JP3866076B2 - Cerium phosphate-titanium phosphate UV blocking agent and method for producing the same - Google Patents
Cerium phosphate-titanium phosphate UV blocking agent and method for producing the same Download PDFInfo
- Publication number
- JP3866076B2 JP3866076B2 JP2001319100A JP2001319100A JP3866076B2 JP 3866076 B2 JP3866076 B2 JP 3866076B2 JP 2001319100 A JP2001319100 A JP 2001319100A JP 2001319100 A JP2001319100 A JP 2001319100A JP 3866076 B2 JP3866076 B2 JP 3866076B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- cerium
- titanium
- blocking agent
- ultraviolet blocking
- 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 - Fee Related
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- 239000002981 blocking agent Substances 0.000 title claims description 62
- XCAGBXIDDZMARO-UHFFFAOYSA-H [Ti+4].[Ce+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Ti+4].[Ce+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XCAGBXIDDZMARO-UHFFFAOYSA-H 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 17
- 239000002537 cosmetic Substances 0.000 claims description 16
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 5
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims 1
- GQSRAMKUYVXYIJ-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Ti+4].[Ti+4] Chemical compound P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Ti+4].[Ti+4] GQSRAMKUYVXYIJ-UHFFFAOYSA-H 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 description 26
- -1 cerium ions Chemical class 0.000 description 25
- 239000000843 powder Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 16
- 229910052684 Cerium Inorganic materials 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- 239000003973 paint Substances 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- MEXSQFDSPVYJOM-UHFFFAOYSA-J cerium(4+);disulfate;tetrahydrate Chemical compound O.O.O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MEXSQFDSPVYJOM-UHFFFAOYSA-J 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 7
- 229940048086 sodium pyrophosphate Drugs 0.000 description 7
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000011180 diphosphates Nutrition 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 230000000475 sunscreen effect Effects 0.000 description 4
- 239000000516 sunscreening agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRXGUZPUZBCGST-UHFFFAOYSA-N [2-(hydroxymethoxy)phenyl]-phenylmethanone Chemical compound OCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 YRXGUZPUZBCGST-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 239000004431 polycarbonate resin Substances 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- MVGWWCXDTHXKTR-UHFFFAOYSA-J tetralithium;phosphonato phosphate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]P([O-])(=O)OP([O-])([O-])=O MVGWWCXDTHXKTR-UHFFFAOYSA-J 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- 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 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- GLLSGHWYBGERSE-UHFFFAOYSA-N [2-(hydroxymethoxy)phenyl]-phenylmethanone;sodium Chemical compound [Na].OCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 GLLSGHWYBGERSE-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
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- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- VCNAMBGKEDPVGQ-UHFFFAOYSA-J azane;cerium(4+);hydrogen sulfate;dihydrate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VCNAMBGKEDPVGQ-UHFFFAOYSA-J 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
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- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
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- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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- DDXPLCBTGWFAIG-UHFFFAOYSA-N triazanium;phosphate;trihydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.[O-]P([O-])([O-])=O DDXPLCBTGWFAIG-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- Cosmetics (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、透明性が非常に高く、安定性、安全性に優れたリン酸セリウム−リン酸チタン系紫外線遮断剤、およびその製造方法に関する。
【０００２】
【従来の技術】
紫外線はプラスチック等の有機材料を劣化させるのみならず、生体に対して悪影響を及ぼす作用が強く、波長２８０〜３２０ｎｍのＵＶ−Ｂ領域の紫外線は皮膚の炎症を引き起こし、また波長３２０〜４００ｎｍのＵＶ−Ａ領域の紫外線は皮膚を褐色にすることが知られている。その防止法の一つとして、種々の有機系紫外線吸収剤や無機系紫外線散乱剤が開発されてきた。
