）
Ｒ１Ｓｉ（ＯＲ２）３ ・・・・・（２）
（式中、Ｒ１及びＲ２は炭素数が１以上の飽和炭化水素基である。）
（Ｒ１ＣＯＯ）ａＴｉ（ＯＲ２）ｂ ・・・・・（３）
（式中、Ｒ１及びＲ２は炭素数が１以上の飽和炭化水素基である。また、ａ及びｂはそれぞれ１〜３の整数であり、ａ＋ｂ＝４の関係を有する。なお、ここで示されるアルキル基は直鎖状又は分岐状であって、単一鎖長のものであっても複合鎖長のものであっても良い。）
ＣＦ３（ＣＦ２）ｎＣＨ２ＣＨ２Ｓｉ（ＯＲ１）３ ・・・・・（４）
（式中、Ｒ１は炭素数が１以上の飽和炭化水素基であり、ｎは１以上の整数である。）
（式中、ｎは４以上の整数、ｍは１又は２であり、Ｍは１価の金属イオン、アンモニウム塩又はジエタノールアミン塩である。）
（式中、ｎは４以上の整数、Ｍは１価の金属イオン、アンモニウム塩又はジエタノールアミン塩である。）
The method for producing a coated spherical powder according to the third aspect of the invention comprises the step of forming a surface of the spherical powder produced by the method for producing a spherical powder of the second aspect with a polysiloxane represented by the following general formula (1): The alkyl alkoxysilane compound represented by (2), the alkyl titanate compound represented by the following general formula (3), the fluorine represented by the following general formula (4), the following general formula (5) or the following general formula (6). it is characterized in that the coating process with one or more compounds selected from the compounds.
(In the formula, m is an integer of 1 or more, and n is an integer of 0 or more. Also, R 1 to R 3 are hydrogen, an alkyl group, an alkoxyl group, or a phenyl group, and are the same or different. May be.)
R 1 Si (OR 2 ) 3 (2)
(In the formula, R 1 and R 2 are saturated hydrocarbon groups having 1 or more carbon atoms.)
(R 1 COO) a Ti (OR 2 ) b (3)
(In the formula, R 1 and R 2 are each a saturated hydrocarbon group having 1 or more carbon atoms. Further, a and b are each an integer of 1 to 3, and have a relationship of a + b = 4. (The alkyl group shown may be linear or branched and may be of single chain length or of complex chain length.)
CF 3 (CF 2 ) n CH 2 CH 2 Si (OR 1 ) 3 (4)
(In the formula, R 1 is a saturated hydrocarbon group having 1 or more carbon atoms, and n is an integer of 1 or more.)
(In the formula, n is an integer of 4 or more, m is 1 or 2, and M is a monovalent metal ion, ammonium salt or diethanolamine salt.)
(In the formula, n is an integer of 4 or more, and M is a monovalent metal ion, ammonium salt or diethanolamine salt.)
また、第４発明による化粧料の製造方法は、第２発明の球状粉体の製造方法によって製造された球状粉体及び／又は第３発明の被覆球状粉体の製造方法よって製造された被覆球状粉体を配合することを特徴とするものである。 Further, the cosmetic production method according to the fourth invention is a spherical powder produced by the method for producing a spherical powder of the second invention and / or a coated spherical product produced by the method for producing a coated spherical powder of the third invention. It is characterized by blending powder.
第１発明によれば、低コストな方法にて、粒子形態を球状に制御できるとともに、粒子径の制御もでき、かつ粒子表面に小さな凹凸を付与することができ、しかも光触媒活性を低減された金属酸化物・酸化亜鉛固溶体粒子を得ることができる。また、得られた金属酸化物・酸化亜鉛固溶体粒子を４００℃〜１５００℃で焼成することにより、比表面積を１〜１００ｍ２／ｇの範囲に入るように調整し、結晶性を向上させるとともに、吸油量が制御された金属酸化物・酸化亜鉛固溶体粒子を得ることができる。
また、第３発明によれば、第２発明の球状粉体を用いて、その球状粉体の表面を、ポリシロキサン、アルキルシラン化合物、アルキルチタネート化合物、フッ素化合物などの疎水性を示す化合物で被覆することで、疎水性を有する球状粉体を得ることができる。
また、第４発明によれば、前記球状粉体及び／又は被覆球状粉体を化粧料に配合することにより、紫外線遮蔽効果、ソフトフォーカス性及び感触に優れ、光触媒活性が抑えられ、経時安定性に優れた化粧料を得ることができる。
According to the first invention, it is possible to control the particle form to be spherical in a low-cost manner, to control the particle diameter, to impart small irregularities to the particle surface, and to reduce the photocatalytic activity. Metal oxide / zinc oxide solid solution particles can be obtained. Further, by firing the obtained metal oxide-zinc oxide solid solution particles at 4 00 ° C. to 1500 ° C., and adjust the specific surface area as fall within the scope of 1 to 100 m 2 / g, improves the crystallinity In addition, metal oxide / zinc oxide solid solution particles with controlled oil absorption can be obtained.
According to the third invention, the spherical powder of the second invention is used and the surface of the spherical powder is coated with a hydrophobic compound such as polysiloxane, an alkylsilane compound, an alkyl titanate compound, or a fluorine compound. By doing so, a spherical powder having hydrophobicity can be obtained.
Further, according to the fourth invention, by blending the spherical powder and / or the coated spherical powder into the cosmetic, the ultraviolet ray shielding effect, the soft focus property and the touch are excellent, the photocatalytic activity is suppressed, and the temporal stability is improved. Excellent cosmetics can be obtained.
