JP4649102B2 - Amorphous phosphate, and ultraviolet blocking agent, cosmetic, resin molded article and paint containing the same - Google Patents
Amorphous phosphate, and ultraviolet blocking agent, cosmetic, resin molded article and paint containing the same Download PDFInfo
- Publication number
- JP4649102B2 JP4649102B2 JP2003322519A JP2003322519A JP4649102B2 JP 4649102 B2 JP4649102 B2 JP 4649102B2 JP 2003322519 A JP2003322519 A JP 2003322519A JP 2003322519 A JP2003322519 A JP 2003322519A JP 4649102 B2 JP4649102 B2 JP 4649102B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- amorphous
- amorphous phosphate
- crystallization
- ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 117
- 229910019142 PO4 Inorganic materials 0.000 title claims description 94
- 239000010452 phosphate Substances 0.000 title claims description 89
- 229920005989 resin Polymers 0.000 title claims description 51
- 239000011347 resin Substances 0.000 title claims description 51
- 239000002537 cosmetic Substances 0.000 title claims description 24
- 239000002981 blocking agent Substances 0.000 title claims description 22
- 239000003973 paint Substances 0.000 title claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 230000002401 inhibitory effect Effects 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 description 85
- 239000010936 titanium Substances 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000007864 aqueous solution Substances 0.000 description 39
- 238000011156 evaluation Methods 0.000 description 33
- 230000000903 blocking effect Effects 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 150000002500 ions Chemical class 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000010304 firing Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 229940085991 phosphate ion Drugs 0.000 description 19
- 229910052719 titanium Inorganic materials 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 13
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 11
- 238000000862 absorption spectrum Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 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 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- -1 phosphate compound Chemical class 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229940048084 pyrophosphate Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000000475 sunscreen effect Effects 0.000 description 3
- 239000000516 sunscreening agent 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 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 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 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
- 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
- 150000001768 cations Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-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
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 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
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- 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
- 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
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 229910004806 Na2 SiO3.9H2 O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000006750 UV protection Effects 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 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
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- CAEMOCUMMOVWCN-UHFFFAOYSA-N diphosphono hydrogen phosphate phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(=O)OP(O)(O)=O CAEMOCUMMOVWCN-UHFFFAOYSA-N 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
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000003349 gelling agent Substances 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
- 229960004881 homosalate Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 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
- 229960003921 octisalate Drugs 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- WCJLCOAEJIHPCW-UHFFFAOYSA-N octyl 2-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1O WCJLCOAEJIHPCW-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960001173 oxybenzone Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 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
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940098424 potassium pyrophosphate Drugs 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 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 1
- 239000004753 textile Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 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 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Description
本発明は、Ｃｅ及び／又はＴｉのアモルファスリン酸塩、並びに、それを含む紫外線遮断剤、化粧品、樹脂成形品及び塗料に関する。 The present invention relates to an amorphous phosphate of Ce and / or Ti, and an ultraviolet blocking agent, a cosmetic, a resin molded article and a paint containing the same.
紫外線は、有機材料からなる樹脂成形品を劣化させる他、生体に対しても悪影響を及ぼす作用が強い。例えば、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、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。そこで、そのような紫外線の作用を緩和させるため、化粧品や樹脂成形品に含有させるための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いる。 In addition to deteriorating resin molded products made of organic materials, ultraviolet rays have a strong effect on living organisms. For example, it is known that ultraviolet rays in the UV-B region having a wavelength of 280 to 320 nm cause skin irritation, and ultraviolet rays in the UV-A region having a wavelength of 320 to 400 nm make the skin brown. Therefore, in order to alleviate the action of such ultraviolet rays, various organic ultraviolet absorbers and inorganic ultraviolet scattering agents for inclusion in cosmetics and resin molded products have been developed.
有機系紫外線吸収剤は、化粧品や樹脂成形品に含有させた場合に無色且つ透明であるため汎用されていたが、近年になり耐熱性、耐候性の不足やそれ自身或いはその分解生成物の毒性による安全性の面で問題が多いために使用が制限されている。 Organic UV absorbers have been widely used because they are colorless and transparent when they are contained in cosmetics and resin molded products. However, in recent years, heat resistance and weather resistance are insufficient, and the toxicity of the products themselves or their decomposition products. The use is restricted due to many problems in terms of safety.
無機紫外線遮断剤として、例えば、特許文献１には、リン酸セリウムとリン酸チタンとを複合化して得られるリン酸セリウム−リン酸チタン系紫外線遮断剤が開示されている。そして、これによれば、透明性が優れると共に、ＵＶ−Ａ及びＵＶ−Ｂの紫外線遮断性能が優れ、且つ、光・熱触媒活性が極めて低い、と記載されている。
ところで、特許文献１にも記載されているように、リン酸セリウム−リン酸チタン系紫外線遮断剤を高温に加熱すると、リン酸塩がピロリン酸塩からオルトリン酸塩に変化し、紫外線遮断性能が著しく損なわれるという問題がある。 By the way, as described in Patent Document 1, when the cerium phosphate-titanium phosphate UV blocking agent is heated to a high temperature, the phosphate changes from pyrophosphate to orthophosphate, and the UV blocking performance is improved. There is a problem of significant damage.
本発明は、かかる点に鑑みてなされたものであり、その目的とするところは、耐熱性能の優れるアモルファスリン酸塩、並びに、それを含む紫外線遮断剤、化粧品、樹脂成形品及び塗料を提供することにある。 This invention is made | formed in view of this point, The place made into the objective provides the amorphous phosphate which is excellent in heat resistance, and the ultraviolet blocker containing the same, cosmetics, a resin molded product, and a coating material. There is.
本発明者らは、ピロリン酸塩からオルトリン酸塩への変化が結晶化の進行に関与することの確信を得て、Ｃｅ及び／又はＴｉのアモルファスリン酸塩が少なくともアモルファス状態であれば、優れた紫外線遮断性能が発揮されるということを見出して本発明に想到したものである。 The inventors obtained the belief that the change from pyrophosphate to orthophosphate is involved in the progress of crystallization, and if the amorphous phosphate of Ce and / or Ti is at least in an amorphous state, it is excellent. The present inventors have conceived that the present invention has demonstrated that its ultraviolet blocking performance is exhibited.
上記目的を達成することができるその本発明は、Ｃｅ及び／又はＴｉのアモルファスリン酸塩であって、結晶化阻止成分を含有しているものである。 The present invention capable of achieving the above object is an amorphous phosphate of Ce and / or Ti, which contains a crystallization inhibitor component.
上記の構成であれば、加熱を受けても結晶化阻止成分によって結晶化が抑えられるので、高温度までアモルファス状態が維持されて紫外線遮断性能が損なわれない。従って、紫外線遮断性能を示すアモルファスリン酸塩として高い耐熱性能を呈する。 If it is said structure, since it will suppress crystallization by a crystallization inhibitory component even if it receives a heating, an amorphous state will be maintained to high temperature and an ultraviolet-blocking performance will not be impaired. Therefore, it exhibits high heat resistance performance as an amorphous phosphate exhibiting ultraviolet blocking performance.
以上説明したように、本発明によれば、Ｃｅ及び／又はＴｉのアモルファスリン酸塩の優れた耐熱性能を得ることができる。 As described above, according to the present invention, excellent heat resistance performance of Ce and / or Ti amorphous phosphate can be obtained.
以下、本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
（アモルファスリン酸塩の構成）
本発明の実施形態に係るアモルファスリン酸塩は、Ｃｅ及び／又はＴｉのリン酸塩の微粉末であり、例えば、化粧品や樹脂成形品や塗料等に混入される紫外線遮断剤として用いられるものである。「Ｃｅ及び／又はＴｉ」であるので、Ｃｅのアモルファスリン酸塩であっても、Ｔｉのアモルファスリン酸塩であっても、また、Ｃｅ及びＴｉのアモルファス複合リン酸塩であってもよい。そして、本実施形態のアモルファスリン酸塩は、結晶化されていない不定形（非晶質、アモルファス）のものであり、また、特徴として、結晶化阻止成分を含有している。
(Structure of amorphous phosphate)
The amorphous phosphate according to the embodiment of the present invention is a fine powder of Ce and / or Ti phosphate, and is used, for example, as an ultraviolet blocking agent mixed in cosmetics, resin molded products, paints, and the like. is there. Since it is “Ce and / or Ti”, it may be an amorphous phosphate of Ce, an amorphous phosphate of Ti, or an amorphous composite phosphate of Ce and Ti. The amorphous phosphate of the present embodiment is an amorphous (non-crystallized) amorphous material that is not crystallized, and contains a crystallization inhibitor component as a feature.
結晶化阻止成分は、アモルファスリン酸塩において、温度が上昇した際に、陽イオンと陰イオンとが再配列して結晶化するのを規制するものであれば特に限定されるものではない。結晶化阻止成分としては、アモルファスリン酸塩内で不純物として機能するものが好ましく、陽イオンと陰イオンとの再配列を困難にするという観点からは、熱運動性能の低い嵩高く且つ重いものがより好適である。具体的には、結晶化阻止成分として、例えば、Ｂ、Ａｌ、Ｓｉ、Ｚｎ、Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔａ及びＷ等の元素や、その他の化合物を挙げることができる。 The crystallization inhibiting component is not particularly limited as long as it regulates the crystallization of the cations and anions when the temperature rises in the amorphous phosphate. As the crystallization inhibiting component, those that function as impurities in the amorphous phosphate are preferable, and from the viewpoint of making rearrangement of cations and anions difficult, bulky and heavy ones with low thermal motion performance are preferred. More preferred. Specifically, examples of the crystallization inhibiting component include elements such as B, Al, Si, Zn, Ga, Zr, Nb, Mo, Ta, and W, and other compounds.