【０００３】
有機系紫外線吸収剤はプラスチックや化粧料に配合した場合に無色かつ透明であるため汎用されていたが、近年になり耐熱性、耐候性の不足や、分解生成物の毒性による安全性の面で問題が多く使用が制限されている。一方、無機紫外線遮断剤としては、酸化チタンおよび酸化亜鉛が一般的に使用されており、その他にも、酸化セリウムも一部応用されてきている。しかしながら、これらの化合物は紫外線遮断特性、透明性、そして光や熱による触媒活性などの面において一長一短があり、実際の使用に当たっては表面をシリカ、アルミナ、窒化ホウ素等で被覆したものが用いられている。しかし、微粒子になればなるほど表面処理による粒子の凝集も起こってしまうため、粒子の分散性が悪くなり、紫外線吸収能を維持したまま高い透明性と低い触媒活性を同時に達成すること不可能であった。
【０００４】
以上の問題点に対して、たとえば、特開平１１−１８９７６６号や特開平１０−２０４２８８号に見られるように、リン酸セリウム、リン酸チタン又はリン酸ジルコニウムなどの紫外線遮断剤が提案されているが、リン酸セリウムは黄色の着色が強く、とりわけ化粧料においては配合が制限されたり、リン酸チタンやリン酸ジルコニウムはＵＶ−Ａ領域において充分な紫外線遮断効果が得られないなど、依然として致命的な問題点を抱えている。
【０００５】
【発明が解決しようという課題】
それ故、本発明の課題は、従来の技術ならびに製造方法では成し得なかった、透明性に優れ、ＵＶ−ＡおよびＵＶ−Ｂの紫外線遮断能に優れ、かつ光・熱触媒活性が極めて低い紫外線遮断剤およびその製造方法を提供することである。
【０００６】
【課題を解決するための手段】
上記の課題を解決するために、本発明の紫外線遮断剤は、リン酸セリウムとリン酸チタンを複合化したことを特徴とする。この構成とすることにより、リン酸セリウムのすぐれたＵＶ−Ａ遮断特性と、リン酸チタンの優れたＵＶ−Ｂ遮断特性を併せ持つ、優れた紫外線遮断効果が得られる。また、互いに化学的に安定な物質の組み合わせであるので、耐候性及び耐熱性に優れた複合粒子が得られ、例えば厳しい環境にさらされる用途においても紫外線遮断剤として好適に使用できる。
【０００７】
【発明の実施の形態】
本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤は、一般式：ＣｅxＴｉ1-xＰ2Ｏ7・ｎＨ2Ｏ（０＜ｘ＜１）で表され、平均粒径が０．００３〜１μｍである。
【０００８】
さらに本発明の複合粒子は、溶液中において＋４価のセリウムイオンと＋４価のチタンイオンをリン酸イオンにて共沈させ、原子レベルで均一に複合化させ、ピロリン酸塩とすることを特徴とする。従って、本発明で得られるリン酸セリウム−リン酸チタン系紫外線遮断剤におけるセリウムは＋４価として存在する。
【０００９】
また、本発明で得られる複合リン酸塩の屈折率は、酸化物系と比較して小さく、組成にもよるがおよそ１．８〜２．０となる。屈折率が低いことによって、可視光に対する粉体の光散乱性が低下し、とりわけ化粧品、塗料等に配合した場合、従来の酸化物に比べ透明性が向上する。さらに複合リン酸塩とすることにより、従来の無機系紫外線遮断剤の大きな問題のひとつであった光および熱触媒活性が著しく抑制される。
【００１０】
リン酸塩としてはピロリン酸塩の他にもオルトリン酸塩、ポリリン酸塩などが知られており、なかでも一般式：ＭＰＯ４・ｎＨ２Ｏ（Ｍは金属イオン）で表されるオルトリン酸塩は化学的安定性に優れることが知られている。しかしながら、オルトリン酸塩における金属イオンの価数は、＋３価であるため、充分な紫外線遮断効果が得られない。これに対し本発明の紫外線遮断剤を構成するピロリン酸塩では、上述のように金属イオンの価数がいずれも＋４価であるため、良好な紫外線遮断剤を示す。
【００１１】
本発明の複合リン酸塩の一般式：ＣｅxＴｉ1-xＰ2Ｏ7・ｎＨ2Ｏ（０＜ｘ＜１）において、ｘは全率にわたり自由に選択することができ、さらにｘの値により紫外線遮断効果ならびに黄色の着色度を任意に制御することができる。従って用途に応じてｘの値を自由に選ぶことができ、特に限定されないが、例えば日焼け止め化粧料としての応用を考えた場合、紫外線遮断効果を保ちつつ、粉末の黄色への着色を減少させる観点から、好ましいｘの値は０．００１〜０．５であり、より好ましくは０．０１〜０．２である。
【００１２】
また、一般式：ＣｅxＴｉ1-xＰ2Ｏ7・ｎＨ2Ｏ（０＜ｘ＜１）において、ｎは水和水分子の数を示し、化合物を形成する上で必然的に水和水分子が結合するため、０より大きくなる。水に対する溶解性を抑制する観点および撥水処理の困難性を回避する観点から、５以下、好ましくは３以下、より好ましくは２以下である。
【００１３】
上記ｘおよびｎの値は、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤の乾燥粉末におけるＣｅ、Ｔｉ等の元素分析、ならびに熱重量分析を行うことによって求めることができる．本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤は、以上説明したような組成を有する。
【００１４】
本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤は微粒子状の形態を有しており、その大きさは、平均粒径０．００３〜１μｍである。粒子の凝集の激化による分散の困難性を回避する観点から、０．００３μｍ以上、好ましくは０．０１μｍ以上、より好ましくは０．０３μｍ以上であり、紫外線吸収能、ならびに可視光領域における透明性を効果的に発揮させる観点から、１μｍ以下、好ましくは０．１μｍ以下、より好ましくは０．０５μｍ以下である。平均粒径は電子顕微鏡写真から求められる。
【００１５】
また、リン酸セリウム−リン酸チタン系紫外線遮断剤の結晶構造は、製造、乾燥後に高温熱処理あるいは水熱処理を加えない限り不定形（非晶質、アモルファス）となる。水熱処理や加熱処理等により結晶化しても、ピロリン酸塩の構造を保っていれば、本発明の紫外線遮断剤としての性能を損なうことはないが、例えば６５０℃以上で加熱したときのように、オルトリン酸塩に変化すると、紫外線遮断効果が著しく低下すること、また粒子の凝集や成長をできるだけ抑制する観点から、好ましくは不定形のまま用いられる。
【００１６】
本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤は透明性に優れ、光及び熱触媒活性が極めて低く、微粒子状形態をとることから特に紫外線遮断能に優れるという性質を有する。
【００１７】
次に、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤の製造方法について説明する。
【００１８】
本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤の製造方法は、リン酸イオンを含む塩基性水溶液と、＋４価のセリウムイオンと＋４価のチタンイオンを含む水溶液とを、混合後の分散液のｐＨが１〜１１となるように混合し、８０℃で熟成することからなる。
【００１９】
前記リン酸イオンを含む塩基性水溶液としては、リン酸アルカリ金属塩、リン酸アンモニウム塩等の水溶液を用いてもよいし、あらかじめリン酸水溶液を調製したのち、アルカリ水溶液を添加して塩基性にしたものを用いてもよい。リン酸アルカリ金属塩を用いる場合は、例えばピロリン酸ナトリウム、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、ピロリン酸カリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、ピロリン酸リチウム、リン酸二水素リチウム、リン酸水素二リチウム、リン酸三リチウム等があげられ、ピロリン酸塩を効率よく生成させる観点から、ピロリン酸ナトリウム、ピロリン酸カリウム、ピロリン酸リチウムが好ましく用いられる。また、試料中へのアルカリ金属の混入を極力抑える必要がある場合には、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム三水和物等が好ましく用いられる。
【００２０】
リン酸イオンを含む塩基性水溶液中のリン酸イオンの量は、過剰のリン酸および過剰のアルカリを水洗によって除去する手間を少なくする観点から、チタンイオンとセリウムイオンの総モル数に対してモル比で１０以下、好ましくは６．０以下、より好ましくは４．０以下が望ましく、反応を完全に行う観点から、チタンイオンとセリウムイオンの総モル数に対してモル比で１．０以上、好ましくは１．５以上、より好ましくは２．０以上が望ましい。
【００２１】
＋４価のセリウムイオンを含む溶液のセリウムイオン源としては、水溶性または酸溶解性＋４価セリウム化合物であれば特に限定がなく、例えば、硝酸二アンモニウムセリウム（IV）（Ｃｅ（ＮＨ4 ）2 （ＮＯ3 ）6 ）、硫酸四アンモニウムセリウム（IV）二水和物（Ｃｅ（ＮＨ4 ）4 （ＳＯ4 ）4 ・２Ｈ2 Ｏ）、硫酸セリウム（IV）四水和物（Ｃｅ（ＳＯ4 ）4 ・４Ｈ2 Ｏ）等が好適であり、好ましくは硫酸セリウム（IV）四水和物が用いられる。
【００２２】
＋４価のチタンイオンを含む溶液のチタンイオン源としては、水溶性または酸溶解性＋４価チタン化合物であれば特に限定がなく、例えば、塩化チタン（ＴｉＣｌ４）、硫酸チタン（IV）（Ｔｉ （ＳＯ4 ）4）、ヨウ化チタン（ＴｉＩ４）等が好適である。さらに、市販の塩化チタン（IV）や硫酸チタン（IV）の溶液等は、その取り扱いの容易さから好ましく用いられる。
【００２３】