次に、本発明による金属酸化物・酸化亜鉛固溶体粒子の製造方法、球状粉体の製造方法、被覆球状粉体の製造方法及び化粧料の製造方法の具体的な実施の形態について説明する。 Next, a method of manufacturing a metal oxide-zinc oxide solid solution particles, a method for preparing spherical powder, specific embodiment of the manufacturing method and cosmetic method for producing coated spherical powder will be described.
本発明の金属酸化物・酸化亜鉛固溶体粒子の一次粒子径は２〜２００ｎｍ程度であり、その一次粒子が集積し、２０〜５０００ｎｍの球状粉体を形成している。ここで、集積した球状粒子の粒子径は反応の条件によって制御することができる。また、本発明の金属酸化物・酸化亜鉛固溶体粒子の平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）にて観察し、任意の２０個の一次粒子の直径を計測し、その平均値を算出することによって測定することができる。 The primary particle diameter of the metal oxide / zinc oxide solid solution particles of the present invention is about 2 to 200 nm, and the primary particles accumulate to form a spherical powder of 20 to 5000 nm. Here, the particle diameter of the accumulated spherical particles can be controlled by the reaction conditions. Moreover, the average primary particle diameter of the metal oxide / zinc oxide solid solution particles of the present invention is observed with a transmission electron microscope (TEM), and the diameter of any 20 primary particles is measured and the average value is calculated. Can be measured.
本発明の球状粉体は、次のようにして製造される。すなわち、亜鉛とグリコールとアミン化合物とドープする金属塩と水の割合を、混合物全体を１００質量％とするとき、亜鉛の割合が０．０１〜１０．０質量％、グリコールの割合が１０〜５０質量％、アミン化合物の割合が２〜２０質量％、ドープする金属の割合が０．００００１〜０．５質量％、水の割合が４０〜８０質量％の範囲内になるように混合する。その後、５０℃〜１００℃の温度条件下で、１０分〜５時間ソフト溶液反応を行い、水洗、ろ過、乾燥、粉砕を行うことにより、球状粉体を得る。なお、加熱反応中は、目的の粒子サイズにするために、撹拌を行っても構わない。 The spherical powder of the present invention is produced as follows. That is, when the ratio of zinc, glycol, amine compound, metal salt to be doped and water is 100% by mass of the entire mixture, the ratio of zinc is 0.01 to 10.0% by mass and the ratio of glycol is 10 to 50%. It mixes so that the ratio of the mass%, the amine compound may be in the range of 2 to 20 mass%, the ratio of the metal to be doped is 0.00001 to 0.5 mass%, and the ratio of water is in the range of 40 to 80 mass%. Thereafter, a soft solution reaction is performed under a temperature condition of 50 ° C. to 100 ° C. for 10 minutes to 5 hours, and washing with water, filtration, drying, and pulverization are performed to obtain a spherical powder. During the heating reaction, stirring may be performed in order to obtain a target particle size.
前記水溶性亜鉛化合物としては、硝酸亜鉛、硫酸亜鉛、酢酸亜鉛、塩化亜鉛などを用いることができる。 As the water-soluble zinc compound, zinc nitrate, zinc sulfate, zinc acetate, zinc chloride and the like can be used.
グリコールとしては、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，１０−デカンジオール、ピナコール、ジエチレングリコール、トリエチレングリコール等のアルキレングリコールや、シクロペンタン−１，２−ジオール、シクロヘキサン−１，２−ジオール、シクロヘキサン−１，４−ジオール等の脂環式グリコール類や、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、３−メチル−３−メトキシブタノール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、エチレングリコールモノアセテート等のグリコール類のモノエーテル及びモノエステル等の誘導体等が挙げられる。このうち、エチレングリコールが特に好ましい。 Examples of the glycol include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol and other alkylene glycols, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol Alicyclic glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutyl Nord, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, derivatives of monoethers and monoesters of glycols such as ethylene glycol monoacetate, and the like. Of these, ethylene glycol is particularly preferred.
アミン化合物としては、アンモニア、エチルアミン、エタノールアミン、ジエチルアミン、ジエタノールアミン、トリエチルアミン、トリエタノールアミン、ヘキサメチレンテトラミンなどが挙げられる。このうち、トリエタノールアミンが特に好ましい。 Examples of the amine compound include ammonia, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, triethanolamine, hexamethylenetetramine, and the like. Of these, triethanolamine is particularly preferred.
ドープする原子価が４以下の金属イオンの金属塩としては、硝酸鉄、硝酸ジルコニウム、硝酸マグネシウム、硝酸コバルト、硝酸ニッケル、硝酸アルミニウム、硝酸カルシウム、硝酸銅、硝酸クロム、硝酸マンガン、塩化カルシウム、塩化銀、塩化クロム、塩化コバルト、塩化すず、塩化鉄、塩化銅、塩化ニッケル、塩化マグネシウム、硫酸アルミニウム、硫酸カルシウム、硫酸銀、硫酸すず、硫酸鉄、硫酸銅、硫酸ニッケル、硫酸マグネシウム、硫酸マンガンなどが挙げられるが、これらから合成される金属酸化物のドープにより、自由電子および正孔を補足するという条件を満足する限り、特に限定されるものではない。 The metal salts of metal ions with a valence of 4 or less are iron nitrate, zirconium nitrate, magnesium nitrate, cobalt nitrate, nickel nitrate, aluminum nitrate, calcium nitrate, copper nitrate, chromium nitrate, manganese nitrate, calcium chloride, and chloride. Silver, chromium chloride, cobalt chloride, tin chloride, iron chloride, copper chloride, nickel chloride, magnesium chloride, aluminum sulfate, calcium sulfate, silver sulfate, tin sulfate, iron sulfate, copper sulfate, nickel sulfate, magnesium sulfate, manganese sulfate, etc. However, it is not particularly limited as long as it satisfies the condition of capturing free electrons and holes by doping a metal oxide synthesized therefrom.