結晶化阻止成分は、単一種が含有されていても、二種以上が含有されていてもよい。 The crystallization inhibitor component may contain a single species or two or more species.
結晶化阻止成分は、単にアモルファスリン酸塩に混合状態に含有されていても、例えば、結晶化阻止成分が元素の場合、リン酸イオンのＰの一部を置換するような形態で含有されていてもよい。 Even if the crystallization inhibitor component is simply contained in a mixed state in the amorphous phosphate, for example, when the crystallization inhibitor component is an element, it is contained in a form that substitutes part of P of the phosphate ion. May be.
上記後者の例のように、結晶化阻止成分元素がリン酸イオンのＰの一部を置換するような形態で含有されているアモルファスリン酸塩は、結晶化阻止成分元素Ｘとしたとき、
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ （Ｉ）
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０）
で表すことができる。なお、Ｘは単一種であっても複数種であってもよい。また、これには水和水を含んだ
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ・ｎＨ２Ｏ （II）
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０、ｎは任意）
で表されるものも含まれる。
As in the latter example, when the amorphous phosphate contained in such a form that the crystallization inhibitor component element substitutes a part of P of the phosphate ion is used as the crystallization inhibitor component element X,
Composition formula: Ce α Ti 1-α ( P 1-β X β) 2 O 7 + γ (I)
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0)
Can be expressed as X may be a single species or a plurality of species. In addition, this includes a composition formula containing hydration water: Ce α Ti 1-α (P 1-β X β ) 2 O 7 + γ · nH 2 O (II)
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0, n is arbitrary)
The thing represented by is also included.
ここで、αは０〜１の範囲で設定自在であり、このαの値によりアモルファスリン酸塩の有する紫外線遮断性能及び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αの値を自由に選ぶことができ、例えば、日焼け止め化粧品に含有させる場合、紫外線遮断性能と黄色の着色とのバランスを考慮すると、α＝０．００１〜０．５とするのが好適であり、０．０１〜０．２とするのがさらによい。 Here, α can be set in the range of 0 to 1, and the value of α can arbitrarily control the ultraviolet blocking performance and yellow coloration of the amorphous phosphate. Therefore, the value of α can be freely selected according to the application. For example, when it is contained in a sunscreen cosmetic, α = 0.001 to 0.5 in consideration of the balance between the ultraviolet blocking performance and the yellow coloring. And is more preferably 0.01 to 0.2.
βは０より大きく０．５以下の範囲で設定自在であり、このβの値によりアモルファスリン酸塩の耐熱性能を任意に制御することができる。ＸがＰよりも元素番号の大きい元素の場合、βが大きくなってＸの割合が多くなると、アモルファスリン酸塩の単位質量中に含まれるＣｅやＴｉの絶対量が少なくなるため、紫外線遮断性能が低くなってしまう。従って、これを考慮すれば、上記の場合β＝０．２〜０．３とするのが好適である。 β can be set in the range of more than 0 and 0.5 or less , and the heat resistance performance of the amorphous phosphate can be arbitrarily controlled by the value of β. In the case where X is an element having an element number larger than P, if β increases and the proportion of X increases, the absolute amount of Ce and Ti contained in the unit mass of the amorphous phosphate decreases, so that the ultraviolet blocking performance Will be lower. Therefore, in consideration of this, it is preferable that β = 0.2 to 0.3 in the above case.
γはＸの種類によって−０．５〜１．０の範囲で決まる。 γ is determined in the range of −0.5 to 1.0 depending on the type of X.
ｎは水和水分子の数を示し、アモルファスリン酸塩化合物を形成する際に必然的に水和水分子が結合するため０より大きい値となる。水に対する溶解性を抑制する観点及び撥水処理の困難性を回避する観点からは、ｎが５以下、好ましくは３以下、より好ましくは２以下であるのがよい。 n represents the number of hydrated water molecules, and is a value greater than 0 because hydrated water molecules are inevitably bound when forming an amorphous phosphate compound. From the viewpoint of suppressing the solubility in water and avoiding the difficulty of water repellent treatment, n is 5 or less, preferably 3 or less, more preferably 2 or less.
なお、これらのα、β、γ及びｎの値は、アモルファスリン酸塩の乾燥粉末におけるＣｅ、Ｔｉ等の元素分析及び熱重量分析を行うことによって定量することができる。 The values of α, β, γ, and n can be quantified by conducting elemental analysis and thermogravimetric analysis of Ce, Ti, etc. in the dry powder of amorphous phosphate.
このように本実施形態のアモルファスリン酸塩は、結晶化阻止成分を含有しているので、加熱を受けても結晶化が抑えられ、高温度までアモルファス状態が維持されて紫外線遮断性能が損なわれず、高い耐熱性能を呈する。 As described above, since the amorphous phosphate of this embodiment contains a crystallization-inhibiting component, crystallization is suppressed even when heated, and the amorphous state is maintained up to a high temperature without damaging the ultraviolet blocking performance. Exhibits high heat resistance.
本実施形態のアモルファスリン酸塩は、屈折率がＣｅやＴｉの酸化物と比較して小さく、組成にもよるがおよそ１．８〜２．０である。このように屈折率が低いと、微粉末状のアモルファスリン酸塩の可視光に対する光散乱性も低くなるため、とりわけ化粧品、塗料等に含有させた場合、従来の酸化物系のものを用いた場合に比べて高い透明性を得ることができる。さらに、アモルファス複合リン酸塩であれば、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及び熱触媒活性を著しく抑制することができる。つまり、化粧品に含まれた無機系紫外線遮断剤が化粧品の他の成分を分解させる反応を促進させたり、樹脂成形品に含まれた無機系紫外線遮断剤がその樹脂成形品を劣化させる反応を促進させたりすることがない。 The amorphous phosphate of the present embodiment has a refractive index smaller than that of Ce or Ti oxide, and is approximately 1.8 to 2.0 depending on the composition. When the refractive index is low in this way, the light-scattering property of fine powdered amorphous phosphate with respect to visible light is also low, so when used in cosmetics, paints, etc., conventional oxide-based materials were used. High transparency can be obtained compared to the case. Furthermore, if it is an amorphous composite phosphate, it is possible to remarkably suppress the light and thermal catalytic activity, which is one of the major problems of the conventional inorganic ultraviolet blocking agents. In other words, the inorganic UV blocker contained in cosmetics promotes the reaction that decomposes other components of the cosmetics, and the inorganic UV blocker contained in resin molded products promotes the reaction that degrades the resin molded product. I will not let you.
本実施形態のアモルファスリン酸塩は微粉末状であるが、その大きさは、平均粒径が０．００３〜１μｍである。粒子の凝集が激化して分散が困難になるのを回避する観点からは、平均粒径が０．００３μｍ以上、好ましくは０．０１μｍ以上、より好ましくは０．０３μｍ以上であるのがよい。紫外線吸収することによる紫外線遮断性能及び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は、平均粒径が１μｍ以下、好ましくは０．１μｍ以下、より好ましくは０．０５μｍ以下であるのがよい。なお、平均粒径は、複数の粒子について、電子顕微鏡写真からそれらの外径を実測することにより算出することができる。 The amorphous phosphate of this embodiment is in the form of fine powder, but the average particle size is 0.003 to 1 μm. From the viewpoint of preventing the particles from becoming agglomerated and becoming difficult to disperse, the average particle diameter 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 ultraviolet blocking performance by absorbing ultraviolet rays and transparency in the visible light region, the average particle size is 1 μm or less, preferably 0.1 μm or less, more preferably 0.05 μm or less. Good. The average particle diameter can be calculated by actually measuring the outer diameter of a plurality of particles from an electron micrograph.
（アモルファスリン酸塩の製造方法）
次に、上記組成式（Ｉ）で表される本実施形態のアモルファスリン酸塩の製造方法について説明する。
(Method for producing amorphous phosphate)
Next, the manufacturing method of the amorphous phosphate of this embodiment represented by the composition formula (I) will be described.
まず、リン酸イオンを含む塩基性水溶液と、＋４価のＣｅイオン及び／又は＋４価のＴｉイオンを含む水溶液と、Ｘイオンを含む溶液とを、混合後の分散液のｐＨが１〜１１となるように混合する。 First, a basic aqueous solution containing phosphate ions, an aqueous solution containing +4 valent Ce ions and / or +4 valent Ti ions, and a solution containing X ions, the pH of the dispersion after mixing is 1 to 11 Mix to be.
ここで、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としては、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を挙げることができ、ピロリン酸塩を効率よく生成させる観点からは、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を用いるのがよい。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、リン酸第一アンモニウム、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を用いるのがよい。 Here, as the basic aqueous solution containing phosphate ions, an aqueous solution of an alkali metal phosphate, an ammonium phosphate, or the like may be used, or after preparing an aqueous phosphate solution in advance, an alkaline aqueous solution is added to the base solution. You may use what was made. Examples of the alkali metal phosphate include sodium pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, triphosphate phosphate. Examples include potassium, lithium pyrophosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, etc. From the viewpoint of efficiently producing pyrophosphate, sodium pyrophosphate, potassium pyrophosphate, pyrolin It is preferable to use lithium acid. In addition, when it is necessary to suppress alkali metal contamination in the sample as much as possible, it is preferable to use primary ammonium phosphate, diammonium phosphate, triammonium phosphate trihydrate, or the like.