＋４価のセリウムイオンおよび＋４価のチタンイオンを含む溶液中の金属イオン量、すなわちセリウムイオンとチタンイオンの総量は、合成の効率の観点から、リン酸イオンを含む塩基性水溶液と金属イオンを含む水溶液とを混合した反応液中の濃度が、０．０１ｍｏｌ／Ｌ以上、好ましくは０．０５ｍｏｌ／Ｌ以上、より好ましくは０．１ｍｏｌ／Ｌ以上となるような量が望ましく、一方、反応液の粘度が高くなることによる撹拌操作の困難性を回避する観点から、その上限は０．５ｍｏｌ／Ｌ以下、好ましくは０．３ｍｏｌ／Ｌ以下、より好ましくは０．２ｍｏｌ／Ｌ以下となるような量が望ましい。
【００２４】
リン酸イオンを含む塩基性水溶液と＋４価のセリウムイオンおよび＋４価のチタンイオンを含む溶液とを混合した後の分散液のｐＨは、粒径が大きくなり、紫外線吸収能が低下するのを防ぐ観点から、１以上、好ましくは２以上、より好ましくは３以上であり、得られる紫外線遮断剤粉末の水に対する溶解性が高くなるのを防ぐ観点から、１１以下、好ましくは７以下、より好ましくは６以下である。
【００２５】
リン酸イオンを含む塩基性水溶液と＋４価のセリウムイオンおよび＋４価のチタンイオンを含む溶液とを混合する方法としては、例えば、０〜５０℃で、リン酸イオンを含む塩基性水溶液を攪拌下、＋４価のセリウムイオンおよび＋４価のチタンイオンを含む溶液を５秒〜１時間程度かけて添加しながら混合する方法等があげられる。このように混合することにより、非晶質のゲルが生成する。
【００２６】
次に、生成したゲルを８０℃の温度で熟成する。熟成の時間は、均質性の観点から、３０分以上、好ましくは１時間以上が望ましく、製造上の効率性の観点から、５時間以下、好ましくは３時間以下が望ましい。
【００２７】
また、必要に応じ、生成したゲルを１２０℃〜２００℃の温度で水熱処理、あるいは焼成処理して結晶化させてもよい。ただしこのときオルトリン酸塩に変化させてはならない。
【００２８】
結晶化する条件としては、水熱温度または焼成温度が、結晶性の観点から、１２０℃以上、好ましくは１３０℃以上、より好ましくは１４０℃以上であり、凝集及び粒成長を防ぐ観点から、２００℃以下、好ましくは１９０℃以下、より好ましくは１８５℃以下である。
【００２９】
水熱処理または焼成処理の時間は、結晶性の観点から、１時間以上、好ましくは１．５時間以上が望ましく、製造上の効率性の観点から、１０時間以下、好ましくは５時間以下が望ましい。
【００３０】
以上説明したようにして、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を得ることができる。
【００３１】
熟成後は、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を濾過、遠心分離等で回収、洗浄し、必要があれば水をエタノール等の水溶性有機溶剤で置換したのち乾燥する。洗浄手段は遠心分離、濾別、デカンテーションを繰り返すか、セラミックフィルターや限外ろ過膜を使った微粉洗浄装置でもよい。洗浄が終わった粒子は、室温による自然乾燥、あるいはオーブン等を用いた加熱乾燥により乾燥する。このときに真空乾燥機やスプレードライヤーなどを用いても良い。乾燥させる際の温度は８０〜２００℃とすることが好ましい。
【００３２】
また、本発明のリン酸セリウム−リン酸チタン系を水分散系で使用する際には、水洗の最終段階で回収せず、分散液としたまま使用することができる。さらに、本発明の紫外線遮断剤の製造方法は、高温での熱処理が不要であり、８０℃の乾燥でも充分高い紫外線遮断能を有するため、製造上好都合である。
【００３３】
本発明による紫外線遮断剤の用途は、特に制限されるものではなく、紫外線の遮断を必要とするいずれの用途でも使用できるが、例えば、日焼け止めを目的とした紫外線カット化粧品、紫外線防止フィルム、耐紫外線用プラスチック、耐紫外線用塗料等に好ましく使用することができる。なかでも日焼け止め化粧料や紫外線劣化防止用フィルムに特に好適に使用される。
【００３４】
本発明の紫外線遮断剤のうち少なくとも１種類以上を、例えば、化粧料、フィルム、プラスチック、塗料等に配合すれば、可視領域の透明性を損なうことなく、ＵＶ−ＢからＵＶ−Ａ領域のほぼ全域にわたり優れた紫外線遮断効果を示し、また、触媒活性が抑制されるので安定性及び安全性が高い。
【００３５】
さらに、本発明の紫外線遮断剤は粒子そのままの形態で、例えば、化粧品、フィルム、プラスチック、及び塗料等に配合することが出来るだけでなく、ペースト状、分散液状、分散液状などの各種形態で配合することが出来る。
【００３６】
次に本発明により得られたリン酸セリウム−リン酸チタン系紫外線遮断剤を配合したプラスチックについて述べる。一般に、プラスチックは太陽光線に含まれる紫外線を吸収すると劣化をおこすことが知られている。その対策として本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を配合することで光劣化を防止あるいは低減できる。
【００３７】
また、リン酸セリウム−リン酸チタン系紫外線遮断剤のプラスチックに対する配合比率は任意に設定することができるが、好ましくは０．５〜５０重量％の範囲に調整する。配合率が０．５重量％以下では少なすぎて十分な紫外線遮断効果を得られず、一方、５０重量％以上では分散性が低下する。また、配合の際に分散剤等の添加剤を加えても良い。
【００３８】
さらに、本発明による紫外線遮断剤をフィルムに配合し、これを表面保護用途に使用することにより、フィルムより下層にある接着剤、プラスチック板、木板、鋼板及び染料、願料等の着色剤等は、紫外線から保護されるため長期間に亘って、使用することができる資材となる。
【００３９】
一方、本発明の紫外線遮断剤を配合する塗料とは、特に規定するものではなく、いずれの塗料でも良いが、塗装法による分類のうち、常温乾燥塗料及び焼付け塗料が好ましく使用される。
【００４０】
本発明による紫外線遮断剤を配合したプラスチックやフィルム、塗料としては、例えば、照明用カバー、電子基板及びＥＬ等の電気・電子材料、自動車用内装パネル等の自動車部品、機械部品、食品および薬品等の包装や容器、繊維、看板、鋼板、プラスチック板、シート、農業用被覆資材、屋根、テント及び屋外倉庫等の屋外構築物、自動車、車両、船舶、航空機、家庭用電化製品、機械類、建築物外壁、橋梁、事務用品、眼鏡用レンズ、玩具、雑貨等が例示されるが、紫外線遮断性が必要とされるものであれば、いかなるフィルム、プラスチック、塗料等にも使用可能である。
【００４１】
上記プラスチックやフィルム、および塗料の原料となる樹脂としては、熱可塑性樹脂や熱硬化性樹脂が用いられる。熱可塑性樹脂としては、例えば含フッ素樹脂、アクリル樹脂、ポリアミド樹脂、塩化ビニル樹脂、ポリカーボネイト樹脂、オレフィン系樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリエステル樹脂、ポリエーテルイミド樹脂、ポリエーテルスルホン酸樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリアリレート樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリメチルペンテン樹脂、ＡＢＳ樹脂、酢酸ビニル樹脂、およびポリエチレン樹脂等があり、なかでも比較的高温で加熱成形できる含フッ素樹脂、アクリル樹脂、ポリアミド樹脂、ポリカーボネイト樹脂、ポリエステル樹脂が好ましい。
【００４２】
さらに熱硬化性樹脂としては、例えば、メラミン樹脂、フエノール樹脂、ユリア樹脂、フラン樹脂、アルキッド樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、ケイ素樹脂、ポリウレタン樹脂、ポリイミド樹脂、ポリパラバン酸樹脂等が用いられ、なかでもエポキシ樹脂、ジアリルフタレート樹脂、ポリイミド樹脂が好ましい。
【００４３】
次に本発明により得られた紫外線遮断剤を配合した化粧料について述べる。本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を配合した化粧料は透明性が高く、優れた紫外線遮断効果を発揮する。化粧料の剤型としては、例えば、乳液、クリーム、ローション、ファンデーション、コンパクトパウダー、マニキュア、口紅、アイシャドウ、化粧水、整髪料等に用いることができ、日焼け止め化粧料として用いるのが好ましい。配合率は特に限定されないが、０．１〜７０重量％に調節するのが望ましい。配合率が０．５重量％以下であると十分な紫外線遮断効果を得にくくなる場合があり、他方、７０重量％以上配合すると分散性、透明性が低下する場合がある。
【００４４】
さらに、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を化粧料に用いる場合、例えば、分散剤、界面活性剤、油剤、ゲル化剤、高分子、保湿剤、美容成分、色素、防腐剤、粉体、香料等の添加剤を本発明の効果を妨げない範囲で使用することができる。
【００４５】
また、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を上記各製品に配合する場合、本発明の紫外線遮断剤をさらに表面処理したものを用いても良い。表面処理としては、アミノ酸処理、コラーゲン処理、レシチン処理、トリグリセライド処理、シリコーン処理、金属石鹸処理、キチン・キトサン処理等が挙げられる。
【００４６】
加えて、本発明のリン酸セリウム−リン酸チタン系紫外線遮断剤を上記各製品に配合する場合、異なる組成のものを２種類以上組み合わせて用いても良い。
【００４７】