酸化亜鉛にドープされる金属酸化物の割合は、金属酸化物をドープした球状粉体全体の０．０５質量％〜１０質量％が好適である。ドープされる金属酸化物の割合が０．０５質量％未満であると、金属酸化物による光毒性の抑制効果が発揮できず、逆に１０質量％を超えると、紫外線遮蔽効果が低下するなどの問題がある。 The proportion of the metal oxide doped in zinc oxide is preferably 0.05% by mass to 10% by mass of the entire spherical powder doped with the metal oxide. When the proportion of the metal oxide to be doped is less than 0.05% by mass, the effect of suppressing phototoxicity by the metal oxide cannot be exhibited. On the other hand, when it exceeds 10% by mass, the ultraviolet shielding effect is reduced. There's a problem.
前記反応における反応温度は５０℃〜１００℃とするのが好ましいが、最も良い条件としては７０℃以上である。また、オートクレーブやマイクロ波水熱法などの反応方法を用いることによって１００℃以上の高温で行っても構わない。しかし、反応装置が高価であるため、一般的に使用されている反応装置で反応が可能な１００℃以下での反応とするのが好ましい。 The reaction temperature in the reaction is preferably 50 ° C to 100 ° C, but the best condition is 70 ° C or higher. Moreover, you may carry out at high temperature of 100 degreeC or more by using reaction methods, such as an autoclave and a microwave hydrothermal method. However, since the reaction apparatus is expensive, it is preferable to set the reaction at 100 ° C. or lower, which allows the reaction to be performed by a generally used reaction apparatus.
上記方法にて得られた球状粉体を焼成する際の焼成条件としては、３００℃〜１５００℃の温度範囲で行うのが好ましい。より好ましくは、４００℃〜８００℃の範囲である。焼成温度が３００℃未満の場合においても、Ｘ線回折にて分析を行った結果、酸化亜鉛の結晶構造であることが確認できるが、４００℃以上で焼成することによって、結晶の配向性が向上し、結晶中での酸素欠陥などの欠陥が減少する。また、紫外線遮蔽効果も長波長側の波長から紫外線を遮蔽することができる。一方、１５００℃よりも高い温度になると、高温での処理となり、環境への負荷が増大し、形状も酸化亜鉛が融解し球状を維持できない。 As firing conditions when firing the spherical powder obtained by the above method, it is preferable to carry out in a temperature range of 300 ° C to 1500 ° C. More preferably, it is the range of 400 degreeC-800 degreeC. As a result of analysis by X-ray diffraction even when the firing temperature is less than 300 ° C., the crystal structure of zinc oxide can be confirmed, but the orientation of the crystal is improved by firing at 400 ° C. or higher. As a result, defects such as oxygen defects in the crystal are reduced. Further, the ultraviolet ray shielding effect can also shield the ultraviolet ray from the longer wavelength side wavelength. On the other hand, when the temperature is higher than 1500 ° C., the treatment is performed at a high temperature, the load on the environment is increased, and the zinc oxide is melted and the shape cannot be maintained spherical.
次に、本発明に係る疎水性の球状粉体（被覆球状粉体）について説明する。
本発明において、球状粉体がファンデーションやサンスクリーン剤として利用される場合、皮膚に塗布したあと、耐水性が必要となるため、この球状粉体に疎水性を付与する必要がある。粉体に疎水性を付与するには、ポリシロキサン、アルキルシラン化合物、アルキルチタネート化合物、フッ素化合物などの化合物で粉体の表面が被覆される。また、上記の化合物以外にも、従来公知の各種の表面処理を施すことができる。なお、これらの処理は複数組み合わせることも可能である。
Next, the hydrophobic spherical powder (coated spherical powder) according to the present invention will be described.
In the present invention, when the spherical powder is used as a foundation or a sunscreen agent, water resistance is required after it is applied to the skin. In order to impart hydrophobicity to the powder, the surface of the powder is coated with a compound such as polysiloxane, an alkylsilane compound, an alkyl titanate compound, or a fluorine compound. In addition to the above compounds, various conventionally known surface treatments can be applied. A plurality of these processes can be combined.
具体的な表面被覆有機化合物としては、シリコン系化合物として、メチルハイドロジエンポリシロキサン、ジメチルポリシロキサン、アクリルシリコン共重合体が挙げられ、アルキルシラン系として、ｎ−オクチルトリエトキシシランが、アルキルチタネート系として、イソプロピルトリイソステアロイルチタネートが、フッ素系として、パーフルオロアルキルリン酸エステル、パーフルオロアルキルエトキシシランなどが挙げられる。 Specific examples of the surface coating organic compound include methylhydrene polysiloxane, dimethylpolysiloxane, and acrylic silicon copolymer as silicon compounds, and n-octyltriethoxysilane as alkyl titanate as alkylsilane. Isopropyl triisostearoyl titanate, and fluorine-based compounds such as perfluoroalkyl phosphate ester and perfluoroalkylethoxysilane.