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、Ｔｉイオン及び／又はＣｅ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以下とするのが望ましく、反応を完全に行う観点から、Ｔｉイオン及び／又はＣｅ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以上とするのが望ましい。 The amount of phosphate ions in the basic aqueous solution containing phosphate ions is based on the total number of moles of Ti ions and / or Ce ions from the viewpoint of reducing the trouble of removing excess phosphoric acid and excess alkali by washing with water. The molar 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 Ti ions and / or Ce ions. The ratio is 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more.
＋４価のＣｅイオンを含む溶液のＣｅ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・２Ｈ2Ｏ）、
硫酸セリウム（IV）四水和物（Ｃｅ（ＳＯ4）4・４Ｈ2Ｏ）
等が好適であり、好ましくは硫酸セリウム（IV）四水和物を用いるのがよい。
The Ce ion source of the solution containing + tetravalent Ce ions is not particularly limited as long as it is water-soluble or acid-soluble + tetravalent cerium compound.
Diammonium cerium (IV) nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ),
Tetraammonium cerium (IV) sulfate dihydrate (Ce (NH 4 ) 4 (SO 4 ) 4 .2H 2 O),
Cerium sulfate (IV) tetrahydrate (Ce (SO 4 ) 4 · 4H 2 O)
Etc., and cerium (IV) sulfate tetrahydrate is preferably used.
＋４価のＴｉイオンを含む溶液のＴｉ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。
The Ti ion source of the solution containing + 4-valent Ti ions is not particularly limited as long as it is water-soluble or acid-soluble + 4-valent titanium compound.
Titanium chloride (TiCl 4 ),
Titanium (IV) sulfate (Ti (SO 4 ) 4 ),
Titanium iodide (TiI 4 )
Etc. are suitable. Furthermore, commercially available solutions of titanium chloride (IV), titanium sulfate (IV) and the like are preferably used because of their easy handling.
Ｘイオンを含む溶液としては、水溶性、エタノール可溶性、或いは酸可溶性の化合物の溶液等、特に限定されるものではなく、例えば、ＸがＮｂ或いはＭｏの場合にはこれらの塩化物（ＸＣｌ5）をエタノール等に溶解させた溶液、ＸがＳｉの場合には珪酸ナトリウム水溶液、ＸがＢの場合にはホウ酸水溶液、ＸがＡｌの場合には硫酸アルミニウム、硝酸アルミニウム、塩化アルミニウムの水又は酸或いはエタノール溶液、ＸがＺｎの場合には硫酸亜鉛、塩化亜鉛の水溶液、ＸがＧａの場合には塩化ガリウムの酸溶液、ＸがＺｒの場合には硫酸ジルコニウム、塩化ジルコニウム、オキシ硝酸ジルコニウム、オキシ塩化ジルコニウムの水又は酸溶液などが好適に用いられる。 The solution containing X ions is not particularly limited, such as a solution of a water-soluble, ethanol-soluble, or acid-soluble compound. For example, when X is Nb or Mo, these chlorides (XCl 5 ) A solution in which ethanol is dissolved, an aqueous solution of sodium silicate when X is Si, an aqueous solution of boric acid when X is B, an aqueous solution of aluminum sulfate, aluminum nitrate, aluminum chloride or an acid when X is Al Alternatively, an ethanol solution, an aqueous solution of zinc sulfate or zinc chloride when X is Zn, an acid solution of gallium chloride when X is Ga, zirconium sulfate, zirconium chloride, zirconium oxynitrate, or oxy when X is Zr A water or acid solution of zirconium chloride is preferably used.
＋４価のＣｅイオン及び／又は＋４価のＴｉイオンを含む溶液中の金属イオン量、すなわちＣｅイオン及び／又はＴｉイオンの総量は、合成の効率化の観点から、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。 The amount of metal ions in the solution containing +4 valent Ce ions and / or +4 valent Ti ions, that is, the total amount of Ce ions and / or Ti ions is a basic aqueous solution containing phosphate ions from the viewpoint of efficient synthesis. The amount in the reaction solution in which the aqueous solution containing metal ions is mixed is 0.01 mol / L or more, preferably 0.05 mol / L or more, more preferably 0.1 mol / L or more. On the other hand, 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, from the viewpoint of avoiding the difficulty of stirring operation due to the increase in the viscosity of the reaction solution. Such an amount is desirable.
リン酸イオンを含む塩基性水溶液と、＋４価のＣｅイオン及び／又は＋４価のＴｉイオンを含む溶液と、Ｘイオンを含む溶液と、を混合した後の分散液のｐＨは、粒径が大きくなって紫外線遮断性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以上とするのがよく、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９以下、より好ましくは８以下とするのがよい。 The pH of the dispersion after mixing a basic aqueous solution containing phosphate ions, a solution containing +4 valent Ce ions and / or +4 valent Ti ions, and a solution containing X ions has a large particle size. 1 or more, preferably 2 or more, and more preferably 3 or more from the viewpoint of preventing the UV blocking performance from being lowered, and preventing the resulting UV blocking agent powder from becoming highly soluble in water. From the viewpoint, it is 11 or less, preferably 9 or less, more preferably 8 or less.
リン酸イオンを含む塩基性水溶液と、＋４価のＣｅイオン及び／又は＋４価のＴｉイオンを含む溶液と、Ｘ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の攪拌下、＋４価のＣｅイオン及び／又は＋４価のＴｉイオンを含む溶液及びＸ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、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。 As a method of mixing a basic aqueous solution containing phosphate ions, a solution containing +4 valent Ce ions and / or +4 valent Ti ions, and a solution containing X ions, for example, at 0 to 50 ° C., phosphorus A method of mixing while adding a solution containing +4 valent Ce ions and / or +4 valent Ti ions and a solution containing X ions over about 5 seconds to 1 hour while stirring a basic aqueous solution containing acid ions. By mixing in this way, an amorphous gel is formed.
次いで、生成したゲルを８０℃の温度で熟成させる。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。また、必要に応じ、生成したゲルを１２０℃〜２００℃の温度で水熱処理してもよい。 The resulting gel is then 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. Moreover, you may hydrothermally process the produced | generated gel at the temperature of 120 to 200 degreeC as needed.
そして、濾過、遠心分離等により生成したゲルからアモルファスリン酸塩を回収、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、デカンテーションの繰り返しか、セラミックフィルタ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よい。乾燥させる際の温度は８０〜２００℃とすることが好ましい。 And amorphous phosphate is collect | recovered and wash | cleaned from the gel produced | generated by filtration, centrifugation, etc., and if necessary, after replacing water with water-soluble organic solvents, such as ethanol, it dries. The washing means may be centrifugal separation, filtration separation, decantation repetition, or a fine powder washing apparatus using a ceramic filter or an 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.
以上により、微粉末状のアモルファスリン酸塩を得ることができる。なお、アモルファスリン酸塩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もできる。このアモルファスリン酸塩の製造方法は、高温での熱処理が不要であり、８０℃で乾燥したものでも充分高い紫外線遮断性能を有する。 In this way, a fine powdery amorphous phosphate can be obtained. When the amorphous phosphate is used in an aqueous dispersion, it can be used as a dispersion without being recovered at the final stage of washing with water. This method for producing an amorphous phosphate does not require a heat treatment at a high temperature and has a sufficiently high ultraviolet blocking performance even when dried at 80 ° C.
（アモルファスリン酸塩の用途）
本実施形態のアモルファスリン酸塩は、紫外線遮断剤としていずれの用途でも使用できる。例えば、日焼け止めを目的とした紫外線カット化粧品、耐紫外線性能を有する樹脂フィルムやプラスチックボックスなどの樹脂成形品、塗料等に好ましく使用することができる。
(Use of amorphous phosphate)
The amorphous phosphate of this embodiment can be used for any application as an ultraviolet blocking agent. For example, it can be preferably used for UV-cutting cosmetics for the purpose of sunscreen, resin-molded products such as resin films and plastic boxes having UV resistance, and paints.
本実施形態のアモルファスリン酸塩を、例えば、化粧品や、樹脂フィルムやプラスチックボックス等の樹脂成形品や塗料に含有させれば、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。 If the amorphous phosphate of the present embodiment is contained in, for example, cosmetics, resin molded products such as resin films and plastic boxes and paints, UV-B to UV-A without impairing transparency in the visible region. An excellent ultraviolet blocking effect is exhibited over almost the entire region, and since the catalytic activity is suppressed, stability and safety are high.
なお、本実施形態のアモルファスリン酸塩を化粧品や樹脂成形品や塗料に含有させる場合、微粉末状のものをそのまま混ぜ込んでも、また、ペースト状、分散液状などの各種形態で混ぜ込んでもよい。樹脂成形品に含有させる場合には、予め成形用材料としてのペレットに含有させてマスターバッチとしても、押出成形機や射出成形機にベースの樹脂材料と共に投入して混練してもよい。 In addition, when the amorphous phosphate of this embodiment is contained in cosmetics, resin molded products, and paints, fine powders may be mixed as they are, or may be mixed in various forms such as pastes and dispersions. . When it is contained in a resin molded product, it may be preliminarily contained in a pellet as a molding material to form a master batch, or it may be introduced into an extrusion molding machine or an injection molding machine together with the base resin material and kneaded.
以下、本実施形態のアモルファスリン酸塩を、化粧品、樹脂成形品及び塗料にそれぞれに含有させる場合について詳細に説明する。 Hereinafter, the case where the amorphous phosphate of this embodiment is contained in cosmetics, resin molded articles, and paints will be described in detail.
まず、本実施形態のアモルファスリン酸塩を含有させた化粧品について述べる。 First, a cosmetic containing the amorphous phosphate of this embodiment will be described.