さらに、本発明の紫外線遮断剤に加えて、有機系紫外線吸収剤や無機系紫外線遮断剤を少なくとも１種類以上、製品や環境の汚染等、その使用に起因する問題点を生じない範囲で微量添加し、本発明の紫外線遮断剤と併用することにより両者の利点を同時利用できるようにしてもよい。この場合の有機系紫外線吸収剤としては、例えば、サリチル酸系、ベンゾフェノン系、ベンゾトリアゾール系あるいはシアノアクリレート系、４−ターシャリブチル−４'−メトキシベンゾイルメタン等の各種紫外線遮断剤などがあげられる。具体例として、サリチル酸系紫外線遮断剤としては、サリチル酸オクチル、サリチル酸ホモメンチル、サリチル酸メチル等がある。ベンゾフェノン系紫外線遮断剤としては、ヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、ヒドロキシメトキシベンゾフェノンスルホン酸、ヒドロキシメトキシベンゾフェノンスルホン酸ナトリウム、ヒドロキシメトキシベンゾフェノン、オキシベンゾン等がある。ベンゾトリアゾール系紫外線遮断剤としては、２−（２−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−５−ターシャリブチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−３−５−ジターシャリブチルフェニル）−５−クロロベンゾトリアゾール等がある。シアノアクリレート系紫外線遮断剤としては、２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート、エチル−２−シアノ−３，３−ジフェニルアクリレート等がある。一方、無機系紫外線遮断剤としては酸化チタン、酸化亜鉛、あるいは酸化セリウム等の少なくとも１種類以上が好ましく、より好ましくは平均粒径５０ｎｍ以下の酸化チタン、酸化亜鉛、酸化セリウムが用いられる。
【００４８】
【物性の測定法】
各紫外線遮断剤について、粉末Ｘ線回折測定（マックサイエンス社製、Ｍ１８ＸＨＦ−ＳＨＡ型）により生成相を同定し、また透過型電子顕微鏡（日立製作所製 Ｈ−８００型）観察により、試料粉末の粒子形状および平均粒径を測定した。
【００４９】
紫外線遮断性および可視光透明性は紫外可視分光光度計（島津製作所製、ＵＶ−２５５０型、積分球付き）を用いて測定した。試料の紫外線遮断能を判断するための評価として、硫酸バリウム粉末（和光純薬製、試薬特級）を参照試料とし、上記分光光度計を用いて反射スペクトルを測定した。この反射スペクトルにおける３２０〜４００ｎｍ（ＵＶ−Ａ）、および２５０〜３２０ｎｍ（ＵＶ−Ｂ）の反射率の値が可視光域の反射率に比べて小さいほど、選択的に紫外線を吸収していることを表す。
【００５０】
各紫外線遮断剤粉末の色相（Ｌ*, ａ*, ｂ* ）を、ミノルタ製ＣＲ−３００型色彩色彩計を用いて測定した。
【００５１】
一定量の紫外線遮断剤粉末を、濃塩酸（３５％）に少量の過酸化水素（３０％）を加えて溶解させ、この溶液について、ＩＣＰ発光分析法（島津製作所製ＩＣＰ−Ｓ１０００IV型）によりＴｉ、ＣｅおよびＰの定量分析を行った。
【００５２】
紫外線遮断剤の熱触媒活性は、例えば、粧技誌、第３１巻（１９９７年）第３２９〜３３２頁に記載されている方法に準じ、ひまし油５．０ｇ中に紫外線遮断剤０．３ｇを混合し、１時間あたり１５リットルの空気流通下、１３０℃で加熱しながら流通後の空気を５０ミリリットルの脱イオン水中へ導いて分解生成物を捕集し、３時間後の水の導電率変化を測定することで評価した。さらに、光触媒活性については１３０℃で３時間加熱するかわりに、ソーラシミュレータ（山下電装（株）製、ＹＳＳ−８０型）で９時間光照射した後の水の導電率変化を測定することで評価した。
【００５３】
【実施例】
以下に実施例をあげて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
【００５４】
（実施例１）
リン酸水素二ナトリウムを５００℃で５時間加熱して得られたピロリン酸ナトリウム２．６６ｇを１００ｍｌの水に溶解させ水溶液を得た。これに市販の硫酸セリウム４水和物３．８４ｇと３０％硫酸チタン溶液０．４０ｇを脱イオン水に溶解させた水溶液１００ｍｌを撹拌下、室温で混合すると、直ちに沈殿ゲルが生成した。このゲル分散液のｐＨは２であった。このゲルを８０℃で３０分熟成した後、析出物を遠心分離およびイオン交換水への再分散を繰り返すことにより水洗し、８０℃で２４時間乾燥することにより淡黄色の紫外線遮断剤粉末を得た。
【００５５】
得られた粉末について、前記の測定および評価を行った。結果を表１、図１および図２に示す。図２には、後に述べる実施例２から５の結果も併せて示されているが、この図より明らかなように、本発明の紫外線遮断剤においては、セリウムとチタンの比を変えることによりスペクトルを自在に変化させ、紫外線遮断効果を任意に制御することができる。
【００５６】
【表１】
表１における触媒活性抑制の評価項目と評価基準は以下の通りである。
○：触媒活性が全くみられない。
△：わずかに触媒活性がみられ、実用上好ましくない。
×：触媒活性があり、実用的には使用できない。
【００５８】
図１に示すこの試料のＸ線回折パターンより明らかなように、アモルファス物質に一般的に見られるハロパターンが観察された。ＩＣＰ発光分析により組成の分析を行ったところ、その組成はＴｉ０．０５Ｃｅ０．９５Ｐ２Ｏ７であった。さらに、透過型電子顕微鏡観察を行ったところ、この試料は平均粒径０．０１０μｍ（１０ｎｍ）の超微粒子の粉末であることがわかった。紫外線遮断能は図２および表１に示すように優れており、透明性にも優れるものであった。また、熱・光触媒活性についても全く見られなかった。
【００５９】
（実施例２）
リン酸水素二ナトリウムを５００℃で５時間加熱して得られたピロリン酸ナトリウム２．６６ｇを１００ｍｌの水に溶解させて得た水溶液に、市販の硫酸セリウム４水和物２．０２ｇと３０％硫酸チタン溶液４．００ｇを脱イオン水に溶解させた水溶液１００ｍｌを撹拌下、室温で混合し、アモルファスの沈殿ゲルを得た。以後の操作を実施例１と同様に行って、粉末を得た。得られた粉末について、前記の測定および評価を行った。結果を表１に示す。
【００６０】
（実施例３）
リン酸水素二ナトリウムを５００℃で５時間加熱して得られたピロリン酸ナトリウム２．６６ｇを１００ｍｌの水に溶解させて得た水溶液に、市販の硫酸セリウム４水和物０．４０ｇと３０％硫酸チタン溶液７．２０ｇを脱イオン水に溶解させた水溶液１００ｍｌを撹拌下、室温で混合し、アモルファスの沈殿ゲルを得た。以後の操作を実施例１と同様に行って、粉末を得た。得られた粉末について、前記の測定および評価を行ったところ、図３に見られるように、この試料は平均粒径０．０１０μｍ（１０ｎｍ）の超微粒子の粉末であることがわかった。その他の結果を表１に示す。
【００６１】
（実施例４）
リン酸水素二ナトリウムを５００℃で５時間加熱して得られたピロリン酸ナトリウム３．９９ｇを１５０ｍｌの水に溶解させて得た水溶液に、市販の硫酸セリウム４水和物０．４２ｇと３０％硫酸チタン溶液１１．１８ｇを脱イオン水に溶解させた水溶液１５０ｍｌを撹拌下、室温で混合し、アモルファスの沈殿ゲルを得た。以後の操作を実施例１と同様に行って、粉末を得た。得られた粉末について、前記の測定および評価を行った。結果を表１に示す。
【００６２】
（実施例５）
リン酸水素二ナトリウムを５００℃で５時間加熱して得られたピロリン酸ナトリウム２．６６ｇを１００ｍｌの水に溶解させて得た水溶液に、市販の硫酸セリウム４水和物０．２０ｇと３０％硫酸チタン溶液７．６０ｇを脱イオン水に溶解させた水溶液１００ｍｌを撹拌下、室温で混合し、アモルファスの沈殿ゲルを得た。以後の操作を実施例１と同様に行って、粉末を得た。得られた粉末について、前記の測定および評価を行った。結果を表１に示す。
【００６３】
【比較例】
（比較例１）
市販のルチル型超微粒子酸化チタンを用い、上記記載の方法により、組成、平均粒子径、紫外線遮断性、可視光透明性、熱および光触媒活性、色相についてそれぞれ評価した。結果を表１に示す。
【００６４】
（比較例２）
市販の超微粒子酸化亜鉛を用い、上記記載の方法により、組成、平均粒子径、紫外線遮断性、可視光透明性、熱および光触媒活性、色相についてそれぞれ評価した。結果を表１に示す。
【００６５】
実施例１〜５で製造した紫外線遮断剤、並びに比較例１〜２の紫外線遮断剤の物性測定結果から、例えば図４と表１に見られるように、本発明の紫外線遮断剤の紫外線遮断効果は優れており、さらに熱、光触媒活性のいずれも示さないことがわかる。
【００６６】
【発明の効果】
以上より、本発明の紫外線遮断剤は、透明性、分散性、耐候性、耐熱性に優れ、また組成により紫外線遮断効果ならびに黄色の着色度を任意に制御可能であり、化粧料、フィルム、プラスチックおよび塗料等、各種製品に配合することにより、紫外線による劣化や変質の防止に極めて有効に作用する。
【図面の簡単な説明】
【図１】実施例１で製造したリン酸セリウム−リン酸チタン系紫外線遮断剤のＸ線回折図である。
【図２】実施例１〜５で製造したリン酸セリウム−リン酸チタン系紫外線遮断剤の紫外可視反射スペクトルである。
【図３】実施例３で製造したリン酸セリウム−リン酸チタン系紫外線遮断剤の透過型電子顕微鏡写真である。
【図４】実施例２で製造したリン酸セリウム−リン酸チタン系紫外線遮断剤、および比較例１〜２のルチル型超微粒子酸化チタン、超微粒子酸化亜鉛の紫外可視反射スペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cerium phosphate-titanium phosphate ultraviolet blocking agent having very high transparency and excellent stability and safety, and a method for producing the same.