また、疎水性化合物を表面被覆する処理方法としては、被覆処理される顔料を適当なミキサー中で撹拌し、表面被覆する化合物を液滴下あるいはスプレー噴霧にて加えた後、一定時間高速強撹拌する。その後、撹拌を続けながら８０〜２００℃に加熱熟成させることによって、反応表面被覆処理を行う方法が一般的である。あるいは、表面被覆する化合物をエタノール、イソプロピルアルコール、イソブタノール等のアルコール類、トルエン、ｎ−ヘキサン、シクロヘキサン等の炭化水素系有機溶剤、アセトン、酢酸エチル、酢酸ブチル等の極性有機溶剤などに溶解させておき、この溶液に撹拌中に化粧料用顔料を添加撹拌した後、有機溶剤を完全に蒸発除去し、その後、８０〜２００℃に加熱熟成させることにより、表面被覆処理を行う方法等も挙げられる。 As a treatment method for coating the surface of the hydrophobic compound, the pigment to be coated is stirred in an appropriate mixer, and the compound to be coated is added under a droplet or by spray spraying, and then stirred vigorously at high speed for a certain time. . Then, the method of performing the reaction surface coating process by making it heat-ripen at 80-200 degreeC, continuing stirring is common. Alternatively, the surface coating compound is dissolved in alcohols such as ethanol, isopropyl alcohol and isobutanol, hydrocarbon organic solvents such as toluene, n-hexane and cyclohexane, polar organic solvents such as acetone, ethyl acetate and butyl acetate. In addition, after adding and stirring the cosmetic pigment to the solution while stirring, the organic solvent is completely removed by evaporation, and then the surface coating treatment is performed by heating and aging at 80 to 200 ° C. It is done.
また、混合分散方法としては、溶液の濃度や粘度などに応じて適当な方法を選択することができる。好適な例としては、ディスパー、ヘンシェルミキサー、レディゲミキサー、ニーダー、Ｖ型混合機、ロールミル、ビーズミル、２軸混練機等の混合機による方法や、水溶液と顔料を加熱空気中に噴霧して水分を一気に除去するスプレードライの方法などを選択することができる。また、粉砕を行う場合においては、ハンマーミル、ボールミル、サンドミル、ジェットミル等の通常の粉砕機を用いることができる。これらいずれの粉砕機によっても同等の品質のものが得られるため、特に限定されるものではない。 As the mixing and dispersing method, an appropriate method can be selected according to the concentration and viscosity of the solution. Preferable examples include a method using a mixer such as a disper, a Henschel mixer, a Redige mixer, a kneader, a V-type mixer, a roll mill, a bead mill, or a biaxial kneader, or a water solution by spraying an aqueous solution and a pigment into heated air. It is possible to select a spray drying method or the like that removes at a stroke. When pulverization is performed, a normal pulverizer such as a hammer mill, a ball mill, a sand mill, or a jet mill can be used. Since any of these pulverizers can obtain the same quality, it is not particularly limited.
この場合、顔料の表面被覆処理に用いられる化合物である成分の質量比は、被覆処理される顔料に対して０．５〜３０質量％である。前記質量比が０．５質量％未満であるとロングラスティング効果と肌への均一な付着性が充分でなく、３０質量％を超えると感触が非常に油っぽく湿った感じとなり、化粧料としては適さない。 In this case, the mass ratio of the component which is a compound used for the pigment surface coating treatment is 0.5 to 30% by mass with respect to the pigment to be coated. When the mass ratio is less than 0.5% by mass, the long lasting effect and the uniform adhesion to the skin are not sufficient, and when it exceeds 30% by mass, the feel becomes very oily and moist. Not suitable for.
また、本発明の表面被覆された球状粉体（被覆球状粉体）を配合する化粧料の形態は特に限定されないが、ファンデーション、サンスクリーン、美容液、化粧水、口紅、美容クリーム、洗顔剤、香水、口内清涼剤、口臭予防剤、うがい剤、歯磨き、入浴剤、制汗剤、石鹸、シャンプー、リンス、ボディーソープ、ボディーローション、デオドラント剤、ヘアクリーム剤、色白剤、美肌剤、育毛剤などが挙げられる。 Further, the form of the cosmetic compounding the surface-coated spherical powder (coated spherical powder) of the present invention is not particularly limited, but foundation, sunscreen, cosmetic liquid, lotion, lipstick, cosmetic cream, facial cleanser, Perfumes, mouth refreshers, bad breath prevention agents, gargles, toothpastes, bathing agents, antiperspirants, soaps, shampoos, rinses, body soaps, body lotions, deodorants, hair creams, whitening agents, skin care agents, hair restorers, etc. Is mentioned.
また、本発明の球状粉体が配合される化粧料においては、その球状粉体以外に、通常の化粧料に用いられる油剤、粉体(顔料、色素、樹脂)、フッ素化合物、樹脂、界面活性剤、粘剤、防腐剤、香料、保湿剤、生理活性成分、塩類、溶媒、キレート剤、中和剤、ｐＨ調整剤等の成分を同時に配合することができる。ここで、前記粉体としては、例えば、赤色１０４号、赤色２０１号、黄色４号、青色１号、黒色４０１号等の色素、黄色４号アルミニウムレーキ、黄色２０３号バリウムレーキ等のレーキ色素、ナイロンパウダー、シルクパウダー、ウレタンパウダー、テフロンパウダー（テフロン：登録商標）、シリコンパウダー、セルロースパウダー、シリコンエラストマー等の高分子、黄酸化鉄、赤色酸化鉄、黒酸化鉄、酸化クロム、カーボンブラック、群青、紺青等の有色顔料、酸化チタン、酸化セリウム等の白色顔料、タルク、マイカ、セリサイト、カオリン等の体質顔料、雲母チタン等のパール顔料、硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸アルミニウム、ケイ酸マグネシウム等の金属塩、シリカ、窒化ホウ素等の無機粉体、微粒子酸化チタン、微粒子酸化鉄、アルミナ処理微粒子酸化チタン、シリカ処理微粒子酸化チタン、ベントナイト、スメクタイト等が挙げられる。これらの粉体の形状、大きさに特に制限はない。また、これらの粉体は従来公知の各種の表面処理が施されていてもいなくても構わない。表面処理の例としては、例えばアクリルシリコン処理、メチルハイドロジェンポリシロキサン処理、シリコーンレジン処理、オクチルトリエトキシシラン処理、Ｎ−アシル化リジン処理、有機チタネート処理、シリカ処理、アルミナ処理、セルロース処理、パーフルオロポリエーテル処理、フッ素化シリコーンレジン処理など親水性、親油性、撥水性の各種の処理を用いることが可能である。