本実施形態のアモルファスリン酸塩を含有させた化粧品は、透明性が高く且つ優れた紫外線遮断効果を発揮し、日焼け止め化粧料として用いるのが好ましい。化粧品の種類としては、特に限定されるものではなく、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、整髪料等を挙げることができる。配合率も特に限定されないが、０．１〜７０質量％に調節するのが望ましい。配合率が０．１質量％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質量％以上配合すると分散性、透明性が低下する場合がある。 The cosmetic containing the amorphous phosphate of the present embodiment is preferably used as a sunscreen cosmetic because of its high transparency and excellent UV blocking effect. The types of cosmetics are not particularly limited, and examples thereof include emulsions, creams, lotions, foundations, compact powders, nail varnishes, lipsticks, eye shadows, lotions, and hair conditioners. The mixing ratio is not particularly limited, but it is desirable to adjust to 0.1 to 70% by mass. When the blending ratio is 0.1% by mass or less, it may be difficult to obtain a sufficient ultraviolet blocking effect. On the other hand, when 70% by mass or more is blended, dispersibility and transparency may be deteriorated.
本実施形態のアモルファスリン酸塩を化粧品に含有させる場合、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、香料等の添加剤を一緒に含有させてもよい。また、アモルファスリン酸塩に対し、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・キトサン処理等の表面処理を施してもよい。 When the amorphous phosphate of this embodiment is contained in a cosmetic, for example, a dispersant, a surfactant, an oil agent, a gelling agent, a polymer, a moisturizer, a cosmetic ingredient, a pigment, an antiseptic, a powder, a fragrance, etc. Additives may be included together. The amorphous phosphate may be subjected to a surface treatment such as amino acid treatment, collagen treatment, lecithin treatment, triglyceride treatment, silicone treatment, metal soap treatment, chitin / chitosan treatment or the like.
本実施形態のアモルファスリン酸塩の異なる組成のものを２種以上組み合わせて含有させてもよい。また、本実施形態のアモルファスリン酸塩に加えて、有機系紫外線吸収剤や他の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てもよい。こうすることにより、両者の利点を同時利用できる。この場合、有機系紫外線吸収剤として、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等を挙げることができる。具体的には、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である。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、オキシベンゾン等である。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である。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である。一方、無機系紫外線遮断剤として、酸化チタン、酸化亜鉛、或いは、酸化セリウム等を挙げることができ、平均粒径５０ｎｍ以下の酸化チタン、酸化亜鉛、酸化セリウムを用いるのが好適である。 Two or more kinds of amorphous phosphates having different compositions may be contained in combination. Further, in addition to the amorphous phosphate of the present embodiment, at least one organic ultraviolet absorber and other inorganic ultraviolet blocking agents are used, and there are no problems caused by the use such as contamination of products and the environment. A small amount may be added within the range. By doing so, both advantages can be used simultaneously. In this case, examples of the organic ultraviolet absorber include various ultraviolet blocking agents such as salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and 4-tert-butyl-4′-methoxybenzoylmethane. . Specifically, examples of the salicylic acid-based ultraviolet blocking agent 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, examples of the inorganic ultraviolet blocking agent include titanium oxide, zinc oxide, cerium oxide, and the like, and it is preferable to use titanium oxide, zinc oxide, cerium oxide having an average particle size of 50 nm or less.
次に、本実施形態のアモルファスリン酸塩を含有させた樹脂成形品や塗料について述べる。 Next, the resin molded product and paint containing the amorphous phosphate of this embodiment will be described.
一般に、樹脂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。その対策として本実施形態のアモルファスリン酸塩を紫外線遮断剤として含有させることで光劣化を防止あるいは低減できる。アモルファスリン酸塩の樹脂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質量％の範囲に調製するのがよい。配合率が０．５質量％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質量％以上では分散性が低下する。なお、配合の際に分散剤等の添加剤を加えてもよい。 In general, it is known that a resin deteriorates when it absorbs ultraviolet rays contained in sunlight. As a countermeasure, it is possible to prevent or reduce photodegradation by including the amorphous phosphate of this embodiment as an ultraviolet blocking agent. The blending ratio of the amorphous phosphate to the resin can be arbitrarily set, but is preferably adjusted in the range of 0.5 to 50% by mass. If the blending ratio is 0.5% by mass or less, it is too small to obtain a sufficient ultraviolet blocking effect, while if it is 50% by mass or more, dispersibility is lowered. In addition, you may add additives, such as a dispersing agent, in the case of a mixing | blending.
例えば、本実施形態のアモルファスリン酸塩の紫外線遮断剤を樹脂フィルムに含有させ、その樹脂フィルムを表面保護用途に使用することにより、樹脂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。また、本実施形態のアモルファスリン酸塩は、耐熱性能が特に優れるので、紫外線に対する暴露時間が長いビニールハウス等への用途に好適である。 For example, an amorphous phosphate ultraviolet blocking agent of this embodiment is contained in a resin film, and the resin film is used for surface protection, thereby providing an adhesive, a plastic plate, a wooden plate, a steel plate, and a lower layer than the resin film. Colorants such as dyes and application materials are materials that can be used for a long period of time because they are protected from ultraviolet rays. In addition, the amorphous phosphate of the present embodiment is particularly excellent in heat resistance, and thus is suitable for use in a greenhouse or the like having a long exposure time to ultraviolet rays.
本実施形態のアモルファスリン酸塩を含有させた塗料は、特に限定されるものではなく、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適である。 The coating material containing the amorphous phosphate of the present embodiment is not particularly limited, and any coating material may be used, but a room temperature drying coating material and a baking coating material are preferable among the classifications based on the coating method.
本実施形態のアモルファスリン酸塩を含有させた樹脂フィルムやプラスチックボックス等の樹脂成形品や塗料としては、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、いかなる樹脂成形品、塗料等にも使用可能である。 Examples of resin molded articles and paints such as resin films and plastic boxes containing amorphous phosphate according to the present embodiment include lighting covers, electrical / electronic materials such as electronic substrates and EL, interior panels for automobiles, etc. Automotive parts, machine parts, packaging and containers for food and medicine, textiles, signs, steel plates, plastic plates, sheets, agricultural covering materials, roofs, tents, outdoor structures such as outdoor warehouses, automobiles, vehicles, ships, aircraft, Examples include household appliances, machinery, building outer walls, bridges, office supplies, eyeglass lenses, toys, sundries, etc., but any resin molded product or paint as long as UV blocking is required Etc. can also be used.
上記樹脂成形品や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。 A thermoplastic resin or a thermosetting resin is used as the resin used as a raw material for the resin molded product or 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.
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。 Examples of the thermosetting resin include melamine resin, phenol resin, urea resin, furan resin, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, polyurethane resin, polyimide resin, and polyparabanic acid resin. Among them, epoxy resin, diallyl phthalate resin, and polyimide resin are preferable.
［試験評価１］
（試験評価試料）
以下の各例に係るＣｅＰ2Ｏ7系アモルファスリン酸塩を調製した。
[Test Evaluation 1]
(Test evaluation sample)
CeP 2 O 7 -based amorphous phosphates according to the following examples were prepared.
＜例１−１＞
硫酸セリウム（IV）四水和物１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液を、Ｎａ4Ｐ2Ｏ7１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液に滴下し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるセリウムのアモルファスリン酸塩を例１−１とした
（ＣｅＰ2Ｏ7）。
<Example 1-1>
An aqueous solution in which 10 mmol of cerium (IV) sulfate tetrahydrate was dissolved in 100 ml of deionized water was added dropwise to an aqueous solution in which 10 mmol of Na 4 P 2 O 7 was dissolved in 100 ml of deionized water, and this was added at 80 ° C. for 30 minutes. A cerium amorphous phosphate obtained by heating and then separating the precipitate by centrifugation, washing with water, and drying at 80 ° C. for 24 hours was defined as Example 1-1 (CeP 2 O 7 ).
＜例１−２＞
硫酸セリウム（IV）四水和物５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液と、ＮｂＣｌ5１ｍｍｏｌをエタノール４０ｍｌに溶解させた溶液とを、Ｎａ4Ｐ2Ｏ7４．５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液に滴下し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるセリウムのアモルファスリン酸塩を例１−２とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち１０％がＮｂで置換されたものであった
（Ｃｅ（Ｐ0.9Ｎｂ0.1）2Ｏ7）。
<Example 1-2>
An aqueous solution in which 5 mmol of cerium (IV) sulfate tetrahydrate was dissolved in 50 ml of deionized water, a solution in which 1 mmol of NbCl 5 was dissolved in 40 ml of ethanol, and 4.5 mmol of Na 4 P 2 O 7 in 50 ml of deionized water. An example of cerium amorphous phosphate obtained by dripping into an aqueous solution dissolved in the solution, heating it at 80 ° C. for 30 minutes, separating the precipitate by centrifugation, washing with water, and drying at 80 ° C. for 24 hours. 1-2. In this amorphous phosphate, 10% of the phosphate ion P was substituted with Nb (Ce (P 0.9 Nb 0.1 ) 2 O 7 ).
＜例１−３＞
硫酸セリウム（IV）四水和物５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液と、ＴａＣｌ5１ｍｍｏｌをエタノール４０ｍｌに溶解させた溶液とを、Ｎａ4Ｐ2Ｏ7４．５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液に滴下し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるセリウムのアモルファスリン酸塩を例１−３とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち１０％がＴａで置換されたものであった
（Ｃｅ（Ｐ0.9Ｔａ0.1）2Ｏ7）。
<Example 1-3>
An aqueous solution in which 5 mmol of cerium (IV) sulfate tetrahydrate was dissolved in 50 ml of deionized water, a solution in which 1 mmol of TaCl 5 was dissolved in 40 ml of ethanol, and 4.5 mmol of Na 4 P 2 O 7 in 50 ml of deionized water. An example of cerium amorphous phosphate obtained by dripping into an aqueous solution dissolved in the solution, heating it at 80 ° C. for 30 minutes, separating the precipitate by centrifugation, washing with water, and drying at 80 ° C. for 24 hours. 1-3. In this amorphous phosphate, 10% of the phosphate ion P was replaced by Ta (Ce (P 0.9 Ta 0.1 ) 2 O 7 ).