[0002]
[Prior art]
Ultraviolet rays not only deteriorate organic materials such as plastics, but also have a strong adverse effect on living organisms. Ultraviolet rays in the UV-B region having a wavelength of 280 to 320 nm cause skin inflammation, and UV having a wavelength of 320 to 400 nm. UV radiation in the -A region is known to make the skin brown. As one of the prevention methods, various organic ultraviolet absorbers and inorganic ultraviolet scattering agents have been developed.
[0003]
Organic UV absorbers have been widely used because they are colorless and transparent when blended with plastics and cosmetics. There are many problems and usage is restricted. On the other hand, titanium oxide and zinc oxide are generally used as the inorganic ultraviolet blocking agent, and in addition, cerium oxide has also been partially applied. However, these compounds have advantages and disadvantages in terms of ultraviolet blocking properties, transparency, and catalytic activity due to light and heat. In actual use, those whose surfaces are coated with silica, alumina, boron nitride, etc. are used. Yes. However, the finer the particles, the more the particles are agglomerated by the surface treatment, so the dispersibility of the particles deteriorates, and it is impossible to simultaneously achieve high transparency and low catalytic activity while maintaining the ultraviolet absorbing ability. It was.
[0004]
In order to solve the above problems, for example, as shown in JP-A-11-189766 and JP-A-10-204288, ultraviolet blocking agents such as cerium phosphate, titanium phosphate or zirconium phosphate have been proposed. However, cerium phosphate has a strong yellow coloration, especially in cosmetics, and its composition is limited, and titanium phosphate and zirconium phosphate are still fatal, such as a sufficient UV blocking effect in the UV-A region. Have some problems.
[0005]
[Problems to be solved by the invention]
Therefore, the object of the present invention is excellent in transparency, UV-A and UV-B ultraviolet blocking ability, and extremely low photo / thermal catalytic activity, which could not be achieved by conventional techniques and production methods. An ultraviolet blocking agent and a method for producing the same are provided.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the ultraviolet blocking agent of the present invention is characterized in that cerium phosphate and titanium phosphate are combined. By adopting this configuration, an excellent ultraviolet blocking effect having both the excellent UV-A blocking property of cerium phosphate and the excellent UV-B blocking property of titanium phosphate can be obtained. Moreover, since it is a combination of substances that are chemically stable to each other, composite particles having excellent weather resistance and heat resistance can be obtained, and can be suitably used as an ultraviolet blocking agent, for example, in applications exposed to harsh environments.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The cerium phosphate-titanium phosphate UV-blocking agent of the present invention has a general formula: Ce x Ti 1-x P 2 O 7 ・ NH 2 O ( 0 <x <1 The average particle size is 0.003 to 1 μm.
[0008]
Furthermore, the composite particles of the present invention are characterized in that +4 valent cerium ions and +4 valent titanium ions are co-precipitated with phosphate ions in a solution and uniformly formed at the atomic level to form pyrophosphate. To do. Therefore, cerium in the cerium phosphate-titanium phosphate UV blocking agent obtained in the present invention exists as +4 valence.
[0009]
In addition, the refractive index of the composite phosphate obtained in the present invention is smaller than that of the oxide system, and is approximately 1.8 to 2.0 depending on the composition. When the refractive index is low, the light scattering property of the powder with respect to visible light is reduced, and in particular, when blended in cosmetics, paints, etc., the transparency is improved as compared with conventional oxides. Furthermore, by using a composite phosphate, the light and thermal catalytic activity, which is one of the major problems of the conventional inorganic ultraviolet blocking agents, are remarkably suppressed.
[0010]
In addition to pyrophosphate, orthophosphate, polyphosphate, and the like are known as phosphates. Among them, general formula: MPO 4 ・ NH 2 It is known that orthophosphate represented by O (M is a metal ion) is excellent in chemical stability. However, since the valence of metal ions in orthophosphate is +3, a sufficient ultraviolet blocking effect cannot be obtained. On the other hand, the pyrophosphates constituting the ultraviolet blocking agent of the present invention show a good ultraviolet blocking agent because the valences of the metal ions are all +4 as described above.
[0011]
General formula of the composite phosphate of the present invention: Ce x Ti 1-x P 2 O 7 ・ NH 2 O ( 0 <x <1 ), X can be freely selected over the entire ratio, and the ultraviolet blocking effect and the yellow coloring degree can be arbitrarily controlled by the value of x. Therefore, the value of x can be freely selected according to the use, and is not particularly limited. For example, when considering application as a sunscreen cosmetic, the coloration of the powder to yellow is reduced while maintaining the UV blocking effect. From the viewpoint, a preferable value of x is 0.001 to 0.5, and more preferably 0.01 to 0.2.
[0012]
In addition, the general formula: Ce x Ti 1-x P 2 O 7 ・ NH 2 O ( 0 <x <1 ), N represents the number of hydrated water molecules, and is inevitably larger than 0 because the hydrated water molecules are inevitably bound to form a compound. From the viewpoint of suppressing solubility in water and from the viewpoint of avoiding the difficulty of water repellent treatment, it is 5 or less, preferably 3 or less, more preferably 2 or less.
[0013]
The values of x and n can be determined by conducting elemental analysis of Ce, Ti, etc., and thermogravimetric analysis in the dry powder of the cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention. The cerium phosphate-titanium phosphate UV blocking agent of the present invention has the composition as described above.
[0014]
The cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention has a fine particle form, and the average particle size is 0.003 to 1 μm. From the viewpoint of avoiding the difficulty of dispersion due to intensification of particle aggregation, it is 0.003 μm or more, preferably 0.01 μm or more, more preferably 0.03 μm or more. From the viewpoint of effectively exhibiting, it is 1 μm or less, preferably 0.1 μm or less, more preferably 0.05 μm or less. The average particle size is determined from an electron micrograph.
[0015]
Further, the crystal structure of the cerium phosphate-titanium phosphate UV blocker is indefinite (amorphous or amorphous) unless high-temperature heat treatment or hydrothermal treatment is applied after production and drying. Even if it is crystallized by hydrothermal treatment, heat treatment or the like, as long as the structure of pyrophosphate is maintained, the performance as the ultraviolet blocking agent of the present invention is not impaired. For example, when heated at 650 ° C. or higher When changed to orthophosphate, the ultraviolet blocking effect is remarkably lowered, and from the viewpoint of suppressing aggregation and growth of particles as much as possible, it is preferably used in an indefinite form.
[0016]
The cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention has excellent transparency, extremely low light and thermal catalytic activity, and has a property of being particularly excellent in ultraviolet blocking ability because of its particulate form.