前記油剤としては、例えばセチルアルコール、イソステアリルアルコール、ラウリルアルコール、ヘキサデシルアルコール、オクチルドデカノール等の高級アルコール、イソステアリン酸、ウンデシレン酸、オレイン酸等の脂肪酸、グリセリン、ソルビトール、エチレングリコール、プロピレングリコール、ポリエチレングリコール等の多価アルコール、ミリスチン酸ミリスチン、ラウリル酸ヘキシル、オレイン酸デシル、ミリスチン酸イソプロピル、ジメチルオクタン酸ヘキシルデシル、モノステアリン酸グリセリン、フタル酸ジエチル、モノステアリン酸エチレングリコール、オキシステアリン酸オクチル等のエステル類、流動パラフィン、ワセリン、スクワラン等の炭化水素、ラノリン、還元ラノリン、カルナバロウ等のロウ、ミンク油、カカオ油、ヤシ油、バーム核油、ツバキ油、ゴマ油、ヒマシ油、オリーブ油等の油脂、エチレン・α−オレフィン・コオリゴマー等が挙げられる。また、メチルハイドロジェンポリシロキサン、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ポリエーテル変性オルガノポリシロキサン、フルオロアルキル・ポリオキシアルキレン共変性オルガノポリシロキサン、アルキル変性オルガノポリシロキサン、フッ素変性オルガノポリシロキサン、アモジメチコン、アミノ変性オルガノポリシロキサン、シリコンゲル、アクリルシリコン、トリメチルシロキシケイ酸、シリコンＲＴＶゴム等のシリコン化合物、パーフルオロポリエーテル、フッ化ピッチ、フルオロカーボン、フルオロアルコール、フッ素化シリコーンレジン等のフッ素化合物が挙げられる。また、前記界面活性剤としては、例えばアニオン型界面活性剤、カチオン型界面活性剤、ノニオン型界面活性剤、べタイン型界面活性剤を用いることができる。前記溶媒としては、精製水、エタノール、軽質流動イソパラフィン、低級アルコール、エーテル類、ＬＰＧ、フルオロカーボン、Ｎ−メチルピロリドン、フルオロアルコール、パーフルオロポリエーテル、代替フロン、揮発性シリコン等が挙げられる。 In addition, in cosmetics formulated with the spherical powder of the present invention, in addition to the spherical powder, oils, powders (pigments, pigments, resins), fluorine compounds, resins, surfactants used in ordinary cosmetics Components such as an agent, a sticking agent, a preservative, a fragrance, a humectant, a physiologically active ingredient, a salt, a solvent, a chelating agent, a neutralizing agent, and a pH adjusting agent can be blended at the same time. Here, as the powder, for example, red 104, red 201, yellow 4, blue 1, black 401 and other dyes, yellow 4 aluminum lake, yellow 203 barium lake and other lake dyes, Nylon powder, silk powder, urethane powder, Teflon powder (Teflon: registered trademark), silicon powder, cellulose powder, polymers such as silicon elastomer, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine , Colored pigments such as bitumen, white pigments such as titanium oxide and cerium oxide, extender pigments such as talc, mica, sericite and kaolin, pearl pigments such as mica titanium, barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, Metal salts such as magnesium silicate, inorganic powders such as silica and boron nitride, Particles of titanium oxide, fine particles of iron oxide, alumina-treated fine titanium oxide particles, silica treated ultrafine titanium dioxide, bentonite, smectite, and the like. There are no particular restrictions on the shape and size of these powders. These powders may or may not be subjected to various conventionally known surface treatments. Examples of surface treatments include, for example, acrylic silicon treatment, methyl hydrogen polysiloxane treatment, silicone resin treatment, octyltriethoxysilane treatment, N-acylated lysine treatment, organic titanate treatment, silica treatment, alumina treatment, cellulose treatment, par Various hydrophilic, lipophilic, and water-repellent treatments such as fluoropolyether treatment and fluorinated silicone resin treatment can be used. Examples of the oil include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, fatty acids such as isostearic acid, undecylenic acid, oleic acid, glycerin, sorbitol, ethylene glycol, propylene glycol, Polyhydric alcohols such as polyethylene glycol, myristic myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, etc. Esters, hydrocarbons such as liquid paraffin, petrolatum, squalane, lanolin, reduced lanolin, wax such as carnauba wax, mink , Cacao oil, coconut oil, balm kernel oil, camellia oil, sesame oil, castor oil, oils such as olive, ethylene-alpha-olefin co-oligomer, and the like. In addition, methyl hydrogen polysiloxane, dimethyl polysiloxane, methyl phenyl polysiloxane, polyether-modified organopolysiloxane, fluoroalkyl / polyoxyalkylene co-modified organopolysiloxane, alkyl-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone , Silicon compounds such as amino-modified organopolysiloxane, silicon gel, acrylic silicon, trimethylsiloxysilicic acid, silicon RTV rubber, and fluorine compounds such as perfluoropolyether, fluorinated pitch, fluorocarbon, fluoroalcohol, and fluorinated silicone resin It is done. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant. Examples of the solvent include purified water, ethanol, light liquid isoparaffin, lower alcohol, ethers, LPG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, perfluoropolyether, alternative chlorofluorocarbon, and volatile silicon.