（試験評価方法）
＜結晶・非結晶性＞
粉末Ｘ線回折測定装置（リガク社製、ＭｕｌｔｉＦｌｅｘ型）を用いて、例１−１について、未焼成のもの、並びに、２００℃、３００℃、３５０℃、４００℃、４５０℃、５００℃、５５０℃、６００℃及び６５０℃の各温度で５時間焼成したものの生成相を同定した。例１−２及び例１−３のそれぞれについて、未焼成のもの、並びに、２００℃、３００℃、３５０℃、４００℃、４５０℃、５００℃、５５０℃及び６００℃の各温度で焼成したものの生成相を同定した。
(Test evaluation method)
<Crystal / Amorphous>
About Example 1-1 using a powder X-ray diffractometer (manufactured by Rigaku Corporation, MultiFlex type), unfired ones, and 200 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 550 The product phases of those fired at 5 ° C., 600 ° C. and 650 ° C. for 5 hours were identified. About each of Example 1-2 and Example 1-3, what was baked, and what was baked at each temperature of 200 degreeC, 300 degreeC, 350 degreeC, 400 degreeC, 450 degreeC, 500 degreeC, 550 degreeC, and 600 degreeC The product phase was identified.
＜色相＞
色彩色度計（ミノルタ製ＣＲ−３００型）を用いて、例１−１〜例１−３のそれぞれについて（Ｌ*，ａ*，ｂ*）を測定した。
<Hue>
(L *, a *, b *) was measured for each of Examples 1-1 to 1-3 using a color chromaticity meter (CR-300 manufactured by Minolta).
（試験評価結果）
表１〜３は、例１−１〜例１−３の試験評価結果をそれぞれ示す。
(Test evaluation results)
Tables 1-3 show the test evaluation results of Examples 1-1 to 1-3, respectively.
例１−１では、表１によれば、粉末Ｘ線回折（以下「ＸＲＤ」という。）の結果より４５０℃までアモルファス状態を維持できるということが分かる。また、色相は、焼成温度が高くなると黄色さを表すｂ値が小さくなり、黄色が薄くなることが分かる。 In Example 1-1, it can be seen from Table 1 that the amorphous state can be maintained up to 450 ° C. from the results of powder X-ray diffraction (hereinafter referred to as “XRD”). Further, it can be seen that the hue shows a lower b value indicating yellowness when the firing temperature is higher, and the yellow becomes lighter.
例１−２では、表２によれば、ＸＲＤの結果より、５５０℃までアモルファス状態を維持できるということが分かる。例１−１に対し、リン酸イオンのＰのうち１０％をＮｂで置換することにより、かかる耐熱性向上効果が得られた。また、色相は、焼成温度が高くなるとｂ値が小さくなり、黄色が薄くなることが分かる。 In Example 1-2, according to Table 2, it can be seen from the XRD results that the amorphous state can be maintained up to 550 ° C. In Example 1-1, the effect of improving heat resistance was obtained by substituting 10% of P of phosphate ion with Nb. Further, it can be seen that the hue value b decreases and the yellow color decreases as the firing temperature increases.
例１−３では、表３によれば、ＸＲＤの結果より、５５０℃までアモルファス状態を維持できるということが分かる。例１−１に対し、リン酸イオンのＰのうち１０％をＴａで置換することにより、かかる耐熱性向上効果が得られた。また、色相は、焼成温度が高くなるとｂ値が小さくなり、黄色が薄くなることが分かる。 In Example 1-3, according to Table 3, it can be seen from the XRD results that the amorphous state can be maintained up to 550 ° C. In Example 1-1, the effect of improving the heat resistance was obtained by substituting 10% of the phosphate ion P with Ta. Further, it can be seen that the hue value b decreases and the yellow color decreases as the firing temperature increases.
以上、例１−１〜例１−３を比較すると、Ｎｂ又はＴａを含有している例１−２や例１−３は、それらの元素が結晶化阻止成分として機能するため、それらを含有しない例１−１が結晶化する温度では結晶化せずに、それよりも高温度で結晶化する。 As described above, when Examples 1-1 to 1-3 are compared, Example 1-2 and Example 1-3 containing Nb or Ta contain these elements because they function as crystallization inhibiting components. Not crystallized at the temperature at which Example 1-1 crystallizes, but crystallizes at a higher temperature than that.
［試験評価２］
（試験評価試料）
以下の各例に係るＴｉＰ2Ｏ7系アモルファスリン酸塩を調製した。
[Test evaluation 2]
(Test evaluation sample)
TiP 2 O 7 -based amorphous phosphates according to the following examples were prepared.
＜例２−１＞
硫酸チタン１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液を、沈殿剤としてのＮａ4Ｐ2Ｏ7１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液に滴下し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−１とした（ＴｉＰ2Ｏ7）。
<Example 2-1>
An aqueous solution in which 10 mmol of titanium sulfate was dissolved in 100 ml of deionized water was added dropwise to an aqueous solution in which 10 mmol of Na 4 P 2 O 7 as a precipitant was dissolved in 100 ml of deionized water, which was heated at 80 ° C. for 30 minutes, Thereafter, the precipitate was separated by centrifugation, washed with water, and dried at 80 ° C. for 24 hours, and titanium amorphous phosphate obtained as Example 2-1 (TiP 2 O 7 ).
＜例２−２＞
硫酸チタン５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液及びＮｂＣｌ5１ｍｍｏｌをエタノール４０ｍｌに溶解させた溶液を、４．５ｍｍｏｌのＮａ4Ｐ2Ｏ7を脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−２とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち１０％がＮｂで置換されたものであった
（Ｔｉ（Ｐ0.9Ｎｂ0.1）2Ｏ7）。
<Example 2-2>
An aqueous solution in which 5 mmol of titanium sulfate is dissolved in 50 ml of deionized water and a solution in which 1 mmol of NbCl 5 is dissolved in 40 ml of ethanol are dropped into an aqueous solution in which 4.5 mmol of Na 4 P 2 O 7 is dissolved in 50 ml of deionized water. Example 2-2 is a titanium amorphous phosphate which is stirred overnight and heated at 80 ° C. for 30 minutes, after which the precipitate is separated by centrifugation, washed with water and dried at 80 ° C. for 24 hours. It was. In this amorphous phosphate, 10% of phosphate ion P was substituted with Nb (Ti (P 0.9 Nb 0.1 ) 2 O 7 ).
＜例２−３＞
硫酸チタン５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液及びＮｂＣｌ5２ｍｍｏｌをエタノール４０ｍｌに溶解させた溶液を、４ｍｍｏｌのＮａ4Ｐ2Ｏ7を脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−３とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち２０％がＮｂで置換されたものであった
（Ｔｉ（Ｐ0.8Ｎｂ0.2）2Ｏ7）。
<Example 2-3>
An aqueous solution in which 5 mmol of titanium sulfate was dissolved in 50 ml of deionized water and a solution in which 2 mmol of NbCl 5 were dissolved in 40 ml of ethanol were added dropwise to an aqueous solution in which 4 mmol of Na 4 P 2 O 7 was dissolved in 50 ml of deionized water. Example 2-3 was a titanium amorphous phosphate which was stirred overnight and heated at 80 ° C. for 30 minutes, after which the precipitate was separated by centrifugation, washed with water and dried at 80 ° C. for 24 hours. . In this amorphous phosphate, 20% of phosphate ion P was substituted with Nb (Ti (P 0.8 Nb 0.2 ) 2 O 7 ).
＜例２−４＞
硫酸チタン５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液及びＮｂＣｌ5３ｍｍｏｌをエタノール４０ｍｌに溶解させた溶液を、３．５ｍｍｏｌのＮａ4Ｐ2Ｏ7を脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−４とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち３０％がＮｂで置換されたものであった
（Ｔｉ（Ｐ0.7Ｎｂ0.3）2Ｏ7）。
<Example 2-4>
An aqueous solution in which 5 mmol of titanium sulfate is dissolved in 50 ml of deionized water and a solution in which 3 mmol of NbCl 5 are dissolved in 40 ml of ethanol are dropped into an aqueous solution in which 3.5 mmol of Na 4 P 2 O 7 is dissolved in 50 ml of deionized water. The titanium amorphous phosphate obtained by stirring the mixture overnight, heating it at 80 ° C. for 30 minutes, separating the precipitate by centrifugation, washing with water, and drying at 80 ° C. for 24 hours is shown in Example 2-4. It was. In this amorphous phosphate, 30% of the phosphate ion P was substituted with Nb (Ti (P 0.7 Nb 0.3 ) 2 O 7 ).