[0017]
Next, the manufacturing method of the cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention will be described.
[0018]
The method for producing a cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention comprises a dispersion after mixing a basic aqueous solution containing phosphate ions and an aqueous solution containing +4 valent cerium ions and +4 valent titanium ions. It mixes so that pH of a liquid may be set to 1-11, and consists of ageing | curing | ripening at 80 degreeC.
[0019]
As the basic aqueous solution containing phosphate ions, an aqueous solution of an alkali metal phosphate, ammonium phosphate, or the like may be used. After preparing an aqueous phosphate solution in advance, an alkaline aqueous solution is added to make the solution basic. You may use what you did. When using alkali metal phosphate, for example, sodium pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid Examples include tripotassium, lithium pyrophosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, and trilithium phosphate. From the viewpoint of efficiently producing pyrophosphate, sodium pyrophosphate, potassium pyrophosphate, lithium pyrophosphate Is preferably used. In addition, when it is necessary to suppress alkali metal contamination in the sample as much as possible, monoammonium phosphate, diammonium phosphate, triammonium phosphate trihydrate and the like are preferably used.
[0020]
The amount of phosphate ion in the basic aqueous solution containing phosphate ion is less than the total number of moles of titanium ion and cerium ion from the viewpoint of reducing the trouble of removing excess phosphoric acid and excess alkali by washing with water. The ratio is 10 or less, preferably 6.0 or less, and more preferably 4.0 or less. From the viewpoint of complete reaction, the molar ratio with respect to the total number of moles of titanium ions and cerium ions is 1.0 or more, Preferably it is 1.5 or more, more preferably 2.0 or more.
[0021]
The cerium ion source of the solution containing + tetravalent cerium ions is not particularly limited as long as it is water-soluble or acid-soluble + tetravalent cerium compound. For example, diammonium cerium nitrate (IV) (Ce (NH Four ) 2 (NO Three ) 6 ), Tetraammonium cerium (IV) sulfate dihydrate (Ce (NH Four ) Four (SO Four ) Four ・ 2H 2 O), cerium (IV) sulfate tetrahydrate (Ce (SO Four ) Four ・ 4H 2 O) and the like are suitable, and cerium (IV) sulfate tetrahydrate is preferably used.
[0022]
The titanium ion source of the solution containing +4 valent titanium ions is not particularly limited as long as it is a water-soluble or acid-soluble +4 valent titanium compound. For example, titanium chloride (TiCl 4 ), Titanium sulfate (IV) (Ti (SO Four ) Four ), Titanium iodide (TiI 4 And the like are preferred. Furthermore, commercially available solutions of titanium chloride (IV), titanium sulfate (IV) and the like are preferably used because of their easy handling.
[0023]
The amount of metal ions in a solution containing +4 valent cerium ions and +4 valent titanium ions, that is, the total amount of cerium ions and titanium ions includes a basic aqueous solution containing phosphate ions and metal ions from the viewpoint of the efficiency of synthesis. It is desirable that the concentration in the reaction solution mixed with the aqueous solution is 0.01 mol / L or more, preferably 0.05 mol / L or more, more preferably 0.1 mol / L or more. From the viewpoint of avoiding difficulty in stirring operation due to an increase in viscosity, the upper limit is 0.5 mol / L or less, preferably 0.3 mol / L or less, more preferably 0.2 mol / L or less. Is desirable.
[0024]
The pH of the dispersion after mixing the basic aqueous solution containing phosphate ions and the solution containing +4 valent cerium ions and +4 valent titanium ions prevents the particle size from increasing and the UV absorption ability from decreasing. From the viewpoint, it is 1 or more, preferably 2 or more, more preferably 3 or more, and from the viewpoint of preventing the solubility of the obtained ultraviolet blocking agent powder in water from 11 or less, preferably 7 or less, more preferably 6 or less.
[0025]
As a method of mixing a basic aqueous solution containing phosphate ions and a solution containing +4 valent cerium ions and +4 valent titanium ions, for example, the basic aqueous solution containing phosphate ions is stirred at 0 to 50 ° C. And a method of mixing while adding a solution containing +4 valent cerium ions and +4 valent titanium ions over about 5 seconds to 1 hour. By mixing in this way, an amorphous gel is formed.
[0026]
Next, the produced gel is aged at a temperature of 80 ° C. The aging time is 30 minutes or more, preferably 1 hour or more from the viewpoint of homogeneity, and 5 hours or less, preferably 3 hours or less, from the viewpoint of production efficiency.
[0027]
Moreover, you may crystallize the produced | generated gel by hydrothermal treatment or the baking processing at the temperature of 120 to 200 degreeC as needed. However, it should not be changed to orthophosphate at this time.
[0028]
As conditions for crystallization, the hydrothermal temperature or the firing temperature is 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher, from the viewpoint of crystallinity. From the viewpoint of preventing aggregation and grain growth, 200 ° C or lower, preferably 190 ° C or lower, more preferably 185 ° C or lower.
[0029]
The hydrothermal treatment or firing treatment time is 1 hour or more, preferably 1.5 hours or more from the viewpoint of crystallinity, and 10 hours or less, preferably 5 hours or less, from the viewpoint of production efficiency.
[0030]
As described above, the cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention can be obtained.
[0031]
After aging, the cerium phosphate-titanium phosphate UV blocking agent of the present invention is collected and washed by filtration, centrifugation, etc., and if necessary, water is replaced with a water-soluble organic solvent such as ethanol and then dried. The washing means may be a fine powder washing apparatus that repeats centrifugation, filtration, and decantation, or uses a ceramic filter or ultrafiltration membrane. The washed particles are dried by natural drying at room temperature or by heat drying using an oven or the like. At this time, a vacuum dryer or a spray dryer may be used. The drying temperature is preferably 80 to 200 ° C.
[0032]
Further, when the cerium phosphate-titanium phosphate system of the present invention is used in an aqueous dispersion, it can be used as a dispersion without being recovered at the final stage of washing with water. Furthermore, the method for producing an ultraviolet blocking agent of the present invention is advantageous in production because it does not require heat treatment at a high temperature and has a sufficiently high ultraviolet blocking ability even when dried at 80 ° C.
[0033]
The application of the ultraviolet blocking agent according to the present invention is not particularly limited, and can be used in any application that requires blocking ultraviolet rays. For example, UV-cutting cosmetics intended for sunscreen, UV-resistant films, It can be preferably used for UV plastics, UV resistant paints, and the like. Among them, it is particularly preferably used for sunscreen cosmetics and UV deterioration preventing films.
[0034]
If at least one of the ultraviolet blocking agents of the present invention is blended in, for example, cosmetics, films, plastics, paints, etc., the UV-B to UV-A region can be obtained without impairing the transparency in the visible region. Excellent ultraviolet blocking effect over the entire area, and since the catalytic activity is suppressed, stability and safety are high.
[0035]
Furthermore, the ultraviolet blocking agent of the present invention can be blended in various forms such as paste, dispersed liquid, and dispersed liquid as well as in the form of particles as it is, for example, in cosmetics, films, plastics, and paints. I can do it.
[0036]
Next, a plastic containing a cerium phosphate-titanium phosphate ultraviolet blocking agent obtained by the present invention will be described. In general, it is known that plastics deteriorate when absorbing ultraviolet rays contained in sunlight. As a countermeasure, photodegradation can be prevented or reduced by blending the cerium phosphate-titanium phosphate UV blocking agent of the present invention.
[0037]
The blending ratio of the cerium phosphate-titanium phosphate UV blocking agent to the plastic can be arbitrarily set, but is preferably adjusted to a range of 0.5 to 50% by weight. When the blending ratio is 0.5% by weight or less, it is too small to obtain a sufficient ultraviolet blocking effect, whereas when it is 50% by weight or more, dispersibility is lowered. Moreover, you may add additives, such as a dispersing agent, in the case of a mixing | blending.