次に、本発明による金属酸化物・酸化亜鉛固溶体粒子の製造方法、球状粉体の製造方法、被覆球状粉体の製造方法及び化粧料の製造方法の具体的な実施例について、図面を参照しつつ説明する。なお、本発明は以下に述べる実施例に限定されるものではない。以下、球状粉体を調製する実施例を「製造実施例」と称し、この球状粉体を用いて化粧料を調製する実施例を単に「実施例」と称することとする。 Next, specific examples of a method for producing metal oxide / zinc oxide solid solution particles, a method for producing a spherical powder, a method for producing a coated spherical powder, and a method for producing a cosmetic according to the present invention will be described with reference to the drawings. I will explain. In addition, this invention is not limited to the Example described below. Hereinafter, an example of preparing a spherical powder is referred to as “manufacturing example”, and an example of preparing a cosmetic using the spherical powder is simply referred to as “example”.
（製造実施例１）
硝酸亜鉛６水和物１４．８７ｇに水を加え、全量が５００ｍｌになるように溶解した。その溶液に、硝酸マグネシウム・６水和物０．１２８ｇを加え溶解した。さらにエチレングリコール２５０ｇを添加した後、トリエタノールアミン６２．５ｇを加え撹拌した。その後、２℃／分の昇温速度にて９０℃にまで加温し、９０℃に到達してから１時間９０℃を保持した。その後、水洗、ろ過、乾燥を行い、一次粒子径が１０ｎｍで、球状に集積した状態で、３００ｎｍの球状粉体を得た。その後、４００℃にて２時間焼成を行い、酸化マグネシウムをドープした球状粉体を得た。
図１には、製造実施例１にて得られた酸化マグネシウムをドープしてなる金属酸化物・酸化亜鉛固溶体粒子が集積した球状粉体を、透過型電子顕微鏡にて観察した写真（ａ）と、同球状粉体を走査型電子顕微鏡にて観察した写真（ｂ）とがそれぞれ示されている。
(Production Example 1)
Water was added to 14.87 g of zinc nitrate hexahydrate and dissolved so that the total amount became 500 ml. To the solution, 0.128 g of magnesium nitrate hexahydrate was added and dissolved. Further, 250 g of ethylene glycol was added, and then 62.5 g of triethanolamine was added and stirred. Then, it heated up to 90 degreeC with the temperature increase rate of 2 degree-C / min, and after reaching 90 degreeC, 90 degreeC was hold | maintained for 1 hour. Thereafter, washing with water, filtration and drying were performed to obtain a spherical powder having a primary particle diameter of 10 nm and a spherical powder having a particle diameter of 300 nm. Then, it baked at 400 degreeC for 2 hours, and obtained the spherical powder doped with magnesium oxide.
FIG. 1 shows a photograph (a) obtained by observing, with a transmission electron microscope, a spherical powder obtained by collecting magnesium oxide-doped metal oxide / zinc oxide solid solution particles obtained in Production Example 1. A photograph (b) of the same spherical powder observed with a scanning electron microscope is shown.
（製造実施例２〜５）
ドープする金属塩を亜鉛に対してモル比で１：１００になるように加えたこと以外は、製造実施例１と同様にして球状粉体を得た。ドープした金属酸化物の金属塩としては、硝酸鉄・９水和物、硝酸コバルト・６水和物、硝酸ニッケル・６水和物、硝酸ジルコニル・２水和物を用いた。
(Production Examples 2 to 5)
A spherical powder was obtained in the same manner as in Production Example 1, except that the metal salt to be doped was added at a molar ratio of 1: 100 with respect to zinc. As the metal salt of the doped metal oxide, iron nitrate · 9 hydrate, cobalt nitrate · hexahydrate, nickel nitrate · hexahydrate, zirconyl nitrate · dihydrate was used.
（製造実施例６）
製造実施例１にて得られた球状粉体に、メチルハイドロジェンポリシロキサンにて表面被覆処理を施した。
ヘンシェルミキサーに製造実施例１で得られた球状酸化亜鉛１０００質量部を入れ、続いてメチルハイドロジェンポリシロキサン２０．４質量部をイソプロピルアルコール１２５質量部に溶解させた溶液を滴下混合し、板状ベーマイトと良く混合した。その後、ヘンシェルミキサー内を加熱及び減圧し、イソプロピルアルコールを除去した。処理された粉体をヘンシェルミキサーから取り出し、粉砕して加熱処理を行い、シリコン化合物が２質量％処理された被覆球状粉体を得た。
(Production Example 6)
The spherical powder obtained in Production Example 1 was subjected to a surface coating treatment with methyl hydrogen polysiloxane.
In a Henschel mixer, 1000 parts by mass of the spherical zinc oxide obtained in Production Example 1 was added, and then a solution in which 20.4 parts by mass of methylhydrogenpolysiloxane was dissolved in 125 parts by mass of isopropyl alcohol was dropped and mixed to form a plate. Mix well with boehmite. Thereafter, the interior of the Henschel mixer was heated and depressurized to remove isopropyl alcohol. The treated powder was taken out of the Henschel mixer, pulverized and heat-treated to obtain a coated spherical powder treated with 2% by mass of the silicon compound.