＜例２−５＞
硫酸チタン１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液と、ＮｂＣｌ5３ｍｍｏｌ及びＴａＣｌ5３ｍｍｏｌをエタノール８０ｍｌに溶解させた溶液とを、Ｎａ4Ｐ2Ｏ7７ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−５とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち１５％がＮｂで且つ１５％がＴａで置換されたものであった（Ｔｉ（Ｐ0.7Ｎｂ0.15Ｔａ0.15）2Ｏ7）。
<Example 2-5>
Aqueous solutions and aqueous solution prepared by dissolving titanium sulfate 10mmol deionized
＜例２−６＞
硫酸チタン５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液と、ＮｂＣｌ5３ｍｍｏｌ及びＴａＣｌ5２ｍｍｏｌをエタノール５０ｍｌに溶解させた溶液とを、Ｎａ4Ｐ2Ｏ7７ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−６とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち２０％がＮｂで且つ２０％がＴａで置換されたものであった（Ｔｉ（Ｐ0.6Ｎｂ0.2Ｔａ0.2）2Ｏ7）。
<Example 2-6>
Aqueous solutions and aqueous solution prepared by dissolving titanium sulfate 5mmol deionized water 50ml, and a solution prepared by dissolving NbCl 5 3 mmol and TaCl 5 2 mmol of ethanol 50ml, dissolve the Na 4 P 2 O 7 7mmol deionized water 50ml An example is an amorphous phosphate of titanium, which is dripped in and stirred overnight, heated at 80 ° C. for 30 minutes, and then the precipitate is separated by centrifugation, washed with water, and dried at 80 ° C. for 24 hours. 2-6. In this amorphous phosphate, 20% of the phosphate ion P was substituted with Nb and 20% with Ta (Ti (P 0.6 Nb 0.2 Ta 0.2 ) 2 O 7 ).
＜例２−７＞
硫酸チタン１０ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液を、８ｍｍｏｌのＮａ4Ｐ2Ｏ7と４ｍｍｏｌのＮａ2ＳｉＯ3・９Ｈ2Ｏとを脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるチタンのアモルファスリン酸塩を例２−７とした。このアモルファスリン酸塩は、リン酸イオンのＰのうち２０％がＳｉで置換されたものであった（Ｔｉ（Ｐ0.8Ｓｉ0.2）2Ｏ7）。
<Example 2-7>
An aqueous solution in which 10 mmol of titanium sulfate is dissolved in 100 ml of deionized water is added dropwise to an aqueous solution in which 8 mmol of Na 4 P 2 O 7 and 4 mmol of Na 2 SiO 3 .9H 2 O are dissolved in 50 ml of deionized water. Example 2-7 was a titanium amorphous phosphate which was stirred overnight and heated at 80 ° C. for 30 minutes, after which the precipitate was separated by centrifugation, washed with water and dried at 80 ° C. for 24 hours. . This amorphous phosphate was one in which 20% of P of phosphate ions was replaced by Si (Ti (P 0.8 Si 0.2 ) 2 O 7 ).
（試験評価方法）
例２−１〜例２−７について、試験評価１と同様に、結晶性・非結晶性及び色相の試験評価を行った。なお、生成相の同定は、例２−１について、未焼成のもの、並びに、３５０℃、４００℃、５００℃、７００℃、８００℃及び１０００℃の各温度で５時間焼成したものについて行った。例２−２について、未焼成のもの、並びに、３５０℃、４００℃、４５０℃、５００℃、５５０℃、６００℃及び６５０℃の各温度で焼成したものについて行った。例２−３及び例２−４のそれぞれについて、未焼成のもの、並びに、５００℃、５５０℃、６００℃、６５０℃及び７００℃の各温度で焼成したものについて行った。例２−５及び例２−６のそれぞれについて、未焼成のもの、並びに、６００℃、６５０℃、７００℃及び７５０℃の各温度で焼成したものについて行った。例２−７について、未焼成のもの、並びに、３５０℃、４００℃、４５０℃、５００℃、５５０℃、６００℃、６５０℃及び７００℃の各温度で焼成したものについて行った。
(Test evaluation method)
About Example 2-1 to Example 2-7, the test evaluation of crystallinity / non-crystallinity and hue was performed in the same manner as in Test Evaluation 1. In addition, the identification of the production | generation phase was performed about Example 2-1 about what was baked for 5 hours at each temperature of 350 degreeC, 400 degreeC, 500 degreeC, 700 degreeC, 800 degreeC, and 1000 degreeC. . About Example 2-2, it carried out about what was baked, and what was baked at each temperature of 350 degreeC, 400 degreeC, 450 degreeC, 500 degreeC, 550 degreeC, 600 degreeC, and 650 degreeC. About each of Example 2-3 and Example 2-4, it performed about what was baked and what was baked at each temperature of 500 degreeC, 550 degreeC, 600 degreeC, 650 degreeC, and 700 degreeC. About each of Example 2-5 and Example 2-6, it performed about what was baked and what was baked at each temperature of 600 degreeC, 650 degreeC, 700 degreeC, and 750 degreeC. About Example 2-7, it carried out about what was baked at each temperature of 350 degreeC, 400 degreeC, 450 degreeC, 500 degreeC, 550 degreeC, 600 degreeC, 650 degreeC, and 700 degreeC.
また、以下の紫外線遮断性の試験評価も行った。 In addition, the following ultraviolet ray blocking test evaluation was also performed.
＜紫外線遮断性＞
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、例２−１〜例２−７のそれぞれについて紫外線遮断性及び可視光透明性、つまり、紫外線の反射スペクトルを測定した。なお、紫外線遮断性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）を参照試料とした。この反射スペクトルにおける３２０〜４００ｎｍ（ＵＶ−Ａ）及び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。
<UV blocking property>
Using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550 type, with integrating sphere), each of Examples 2-1 to 2-7 has ultraviolet blocking properties and visible light transparency, that is, an ultraviolet reflection spectrum. Was measured. In addition, barium sulfate powder (manufactured by Wako Pure Chemicals, special grade of reagent) was used as a reference sample for evaluation for judging the ultraviolet blocking performance. In this reflection spectrum, as the reflectance values of 320 to 400 nm (UV-A) and 250 to 320 nm (UV-B) are smaller than the reflectance in the visible light region, the ultraviolet rays are selectively absorbed. To express.
（試験評価結果）
表４〜１０は、例２−１〜例２−７の試験評価結果をそれぞれ示す。また、図１ａ〜１ｇは、例２−１〜例２−７の紫外線吸収スペクトルをそれぞれ示す。
(Test evaluation results)
Tables 4 to 10 show the test evaluation results of Example 2-1 to Example 2-7, respectively. 1a to 1g show the ultraviolet absorption spectra of Examples 2-1 to 2-7, respectively.
例２−１では、表４によれば、ＸＲＤの結果より、３５０℃までアモルファス状態を維持できるということが分かる。また、図１ａによれば、紫外線遮断性能は、焼成温度に関わらず、アモルファス状態であれば良好であることが分かる。さらに、表４によれば、色相は、焼成温度が高くなると黄色さを表すｂ値が大きくなり、白色が僅かに黄色がかっていくことが分かる。 In Example 2-1, according to Table 4, it can be seen from the XRD results that the amorphous state can be maintained up to 350 ° C. Further, according to FIG. 1a, it can be seen that the ultraviolet blocking performance is good in the amorphous state regardless of the firing temperature. Furthermore, it can be seen from Table 4 that the b value representing the yellowness increases as the firing temperature increases, and the white color is slightly yellowish.
例２−２では、表５によれば、ＸＲＤの結果より、６００℃までアモルファス状態を維持できるということが分かる。例２−１に対し、リン酸イオンのＰのうち１０％をＮｂで置換することにより、かかる耐熱性向上効果が得られた。また、図１ｂによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表５によれば、色相は、焼成温度に関係なく白色であることが分かる。 In Example 2-2, according to Table 5, it can be seen from the XRD results that the amorphous state can be maintained up to 600 ° C. In Example 2-1, the effect of improving the heat resistance was obtained by substituting 10% of the phosphate ion P with Nb. Further, according to FIG. 1b, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and does not deteriorate in the amorphous state. Furthermore, according to Table 5, it can be seen that the hue is white regardless of the firing temperature.
例２−３では、表６によれば、ＸＲＤの結果より、６５０℃までアモルファス状態を維持できるということが分かる。例２−１に対し、リン酸イオンのＰのうち２０％をＮｂで置換することにより、かかる耐熱性向上効果が得られた。また、図１ｃによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表６によれば、色相は、焼成温度に関係なくアモルファス状態では白色であるが、結晶化するとｂ値が増大してやや黄色がかってくることが分かる。 In Example 2-3, according to Table 6, it can be seen from the XRD results that the amorphous state can be maintained up to 650 ° C. In Example 2-1, the effect of improving heat resistance was obtained by substituting 20% of the phosphate ion P with Nb. Further, according to FIG. 1c, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and is not deteriorated in an amorphous state. Further, according to Table 6, it can be seen that the hue is white in the amorphous state regardless of the firing temperature, but the b value increases and becomes slightly yellow when crystallized.
例２−４では、表７によれば、ＸＲＤの結果より、６５０℃までアモルファス状態を維持できるということが分かる。しかしながら、リン酸イオンのＰのうち２０％をＮｂで置換した例２−３からのさらなる耐熱性向上効果は得られなかった。また、図１ｄによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表７によれば、色相は、焼成温度に関係なくアモルファス状態では白色であるが、結晶化するとｂ値が増大してやや黄色がかってくることが分かる。 In Example 2-4, according to Table 7, it can be seen from the result of XRD that the amorphous state can be maintained up to 650 ° C. However, the further heat resistance improvement effect from Example 2-3 which substituted 20% of P of phosphate ion with Nb was not acquired. Further, according to FIG. 1d, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and does not deteriorate in the amorphous state. Furthermore, according to Table 7, it can be seen that the hue is white in the amorphous state regardless of the firing temperature, but the b value increases and becomes slightly yellow when crystallized.