[0038]
Furthermore, by blending the ultraviolet blocking agent according to the present invention into a film and using it for surface protection, adhesives, plastic plates, wood boards, steel plates and dyes, dyes, etc., etc. under the film are used. Since it is protected from ultraviolet rays, it can be used for a long period of time.
[0039]
On the other hand, the paint blended with the ultraviolet blocking agent of the present invention is not particularly specified, and any paint may be used, but among the classifications based on the coating method, room temperature dry paint and baking paint are preferably used.
[0040]
Examples of plastics, films, and paints that contain the ultraviolet blocking agent according to the present invention include lighting covers, electric and electronic materials such as electronic substrates and EL, automobile parts such as automobile interior panels, machine parts, foods, and medicines. Packaging and containers, textiles, signboards, steel plates, plastic plates, sheets, covering materials for agriculture, roofs, tents, outdoor structures such as outdoor warehouses, automobiles, vehicles, ships, aircraft, household appliances, machinery, buildings Examples include outer walls, bridges, office supplies, spectacle lenses, toys, sundries, etc., but any film, plastic, paint, etc. can be used as long as UV blocking is required.
[0041]
A thermoplastic resin or a thermosetting resin is used as the resin used as a raw material for the plastic, film, and paint. Examples of thermoplastic resins include fluorine-containing resins, acrylic resins, polyamide resins, vinyl chloride resins, polycarbonate resins, olefin resins, epoxy resins, polyacetal resins, polyester resins, polyetherimide resins, polyether sulfonic acid resins, polyethers. There are ether ketone resin, polyphenylene sulfide resin, polysulfone resin, polyarylate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polymethylpentene resin, ABS resin, vinyl acetate resin, polyethylene resin, etc. Fluorine-containing resins, acrylic resins, polyamide resins, polycarbonate resins, and polyester resins that can be molded are preferred.
[0042]
Further, as the thermosetting resin, for example, melamine resin, phenol resin, urea resin, furan resin, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, polyurethane resin, polyimide resin, polyparabanic acid resin, etc. Among them, epoxy resin, diallyl phthalate resin, and polyimide resin are preferable.
[0043]
Next, a cosmetic containing the ultraviolet blocking agent obtained by the present invention will be described. Cosmetics containing the cerium phosphate-titanium phosphate UV blocking agent of the present invention are highly transparent and exhibit an excellent UV blocking effect. As a cosmetic dosage form, for example, it can be used for milky lotion, cream, lotion, foundation, compact powder, nail polish, lipstick, eye shadow, lotion, hair styling, etc., and preferably used as a sunscreen cosmetic. The blending ratio is not particularly limited, but it is desirable to adjust to 0.1 to 70% by weight. If the blending ratio is 0.5% by weight or less, it may be difficult to obtain a sufficient ultraviolet blocking effect. On the other hand, if the blending ratio is 70% by weight or more, dispersibility and transparency may be deteriorated.
[0044]
Furthermore, when the cerium phosphate-titanium phosphate UV-blocking agent of the present invention is used in cosmetics, for example, a dispersant, a surfactant, an oil agent, a gelling agent, a polymer, a moisturizer, a cosmetic ingredient, a pigment, an antiseptic Additives such as agents, powders, and fragrances can be used as long as the effects of the present invention are not impaired.
[0045]
In addition, when the cerium phosphate-titanium phosphate ultraviolet blocking agent of the present invention is blended into the above products, the ultraviolet blocking agent of the present invention may be further surface-treated. Examples of the surface treatment include amino acid treatment, collagen treatment, lecithin treatment, triglyceride treatment, silicone treatment, metal soap treatment, chitin / chitosan treatment and the like.
[0046]
In addition, when the cerium phosphate-titanium phosphate UV-blocking agent of the present invention is blended in the above products, two or more types having different compositions may be used in combination.
[0047]
Furthermore, in addition to the UV blocker of the present invention, at least one organic UV absorber or inorganic UV blocker is added in a range that does not cause problems due to its use, such as product and environmental contamination. However, by using together with the ultraviolet blocking agent of the present invention, both advantages may be used simultaneously. Examples of the organic ultraviolet absorber in this case include salicylic acid-based, benzophenone-based, benzotriazole-based or cyanoacrylate-based, and various ultraviolet blocking agents such as 4-tert-butyl-4′-methoxybenzoylmethane. Specific examples of the salicylic acid-based UV blocker include octyl salicylate, homomenthyl salicylate, and methyl salicylate. Examples of the benzophenone ultraviolet blocking agent include hydroxybenzophenone, tetrahydroxybenzophenone, hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, hydroxymethoxybenzophenone, and oxybenzone. Examples of the benzotriazole ultraviolet blocking agent include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3- 5-ditertiarybutylphenyl) -5-chlorobenzotriazole and the like. Examples of the cyanoacrylate ultraviolet blocking agent include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate. On the other hand, as the inorganic ultraviolet blocking agent, at least one kind of titanium oxide, zinc oxide, cerium oxide or the like is preferable, and titanium oxide, zinc oxide or cerium oxide having an average particle diameter of 50 nm or less is more preferable.
[0048]
[Measurement method of physical properties]
For each ultraviolet blocking agent, the generated phase was identified by powder X-ray diffraction measurement (M18XHF-SHA type, manufactured by Mac Science), and the particles of the sample powder were observed by observation with a transmission electron microscope (H-800 type, manufactured by Hitachi, Ltd.). Shape and average particle size were measured.
[0049]
The ultraviolet blocking property and the visible light transparency were measured using an ultraviolet visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550 type, with integrating sphere). As an evaluation for judging the ultraviolet blocking ability of the sample, barium sulfate powder (manufactured by Wako Pure Chemicals, special grade of reagent) was used as a reference sample, and the reflection spectrum was measured using the above spectrophotometer. As the reflectance values of 320 to 400 nm (UV-A) and 250 to 320 nm (UV-B) in this reflection spectrum are smaller than the reflectance in the visible light range, ultraviolet rays are selectively absorbed. Represents.
[0050]
Hue of each UV blocker powder (L * , a * , b * ) Was measured using a Minolta CR-300 type colorimeter.
[0051]
A certain amount of ultraviolet blocking agent powder was dissolved in concentrated hydrochloric acid (35%) by adding a small amount of hydrogen peroxide (30%), and this solution was dissolved in TiP by ICP emission analysis (ICP-S1000IV type manufactured by Shimadzu Corporation). , Ce and P were quantitatively analyzed.
[0052]
The thermal catalytic activity of the ultraviolet blocking agent is determined by mixing 0.3 g of the ultraviolet blocking agent in 5.0 g of castor oil according to the method described in, for example, Cosmetic Technology, Vol. 31 (1997), pages 329 to 332. Then, while heating at 130 ° C. under an air flow of 15 liters per hour, the air after distribution is introduced into 50 ml of deionized water to collect decomposition products, and the conductivity change of water after 3 hours is changed. It evaluated by measuring. Furthermore, the photocatalytic activity was evaluated by measuring the change in conductivity of water after 9 hours of light irradiation with a solar simulator (YSS-80 model, manufactured by Yamashita Denso Co., Ltd.) instead of heating at 130 ° C. for 3 hours. did.
[0053]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0054]
Example 1
2.66 g of sodium pyrophosphate obtained by heating disodium hydrogen phosphate at 500 ° C. for 5 hours was dissolved in 100 ml of water to obtain an aqueous solution. When 100 ml of an aqueous solution prepared by dissolving 3.84 g of commercially available cerium sulfate tetrahydrate and 0.40 g of 30% titanium sulfate solution in deionized water was mixed with stirring at room temperature, a precipitated gel was immediately formed. The pH of this gel dispersion was 2. After aging this gel at 80 ° C. for 30 minutes, the precipitate was washed with water by repeated centrifugation and redispersion in ion-exchanged water, and dried at 80 ° C. for 24 hours to obtain a pale yellow UV screening powder. It was.
[0055]
About the obtained powder, the said measurement and evaluation were performed. The results are shown in Table 1, FIG. 1 and FIG. FIG. 2 also shows the results of Examples 2 to 5, which will be described later. As is clear from this figure, in the ultraviolet blocking agent of the present invention, the spectrum is changed by changing the ratio of cerium and titanium. Can be freely controlled to arbitrarily control the ultraviolet blocking effect.