製造実施例１〜５で得られた球状粉体をシリコーンオイル（東レ・ダウコーニング株式会社製 ＳＦ８４１７）にて２０質量％になるように混合し、フーバーマーラーにて１００ｒｐｍ、３回の条件で分散させた。その後、５ｃｍ×８ｃｍの石英板の上にトランスポアテープを貼り、上記方法にて分散させた分散体０．０８ｇをテープ上に均一に塗布した。その後１５分間放置した後、ＳＰＦアナライザー（Ｌａｂｓｐｈｅｒｅ社製 ＵＶ−１０００Ｓ）を用いて、Ｓｕｎ Ｐｒｏｔｅｃｔｉｏｎ Ｆａｃｔｏｒ（ＳＰＦ）およびＰｒｏｔｅｃｔｉｏｎ ｇｒａｄｅ ｏｆ ＵＶＡ（ＰＡ）の測定を行った。また、比較品として、市販されている一次粒子径が１００〜２００ｎｍで、比表面積が１０ｍ２／ｇの酸化亜鉛に上記シリコン処理の方法で同様に表面処理したものを用いた。その結果が表１に示されている。ＳＰＦおよびＰＡの測定結果において、市販品（比較品）と比較したところ、高い紫外線遮蔽効果があることが分かった。 The spherical powder obtained in Production Examples 1 to 5 was mixed with silicone oil (SF8417 manufactured by Toray Dow Corning Co., Ltd.) so as to be 20% by mass, and dispersed with a Hoover Marler at 100 rpm for 3 times. I let you. Thereafter, a transpore tape was applied on a 5 cm × 8 cm quartz plate, and 0.08 g of the dispersion dispersed by the above method was uniformly applied on the tape. Then, after standing for 15 minutes, Sun Protection Factor (SPF) and Protection grade of UVA (PA) were measured using an SPF analyzer (UV-1000S manufactured by Labsphere). Further, as a comparative product, a commercially available zinc oxide having a primary particle diameter of 100 to 200 nm and a specific surface area of 10 m 2 / g was similarly surface-treated by the above silicon treatment method. The results are shown in Table 1. In the measurement results of SPF and PA, it was found that there was a high ultraviolet shielding effect when compared with a commercially available product (comparative product).
次に、上記測定に用いた分散体を用いて、透過率の測定を行った。この透過率の測定には、分散体を光路長が０．０３ｍｍの挟み込みセルに仕込み、分光光度計にて透明性の測定を行った。図２に透過率測定結果が示されている。図示のように、製造実施例１〜５にて製造された球状粉体は比較品と比較し、透明性の高いことが分かる。特に製造実施例２にて製造された、酸化鉄ドープ球状粉体は特に高い透明性が得られた。 Next, the transmittance was measured using the dispersion used in the above measurement. For the measurement of the transmittance, the dispersion was charged in a sandwich cell having an optical path length of 0.03 mm, and the transparency was measured with a spectrophotometer. FIG. 2 shows the transmittance measurement results. As shown in the figure, it can be seen that the spherical powders produced in Production Examples 1 to 5 have higher transparency than the comparative products. In particular, the iron oxide-doped spherical powder produced in Production Example 2 has particularly high transparency.
製造実施例１〜５の球状粉体及び比較品について光触媒活性についての測定を行った。光触媒活性の測定方法としては、一酸化窒素の光酸化試験を用いた。すなわち、濃度を１ｐｐｍに調整した一酸化窒素ガスを、光触媒粉体を入れた容器中に通気させ、光触媒粉体に２９０ｎｍ以上または４００ｎｍ以上の光を照射させることによって、活性酸素・フリーラジカルが生成され、一酸化窒素が硝酸イオンに分解が進行する現象を利用し、光触媒活性の測定を行った。
光触媒粉体の試験片は２０ｍｍ×１５ｍｍの平板にし、密閉容器に入れ、そこに濃度が１ｐｐｍの一酸化窒素ガスを２００ｍｌ／分の流量で試験片の入った容器に通気させた。その後、試験片に２９０ｎｍ以上および４００ｎｍ以上の光を照射した時の一酸化窒素ガスの濃度を測定した。光触媒活性の測定結果が表２に示されている。
About the spherical powder of the manufacture examples 1-5, and the comparative product, the measurement about photocatalytic activity was performed. As a method for measuring the photocatalytic activity, a photooxidation test of nitric oxide was used. That is, nitrogen monoxide gas adjusted to a concentration of 1 ppm is passed through a container containing photocatalyst powder, and the photocatalyst powder is irradiated with light of 290 nm or more or 400 nm or more to generate active oxygen / free radicals. The photocatalytic activity was measured using the phenomenon that nitric oxide was decomposed into nitrate ions.
The test piece of photocatalyst powder was made into a flat plate of 20 mm × 15 mm, placed in a sealed container, and nitrogen monoxide gas having a concentration of 1 ppm was passed through the container containing the test piece at a flow rate of 200 ml / min. Thereafter, the concentration of nitric oxide gas when the test piece was irradiated with light of 290 nm or more and 400 nm or more was measured. The measurement results of photocatalytic activity are shown in Table 2.
表２に示されている結果から明らかなように、金属酸化物をドープされた球状粉体は、一酸化窒素の残存率が高くなっていることが分かる。このことより光照射によって生成される光毒性が抑制されていることが判明した。 As is clear from the results shown in Table 2, it can be seen that the spherical powder doped with the metal oxide has a high residual ratio of nitric oxide. This proved that the phototoxicity generated by light irradiation was suppressed.
（実施例１）
〔サンスクリーンの製造〕
表３に示される処方と下記製造方法に従いサンスクリーンを調製した。なお、表中の配合量の単位は質量％である。
Example 1
[Production of sunscreen]
A sunscreen was prepared according to the formulation shown in Table 3 and the following production method. In addition, the unit of the compounding quantity in a table | surface is mass%.
成分ＡおよびＢをそれぞれ８０℃にて混合し、均一に分散したのを確認した後、３０℃まで冷却する。冷却後成分Ｂを成分Ａにホモミキサーにて撹拌しながら少しずつ添加し、均一になるまで良く混合し、球状粉体配合サンスクリーンを得た。
Components A and B are mixed at 80 ° C., and after confirming that they are uniformly dispersed, they are cooled to 30 ° C. After cooling, component B was added to component A little by little with stirring with a homomixer and mixed well until uniform to obtain a spherical powder blended sunscreen.