例２−５では、表８によれば、ＸＲＤの結果より、７００℃までアモルファス状態を維持できるということが分かる。例２−１に対し、リン酸イオンのＰのうち１５％をＮｂで且つ１５％をＴａで置換することにより、かかる耐熱性向上効果が得られた。また、図１ｅによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表８によれば、色相は、焼成温度に関係なくアモルファス状態では白色であるが、結晶化するとｂ値が増大してやや黄色がかってくることが分かる。 In Example 2-5, it can be seen from Table 8 that the amorphous state can be maintained up to 700 ° C. from the result of XRD. Compared to Example 2-1, by replacing 15% of phosphate ion P with Nb and 15% with Ta, such a heat resistance improving effect was obtained. Further, according to FIG. 1e, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and does not deteriorate in the amorphous state. Further, according to Table 8, it can be seen that the hue is white in the amorphous state regardless of the firing temperature, but the b value increases and becomes slightly yellow when crystallized.
例２−６では、表９によれば、ＸＲＤの結果より、７００℃までアモルファス状態を維持できるということが分かる。しかしながら、リン酸イオンのＰのうち１５％をＮｂで且つ１５％をＴａで置換した例２−５からのさらなる耐熱性向上効果は得られなかった。また、図１ｆによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表９によれば、色相は、焼成温度に関係なくアモルファス状態では白色であるが、結晶化するとｂ値が増大してやや黄色がかってくることが分かる。 In Example 2-6, according to Table 9, it can be seen from the XRD results that the amorphous state can be maintained up to 700 ° C. However, no further heat resistance improvement effect was obtained from Example 2-5 in which 15% of phosphate ion P was replaced with Nb and 15% with Ta. Further, according to FIG. 1f, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and does not deteriorate in the amorphous state. Further, according to Table 9, it can be seen that the hue is white in the amorphous state regardless of the firing temperature, but the b value increases and becomes slightly yellow when crystallized.
例２−７では、表１０によれば、ＸＲＤの結果より、６５０℃までアモルファス状態を維持できるということが分かる。例２−１に対し、リン酸イオンのＰのうち２０％をＳｉで置換することにより、かかる耐熱性向上効果が得られた。また、図１ｇによれば、紫外線遮断性能は、アモルファス状態であれば焼成温度の影響を受けず、また、劣化することもないことが分かる。さらに、表１０によれば、色相は、焼成温度に関係なくアモルファス状態では白色であるが、結晶化するとｂ値が増大してやや黄色がかってくることが分かる。 In Example 2-7, it can be seen from Table 10 that the amorphous state can be maintained up to 650 ° C. from the result of XRD. Compared to Example 2-1, such heat resistance improvement effect was obtained by substituting 20% of the phosphate ion P with Si. Further, according to FIG. 1g, it can be seen that the ultraviolet blocking performance is not affected by the firing temperature and does not deteriorate in the amorphous state. Further, according to Table 10, it can be seen that the hue is white in the amorphous state regardless of the firing temperature, but the b value increases and becomes slightly yellow when crystallized.
以上、例２−１〜例２−７を比較すると、Ｎｂ、Ｔａ又はＳｉを含有している例２−２等は、それらの元素が結晶化阻止成分として機能するため、それらを含有しない例２−１が結晶化する温度では結晶化せずに、それよりも高温度で結晶化する。一方、上述のように、アモルファスリン酸塩は、少なくともアモルファス状態であれば良好な紫外線吸収特性を示す。従って、例２−２等のアモルファスリン酸塩は、Ｎｂ、Ｔａ又はＳｉを含有することにより結晶化温度、つまり、アモルファス状態が保持される温度が高められ、それに伴って紫外線遮断性能が保持される温度も高められるので、それらを含有しない例２−１よりも紫外線遮断剤として耐熱性能が優れることとなる。 As described above, when Example 2-1 to Example 2-7 are compared, Example 2-2 containing Nb, Ta, or Si is an example in which those elements function as a crystallization inhibiting component and thus do not contain them. It does not crystallize at a temperature at which 2-1 crystallizes, but crystallizes at a higher temperature. On the other hand, as described above, the amorphous phosphate exhibits good ultraviolet absorption characteristics at least in an amorphous state. Therefore, amorphous phosphates such as Example 2-2 increase the crystallization temperature, that is, the temperature at which the amorphous state is maintained by containing Nb, Ta or Si, and accordingly, the ultraviolet blocking performance is maintained. Therefore, the heat resistance performance is superior as an ultraviolet blocking agent compared to Example 2-1, which does not contain them.
［試験評価３］
（試験評価試料）
以下の各例に係るＣｅ0.5Ｔｉ0.5Ｐ2Ｏ7系アモルファスリン酸塩を調製した。
[Test Evaluation 3]
(Test evaluation sample)
Ce 0.5 Ti 0.5 P 2 O 7 -based amorphous phosphates according to the following examples were prepared.
＜例３−１＞
硫酸セリウム（IV）四水和物５ｍｍｏｌ及び硫酸チタン５ｍｍｏｌを脱イオン水１００ｍｌに溶解させた水溶液を、沈殿剤としての０．１ｍｏｌ／ＬのＮａ4Ｐ2Ｏ7水溶液１００ｍｍｏｌに滴下し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるセリウム・チタンのアモルファス複合リン酸塩を例３−１とした（Ｃｅ0.5Ｔｉ0.5Ｐ2Ｏ7）。
<Example 3-1>
An aqueous solution prepared by dissolving 5 mmol of cerium (IV) sulfate tetrahydrate and 5 mmol of titanium sulfate in 100 ml of deionized water was added dropwise to 100 mmol of a 0.1 mol / L Na 4 P 2 O 7 aqueous solution as a precipitating agent. A cerium-titanium amorphous composite phosphate obtained by heating at 80 ° C. for 30 minutes, then separating the precipitate by centrifugation, washing with water, and drying at 80 ° C. for 24 hours was defined as Example 3-1 (Ce 0.5 Ti 0.5 P 2 O 7 ).
＜例３−２＞
硫酸セリウム（IV）四水和物５ｍｍｏｌ及び硫酸チタン５ｍｍｏｌを脱イオン水５０ｍｌに溶解させた水溶液及びＮｂＣｌ5２ｍｍｏｌをエタノール５０ｍｌに溶解させた溶液を、９ｍｍｏｌのＮａ4Ｐ2Ｏ7を脱イオン水５０ｍｌに溶解させた水溶液に滴下して一晩攪拌し、それを８０℃で３０分間加熱し、しかる後に沈殿物を遠心分離により分離して水洗し、８０℃で２４時間乾燥してなるセリウム・チタンのアモルファス複合リン酸塩を例３−２とした。このアモルファス複合リン酸塩は、ＣｅとＴｉとのモル比が１：１であり、リン酸イオンのＰのうち１０％がＮｂで置換されたものであった（Ｃｅ0.5Ｔｉ0.5（Ｐ0.9Ｎｂ0.1）2Ｏ7）。
<Example 3-2>
An aqueous solution prepared by dissolving 5 mmol of cerium (IV) sulfate tetrahydrate and 5 mmol of titanium sulfate in 50 ml of deionized water and a solution obtained by dissolving 2 mmol of NbCl 5 in 50 ml of ethanol, 9 mmol of Na 4 P 2 O 7 in deionized water A solution of cerium, which was dropped into an aqueous solution dissolved in 50 ml and stirred overnight, heated at 80 ° C. for 30 minutes, and then the precipitate was separated by centrifugation, washed with water, and dried at 80 ° C. for 24 hours. An amorphous composite phosphate of titanium was taken as Example 3-2. The amorphous composite phosphate had a molar ratio of Ce to Ti of 1: 1, and 10% of phosphate ion P was substituted with Nb (Ce 0.5 Ti 0.5 (P 0.9 Nb 0.1) 2 O 7).
（試験評価方法）
例３−１及び例３−２について、試験評価２と同様に、結晶性・非結晶性、紫外線遮断性及び色相の試験評価を行った。なお、生成相の同定は、例３−１について、未焼成のもの、並びに、６５０℃、７００℃及び７５０℃の各温度で５時間焼成したものについて行った。例３−２について、未焼成のもの、並びに、５００℃、６００℃、６５０℃及び７００℃の各温度で焼成したものについて行った。
(Test evaluation method)
About Example 3-1 and Example 3-2, the test evaluation of crystallinity / non-crystallinity, ultraviolet-blocking property, and hue was performed similarly to Test Evaluation 2. In addition, the identification of the production | generation phase was performed about the thing which baked for 5 hours at each temperature of 650 degreeC, 700 degreeC, and 750 degreeC about Example 3-1. About Example 3-2, it carried out about what was baked, and what was baked at each temperature of 500 degreeC, 600 degreeC, 650 degreeC, and 700 degreeC.
（試験評価結果）
表１１及び１２は、例３−１及び例３−２の試験評価結果をそれぞれ示す。また、図２ａ及び２ｂは、例３−１及び例３−２の紫外線吸収スペクトルをそれぞれ示す。
(Test evaluation results)
Tables 11 and 12 show the test evaluation results of Example 3-1 and Example 3-2, respectively. 2a and 2b show the ultraviolet absorption spectra of Example 3-1 and Example 3-2, respectively.
例３−１では、表１１によれば、ＸＲＤの結果より６００℃までアモルファス状態を維持できるということが分かる。Ｃｅだけを含む例１−１が４５０℃までアモルファス状態を維持でき、Ｔｉだけを含む例２−１が３５０℃までアモルファス状態を維持できることから、Ｃｅ・Ｔｉの複合塩とすることによりそれらの相乗効果が得られるということが分かる。また、図２ａによれば、紫外線遮断性能は、焼成温度が５００〜６００℃の範囲でやや低下が認められるものの、焼成温度が６００℃以下では概ね良好であるのが分かる。さらに、表１１によれば、色相は、焼成温度が高くなると黄色さを表すｂ値が小さくなり、黄色が薄くなることが分かる。 In Example 3-1, it can be seen from Table 11 that the amorphous state can be maintained up to 600 ° C. from the result of XRD. Example 1-1 containing only Ce can maintain an amorphous state up to 450 ° C., and Example 2-1 containing only Ti can maintain an amorphous state up to 350 ° C. It turns out that an effect is acquired. Further, according to FIG. 2a, it can be seen that the ultraviolet blocking performance is generally good when the firing temperature is 600 ° C. or less, although a slight decrease is observed in the range of 500 to 600 ° C. Further, according to Table 11, it can be seen that as the hue increases, the b value representing yellowness decreases and the yellow color decreases as the firing temperature increases.