[0056]
[Table 1]
The evaluation items and evaluation criteria for catalyst activity suppression in Table 1 are as follows.
○: No catalytic activity is observed.
Δ: Slight catalytic activity is observed, which is not preferable for practical use.
X: It has catalytic activity and cannot be used practically.
[0058]
As apparent from the X-ray diffraction pattern of this sample shown in FIG. 1, a halo pattern generally observed in amorphous materials was observed. When the composition was analyzed by ICP emission analysis, the composition was Ti 0.05 Ce 0.95 P 2 O 7 Met. Further, observation with a transmission electron microscope revealed that this sample was an ultrafine powder having an average particle size of 0.010 μm (10 nm). The ultraviolet blocking ability was excellent as shown in FIG. 2 and Table 1, and the transparency was also excellent. Further, no thermal / photocatalytic activity was observed.
[0059]
(Example 2)
To an aqueous solution obtained by dissolving 2.66 g of sodium pyrophosphate obtained by heating disodium hydrogen phosphate at 500 ° C. for 5 hours in 100 ml of water, 2.02 g of commercially available cerium sulfate tetrahydrate and 30% 100 ml of an aqueous solution in which 4.00 g of a titanium sulfate solution was dissolved in deionized water was mixed at room temperature with stirring to obtain an amorphous precipitated gel. Subsequent operations were performed in the same manner as in Example 1 to obtain a powder. About the obtained powder, the said measurement and evaluation were performed. The results are shown in Table 1.
[0060]
(Example 3)
To an aqueous solution obtained by dissolving 2.66 g of sodium pyrophosphate obtained by heating disodium hydrogen phosphate at 500 ° C. for 5 hours in 100 ml of water, 0.40 g of commercially available cerium sulfate tetrahydrate and 30% 100 ml of an aqueous solution prepared by dissolving 7.20 g of a titanium sulfate solution in deionized water was mixed at room temperature with stirring to obtain an amorphous precipitated gel. Subsequent operations were performed in the same manner as in Example 1 to obtain a powder. The obtained powder was subjected to the above measurement and evaluation. As shown in FIG. 3, it was found that this sample was an ultrafine particle powder having an average particle size of 0.010 μm (10 nm). Other results are shown in Table 1.
[0061]
Example 4
To an aqueous solution obtained by dissolving 3.99 g of sodium pyrophosphate obtained by heating disodium hydrogen phosphate at 500 ° C. for 5 hours in 150 ml of water, 0.42 g of commercially available cerium sulfate tetrahydrate and 30% 150 ml of an aqueous solution prepared by dissolving 11.18 g of a titanium sulfate solution in deionized water was mixed at room temperature with stirring to obtain an amorphous precipitated gel. Subsequent operations were performed in the same manner as in Example 1 to obtain a powder. About the obtained powder, the said measurement and evaluation were performed. The results are shown in Table 1.
[0062]
(Example 5)
To a solution obtained by dissolving 2.66 g of sodium pyrophosphate obtained by heating disodium hydrogen phosphate at 500 ° C. for 5 hours in 100 ml of water, 0.20 g of commercially available cerium sulfate tetrahydrate and 30% 100 ml of an aqueous solution prepared by dissolving 7.60 g of a titanium sulfate solution in deionized water was mixed at room temperature with stirring to obtain an amorphous precipitated gel. Subsequent operations were performed in the same manner as in Example 1 to obtain a powder. About the obtained powder, the said measurement and evaluation were performed. The results are shown in Table 1.
[0063]
[Comparative example]
(Comparative Example 1)
Using commercially available rutile-type ultrafine particle titanium oxide, the composition, average particle size, ultraviolet blocking property, visible light transparency, heat and photocatalytic activity, and hue were evaluated by the methods described above. The results are shown in Table 1.
[0064]
(Comparative Example 2)
Using commercially available ultrafine zinc oxide, the composition, average particle size, ultraviolet blocking property, visible light transparency, heat and photocatalytic activity, and hue were evaluated by the methods described above. The results are shown in Table 1.
[0065]
From the physical property measurement results of the ultraviolet blocking agents produced in Examples 1 to 5 and the ultraviolet blocking agents of Comparative Examples 1 and 2, as shown in FIG. 4 and Table 1, for example, the ultraviolet blocking effect of the ultraviolet blocking agent of the present invention is shown. Is excellent, and furthermore, neither heat nor photocatalytic activity is shown.
[0066]
【The invention's effect】
As described above, the ultraviolet blocking agent of the present invention is excellent in transparency, dispersibility, weather resistance, and heat resistance, and can arbitrarily control the ultraviolet blocking effect and the yellow coloring degree depending on the composition. Cosmetics, films, plastics In addition, it is extremely effective in preventing deterioration and alteration due to ultraviolet rays by blending into various products such as paints.
[Brief description of the drawings]
1 is an X-ray diffraction pattern of a cerium phosphate-titanium phosphate ultraviolet blocking agent produced in Example 1. FIG.
FIG. 2 is an ultraviolet-visible reflection spectrum of a cerium phosphate-titanium phosphate ultraviolet blocking agent produced in Examples 1 to 5.
3 is a transmission electron micrograph of a cerium phosphate-titanium phosphate ultraviolet blocking agent produced in Example 3. FIG.
4 is an ultraviolet-visible reflection spectrum of the cerium phosphate-titanium phosphate ultraviolet blocking agent produced in Example 2, and the rutile ultrafine titanium oxide and ultrafine zinc oxide of Comparative Examples 1 and 2. FIG.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001319100A JP3866076B2 (en) | 2001-10-17 | 2001-10-17 | Cerium phosphate-titanium phosphate UV blocking agent and method for producing the same |
| PCT/FR2002/003540 WO2003033582A1 (en) | 2001-10-17 | 2002-10-16 | Anti-uv compositions based on cerium and titanium phosphates and method for preparing same |
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| JP2001319100A JP3866076B2 (en) | 2001-10-17 | 2001-10-17 | Cerium phosphate-titanium phosphate UV blocking agent and method for producing the same |
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| JP3866076B2 true JP3866076B2 (en) | 2007-01-10 |
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| JP4649102B2 (en) * | 2003-09-16 | 2011-03-09 | 阿南化成株式会社 | Amorphous phosphate, and ultraviolet blocking agent, cosmetic, resin molded article and paint containing the same |
| DE102009001335A1 (en) | 2009-03-04 | 2010-09-09 | Chemische Fabrik Budenheim Kg | Radiation absorbing material |
| DE102013112387B3 (en) | 2013-11-11 | 2014-12-24 | Chemische Fabrik Budenheim Kg | Doped copper II hydroxide phosphate, process for its preparation and use |
| JP7271235B2 (en) * | 2019-03-08 | 2023-05-11 | Ｄｏｗａエレクトロニクス株式会社 | Method for producing titanium pyrophosphate and method for producing solid electrolyte |
| CN110698191B (en) * | 2019-10-28 | 2021-01-05 | 南京航空航天大学 | Biological ceramic material with ultraviolet high reflection |
| CN116355442A (en) * | 2023-03-17 | 2023-06-30 | 河南佰利联新材料有限公司 | A kind of preparation method of high light resistance titanium dioxide |
| WO2025075004A1 (en) * | 2023-10-05 | 2025-04-10 | 株式会社フジミインコーポレーテッド | Spf booster and cosmetic |
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| JPH10204288A (en) * | 1997-01-20 | 1998-08-04 | Toagosei Co Ltd | Discoloration inhibitor for nylon resin and nylon resin |
| JP3819575B2 (en) * | 1997-12-26 | 2006-09-13 | 花王株式会社 | Cerium phosphate UV absorber and method for producing the same |
| JP3875389B2 (en) * | 1998-01-21 | 2007-01-31 | ポーラ化成工業株式会社 | UV absorber |
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