（比較例１）
製造実施例６で製造されたシリコン処理球状酸化亜鉛の代わりに、シリコン処理された市販されている酸化亜鉛を用いた他は全て実施例１と同様にして製品を得た。
(Comparative Example 1)
A product was obtained in the same manner as in Example 1 except that instead of the silicon-treated spherical zinc oxide produced in Production Example 6, silicon-treated commercial zinc oxide was used.
実施例１及び比較例１で作製した化粧料について、女性パネラー１０名によって、使用感に関する官能評価試験を実施した。試験はアンケート形式で実施し、各項目に０点から５点の間の点数をつけ、０点は評価が悪い、５点は評価が優れるとして数値化し、結果を全パネラーの平均点として表した。従って、点数が高い程評価が優れていることを示す。この評価結果が表４に示されている。 About the cosmetics produced in Example 1 and Comparative Example 1, the sensory evaluation test regarding a usability | use_condition was implemented by 10 female panelists. The test was conducted in a questionnaire format, and each item was scored between 0 and 5 points, 0 points were badly evaluated, 5 points were evaluated as excellent, and the result was expressed as the average score of all panelists. . Therefore, the higher the score, the better the evaluation. The evaluation results are shown in Table 4.
表４の結果より、実施例１は比較例１よりも、使用感、化粧持ち、肌の透明感全てにおいて優れる結果となっていることが分かる。 From the results of Table 4, it can be seen that Example 1 is superior to Comparative Example 1 in terms of usability, makeup retention, and skin transparency.
本発明によれば、一次粒子径が２〜２００ｎｍの粒子が集積し、２０〜５０００ｎｍの球状を形成している光触媒活性を抑制された球状粉体を提供することが可能であり、また、その球状粉体に疎水性化合物を表面被覆した被覆球状粉体を配合することにより、肌へ塗布した時の使用感、透明感、化粧持ちが優れた化粧料を提供することが可能であるので、ファンデーション、アイシャドウ、ほほ紅、口紅などのメイクアップ化粧料あるいはサンスクリーン化粧料に用いて好適であり、産業上の利用可能性が大である。 According to the present invention, it is possible to provide a spherical powder with suppressed primary photocatalytic activity in which particles having a primary particle diameter of 2 to 200 nm are accumulated to form a sphere having a diameter of 20 to 5000 nm. By blending a spherical powder with a coated spherical powder that is coated with a hydrophobic compound, it is possible to provide a cosmetic with excellent usability, transparency, and long-lasting makeup when applied to the skin. It is suitable for use in makeup cosmetics such as foundations, eye shadows, cheeks and lipsticks, or sunscreen cosmetics, and has great industrial applicability.
Claims (4)
（式中、ｍは１以上の整数であり、ｎは０以上の整数である。また、Ｒ１〜Ｒ３は水素、アルキル基、アルコキシル基又はフェニル基であり、同一であっても異なっていても良い。）
Ｒ１Ｓｉ（ＯＲ２）３ ・・・・・（２）
（式中、Ｒ１及びＲ２は炭素数が１以上の飽和炭化水素基である。）
（Ｒ１ＣＯＯ）ａＴｉ（ＯＲ２）ｂ ・・・・・（３）
（式中、Ｒ１及びＲ２は炭素数が１以上の飽和炭化水素基である。また、ａ及びｂはそれぞれ１〜３の整数であり、ａ＋ｂ＝４の関係を有する。なお、ここで示されるアルキル基は直鎖状又は分岐状であって、単一鎖長のものであっても複合鎖長のものであっても良い。）
ＣＦ３（ＣＦ２）ｎＣＨ２ＣＨ２Ｓｉ（ＯＲ１）３ ・・・・・（４）
（式中、Ｒ１は炭素数が１以上の飽和炭化水素基であり、ｎは１以上の整数である。）
（式中、ｎは４以上の整数、ｍは１又は２であり、Ｍは１価の金属イオン、アンモニウム塩又はジエタノールアミン塩である。）
（式中、ｎは４以上の整数、Ｍは１価の金属イオン、アンモニウム塩又はジエタノールアミン塩である。） The surface of the spherical powder produced by the production method of the spherical powder according to claim 2 is a polysiloxane represented by the following general formula (1) and an alkylalkoxysilane compound represented by the following general formula (2). , One or more selected from an alkyl titanate compound represented by the following general formula (3), a fluorine compound represented by the following general formula (4), the following general formula (5) or the following general formula (6) method for producing coated spherical powder, which comprises coating treatment with a compound.
(In the formula, m is an integer of 1 or more, and n is an integer of 0 or more. Also, R 1 to R 3 are hydrogen, an alkyl group, an alkoxyl group, or a phenyl group, and are the same or different. May be.)
R 1 Si (OR 2 ) 3 (2)
(In the formula, R 1 and R 2 are saturated hydrocarbon groups having 1 or more carbon atoms.)
(R 1 COO) a Ti (OR 2 ) b (3)
(In the formula, R 1 and R 2 are each a saturated hydrocarbon group having 1 or more carbon atoms. Further, a and b are each an integer of 1 to 3, and have a relationship of a + b = 4. (The alkyl group shown may be linear or branched and may be of single chain length or of complex chain length.)
CF 3 (CF 2 ) n CH 2 CH 2 Si (OR 1 ) 3 (4)
(In the formula, R 1 is a saturated hydrocarbon group having 1 or more carbon atoms, and n is an integer of 1 or more.)
(In the formula, n is an integer of 4 or more, m is 1 or 2, and M is a monovalent metal ion, ammonium salt or diethanolamine salt.)
(In the formula, n is an integer of 4 or more, and M is a monovalent metal ion, ammonium salt or diethanolamine salt.)
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