例３−２では、表１２によれば、ＸＲＤの結果より、７００℃までアモルファス状態を維持できるということが分かる。例３−１に対し、リン酸イオンのＰのうち１０％をＮｂで置換することにより、かかる耐熱性向上効果が得られた。また、図２ｂによれば、紫外線遮断性能は、焼成温度が高くなると低下することが分かる。さらに、表１２によれば、色相は、焼成温度が高くなるとｂ値が小さくなり、黄色が薄くなることが分かる。 In Example 3-2, according to Table 12, it can be seen from the XRD results that the amorphous state can be maintained up to 700 ° C. In Example 3-1, the effect of improving heat resistance was obtained by substituting 10% of the phosphate ion P with Nb. In addition, according to FIG. 2b, it can be seen that the ultraviolet blocking performance decreases as the firing temperature increases. Furthermore, according to Table 12, it can be seen that the hue value b decreases and the yellow color decreases as the firing temperature increases.
以上、例３−１及び例３−２を比較すると、Ｎｂを含有している例３−２は、Ｎｂが結晶化阻止成分として機能するため、それを含有しない例３−１が結晶化する温度では結晶化せずに、それよりも高温度で結晶化する。一方、上述のように、アモルファスリン酸塩は、アモルファス状態であれば良好な紫外線吸収特性を示す。従って、例３−２のアモルファスリン酸塩は、Ｎｂを含有することにより結晶化温度、つまり、アモルファス状態が保持される温度が高められ、それに伴って紫外線遮断性能が保持される温度も高められるので、それらを含有しない例３−１よりも紫外線遮断剤として耐熱性能が優れることとなる。 As mentioned above, when Example 3-1 and Example 3-2 are compared, since Example 3-2 containing Nb functions as a crystallization inhibiting component, Example 3-1 not containing it crystallizes. It does not crystallize at temperature but crystallizes at a higher temperature. On the other hand, as described above, amorphous phosphate exhibits good ultraviolet absorption characteristics when in an amorphous state. Therefore, the amorphous phosphate of Example 3-2 contains Nb, so that the crystallization temperature, that is, the temperature at which the amorphous state is maintained is increased, and accordingly, the temperature at which the ultraviolet blocking performance is maintained is also increased. Therefore, heat resistance performance will be more excellent as an ultraviolet blocking agent than Example 3-1, which does not contain them.
これらの試験評価１〜３の結果より、Ｃｅ及び／又はＴｉのアモルファスリン酸塩において、Ｐの一部分をＮｂ、Ｔａ或いはＳｉで置換することにより、結晶化温度が高められることが分かる。そして、結晶化温度が高められると、少なくともその温度まではアモルファス状態が保持される、つまり、その温度までは優れた紫外線遮断性能が保持されることとなり、従って、それによって紫外線遮断性能についての耐熱性の改善が図られることとなる。 From the results of these test evaluations 1 to 3, it is understood that the crystallization temperature can be increased by substituting a part of P with Nb, Ta or Si in the Ce and / or Ti amorphous phosphate. When the crystallization temperature is increased, the amorphous state is maintained at least up to that temperature, that is, the excellent UV blocking performance is maintained up to that temperature. The improvement of sex will be achieved.
また、試験評価１及び２と試験評価３とを比較すると、Ｃｅ又はＴｉのアモルファスリン酸塩よりもＣｅ及びＴｉのアモルファス複合リン酸塩の方が耐熱性が優れることが分かる。 Moreover, when test evaluation 1 and 2 and test evaluation 3 are compared, it turns out that the heat resistance of the amorphous composite phosphate of Ce and Ti is superior to the amorphous phosphate of Ce or Ti.
以上説明したように、本発明は、樹脂成形品や塗料等に紫外線遮断剤として含有させるアモルファスリン酸塩について有用である。 As described above, the present invention is useful for an amorphous phosphate contained as a UV blocker in a resin molded product or paint.
Claims (12)
上記結晶化阻止成分は、Ｐの一部を置換するように含有された元素である紫外線遮断剤。 In the ultraviolet blocker according to claim 1,
The crystallization inhibiting component is an ultraviolet blocking agent which is an element contained so as to substitute a part of P.
上記結晶化阻止成分を元素Ｘとしたとき、
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０）
で表される紫外線遮断剤。 In the ultraviolet blocker according to claim 2,
When the crystallization inhibitor component is element X,
Composition formula: Ce α Ti 1-α ( P 1-β X β) 2 O 7 + γ
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0)
UV blocker represented by
上記結晶化阻止成分は、Ｐの一部を置換するように含有された元素である化粧品。 The cosmetic according to claim 4,
Cosmetics which are the elements contained so that the said crystallization inhibitory component may substitute a part of P.
上記結晶化阻止成分を元素Ｘとしたとき、
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０）
で表される化粧品。 The cosmetic according to claim 5,
When the crystallization inhibitor component is element X,
Composition formula: Ce α Ti 1-α ( P 1-β X β) 2 O 7 + γ
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0)
Cosmetics represented by
上記結晶化阻止成分は、Ｐの一部を置換するように含有された元素である樹脂成形品。 In the resin molded product according to claim 7,
The resin crystallized product, wherein the crystallization inhibiting component is an element contained so as to substitute a part of P.
上記結晶化阻止成分を元素Ｘとしたとき、
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０）
で表される樹脂成形品。 In the resin molded product described in claim 8,
When the crystallization inhibitor component is element X,
Composition formula: Ce α Ti 1-α ( P 1-β X β) 2 O 7 + γ
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0)
Resin molded product represented by
上記結晶化阻止成分は、Ｐの一部を置換するように含有された元素である塗料。 In the paint according to claim 10,
The crystallization inhibiting component is a paint which is an element contained so as to substitute a part of P.
上記結晶化阻止成分を元素Ｘとしたとき、
組成式：ＣｅαＴｉ１−α（Ｐ １−β Ｘ β ）２Ｏ７＋γ
（０≦α≦１、０＜β≦０．５、−０．５≦γ≦１．０）
で表される塗料。 The paint according to claim 11,
When the crystallization inhibitor component is element X,
Composition formula: Ce α Ti 1-α ( P 1-β X β) 2 O 7 + γ
(0 ≦ α ≦ 1, 0 <β ≦ 0.5, −0.5 ≦ γ ≦ 1.0)
Paint represented by
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| WO2018180797A1 (en) | 2017-03-30 | 2018-10-04 | 株式会社フジミインコーポレーテッド | Titanium phosphate powder, production method therefor, and white pigment for cosmetics |
| WO2019189665A1 (en) | 2018-03-30 | 2019-10-03 | 株式会社フジミインコーポレーテッド | White pigment for cosmetics, and cosmetic |
| US11638681B2 (en) | 2018-09-20 | 2023-05-02 | Fujimi Incorporated | White pigment for cosmetics, and cosmetic |
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| JP2003119452A (en) * | 2001-10-17 | 2003-04-23 | Kinya Adachi | Cerium phosphate-titanium phosphate ultraviolet screening agent and method for manufacturing the same |
| JP2005505669A (en) * | 2002-10-16 | 2005-02-24 | ロディア エレクトロニクス アンド カタリシス | Ultraviolet protective agent containing phosphate of cerium and titanium and method for producing the same |
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| JPH11209109A (en) * | 1998-01-21 | 1999-08-03 | Pola Chem Ind Inc | Multiple phosphate |
| JP2003119452A (en) * | 2001-10-17 | 2003-04-23 | Kinya Adachi | Cerium phosphate-titanium phosphate ultraviolet screening agent and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018180797A1 (en) | 2017-03-30 | 2018-10-04 | 株式会社フジミインコーポレーテッド | Titanium phosphate powder, production method therefor, and white pigment for cosmetics |
| KR20190113990A (en) | 2017-03-30 | 2019-10-08 | 가부시키가이샤 후지미인코퍼레이티드 | Titanium Phosphate Powder and Manufacturing Method Thereof, White Pigment for Cosmetics |
| KR20200133007A (en) | 2017-03-30 | 2020-11-25 | 가부시키가이샤 후지미인코퍼레이티드 | Titanium phosphate powder, production method therefor, and white pigment for cosmetics |
| KR20210012061A (en) | 2017-03-30 | 2021-02-02 | 가부시키가이샤 후지미인코퍼레이티드 | Pigment for cosmetics comprising titanium phosphate powder, production method therefor |
| US11345596B2 (en) | 2017-03-30 | 2022-05-31 | Fujimi Incorporated | Titanium phosphate powder, production method therefor, and white pigment for cosmetics |
| WO2019189665A1 (en) | 2018-03-30 | 2019-10-03 | 株式会社フジミインコーポレーテッド | White pigment for cosmetics, and cosmetic |
| KR20200136916A (en) | 2018-03-30 | 2020-12-08 | 가부시키가이샤 후지미인코퍼레이티드 | White pigment for cosmetics, cosmetics |
| US11638681B2 (en) | 2018-09-20 | 2023-05-02 | Fujimi Incorporated | White pigment for cosmetics, and cosmetic |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |