JPH022867A - Microcapsule containing ultraviolet absorber, production thereof and cosmetic containing the same microcapsule - Google Patents
Microcapsule containing ultraviolet absorber, production thereof and cosmetic containing the same microcapsuleInfo
- Publication number
- JPH022867A JPH022867A JP15047288A JP15047288A JPH022867A JP H022867 A JPH022867 A JP H022867A JP 15047288 A JP15047288 A JP 15047288A JP 15047288 A JP15047288 A JP 15047288A JP H022867 A JPH022867 A JP H022867A
- Authority
- JP
- Japan
- Prior art keywords
- microcapsules
- benzophenone derivative
- cosmetic
- integer
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 71
- 239000002537 cosmetic Substances 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000010419 fine particle Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 alkali metal sulfonate Chemical class 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000008366 benzophenones Chemical class 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 239000006096 absorbing agent Substances 0.000 abstract description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012965 benzophenone Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical group OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 6
- 239000006071 cream Substances 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 239000001023 inorganic pigment Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical group OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000007794 irritation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 229940032094 squalane Drugs 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OQERFUGURPLBQH-UHFFFAOYSA-N (2-hydroxy-5-methylphenyl)-phenylmethanone Chemical compound CC1=CC=C(O)C(C(=O)C=2C=CC=CC=2)=C1 OQERFUGURPLBQH-UHFFFAOYSA-N 0.000 description 2
- BMIWAAVPVVXJQH-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone;(4-hydroxyphenyl)-phenylmethanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1.OC1=CC=CC=C1C(=O)C1=CC=CC=C1 BMIWAAVPVVXJQH-UHFFFAOYSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- 206010015150 Erythema Diseases 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 235000013871 bee wax Nutrition 0.000 description 2
- 239000012166 beeswax Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 231100000321 erythema Toxicity 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- KIZCNUWGIVQQBK-UHFFFAOYSA-N (2-hydroxy-4-methylphenyl)-phenylmethanone Chemical compound OC1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 KIZCNUWGIVQQBK-UHFFFAOYSA-N 0.000 description 1
- RIFCEURUCJPMOQ-UHFFFAOYSA-N (2-hydroxy-5-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=C(O)C(C(=O)C=2C=CC=CC=2)=C1 RIFCEURUCJPMOQ-UHFFFAOYSA-N 0.000 description 1
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 201000006082 Chickenpox Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010014970 Ephelides Diseases 0.000 description 1
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000003351 Melanosis Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 206010046980 Varicella Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007934 lip balm Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- 239000002304 perfume Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229940093430 polyethylene glycol 1500 Drugs 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- KJCLYACXIWMFCC-UHFFFAOYSA-M sodium;5-benzoyl-4-hydroxy-2-methoxybenzenesulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 KJCLYACXIWMFCC-UHFFFAOYSA-M 0.000 description 1
- 229950004959 sorbitan oleate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 239000003871 white petrolatum Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/025—Applications of microcapsules not provided for in other subclasses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、紫外線吸収剤を内包したマイクロカプセルと
、そのマイクロカプセルの製造方法、並びにその紫外線
吸収剤内包マイクロカプセルを含有する化粧料に関する
ものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to microcapsules containing an ultraviolet absorber, a method for producing the microcapsules, and cosmetics containing the microcapsules containing the ultraviolet absorber. It is.
（従来の技術）
周知のように、紫外線は皮膚に対して種々の影響をもた
らすことが知られている。(Prior Art) As is well known, ultraviolet rays are known to have various effects on the skin.
すなわち、ＵＶ−Ｂ領域（２９０〜３２０ｎｍ）の紫外
線は、皮膚に紅斑や水痘を生ぜしめ、炎症後に皮膚の黒
化をもたらす。That is, ultraviolet rays in the UV-B region (290 to 320 nm) cause erythema and chickenpox on the skin, resulting in darkening of the skin after inflammation.
又、ＵＶ−Ａ領域（３２０〜４００ｎｍ）の紫外線は、
紅斑こそほとんど生じさせないものの、黒化をもたらす
点ではＵＶ−Ｂの紫外線の場合と同様である。In addition, ultraviolet rays in the UV-A region (320 to 400 nm) are
Although it hardly causes erythema, it causes darkening, similar to the case of UV-B ultraviolet rays.
さらに、紫外線は、皮膚にシミ、ソバカス等の色素沈着
を生じさせ、或いは皮膚の老化、変性をももたらす。Furthermore, ultraviolet rays cause pigmentation such as spots and freckles on the skin, and also cause aging and degeneration of the skin.
そこで、このような種々の問題点を解決するために、従
来より種々の紫外線吸収剤が開発されており、たとえば
化粧料等にも含有されている。Therefore, in order to solve these various problems, various ultraviolet absorbers have been developed and are also included in cosmetics, for example.
とりわけ、化粧料の場合には皮膚に対する紫外線遮断の
要請が大であり、従って、上記紫外線吸収剤（主として
有機系のもの、たとえばバラアミノベンゾエート誘導体
、ベンゾ） ＩＪアゾール誘導体、ベンゾフェノン誘導
体、シンナメート誘導体等）の他、たとえば紫外線を反
射しうる二酸化チタン、酸化亜鉛等の無機顔料を含有さ
せることによって紫外線の経皮吸収を防止する化粧料も
市販されている。In particular, in the case of cosmetics, there is a strong need to block UV rays from the skin, and therefore the above-mentioned UV absorbers (mainly organic ones, such as para-aminobenzoate derivatives, benzo), IJ azole derivatives, benzophenone derivatives, cinnamate derivatives, etc. ), there are also commercially available cosmetics that prevent transdermal absorption of ultraviolet rays by containing inorganic pigments such as titanium dioxide and zinc oxide that can reflect ultraviolet rays.
（発明が解決しようとする課題）
（イ）しかしながら、上記有機系の紫外線吸収剤を含有
した化粧料の場合には、その紫外線吸収剤の化粧料基剤
に対する相溶性や使用感が必ずしも良好なものではなか
った。(Problems to be solved by the invention) (a) However, in the case of cosmetics containing the above-mentioned organic ultraviolet absorbers, the compatibility of the ultraviolet absorbers with the cosmetic base and the feeling of use are not necessarily good. It wasn't something.
さらに、皮膚に塗布した場合、紫外線吸収剤自体が皮膚
に刺激を与える他、このような紫外線吸収剤が光エネル
ギーを吸収した場合においても皮膚に一過性の刺激を与
えるという問題があった。Furthermore, when applied to the skin, the ultraviolet absorber itself irritates the skin, and when such an ultraviolet absorber absorbs light energy, it also causes temporary irritation to the skin.
いずれにしても、従来の紫外線吸収剤を含有する化粧料
は、上記のようないずれかの問題点を具有していたため
に、実際に皮膚に使用するに際しては特定の種類のもの
に制限されていた。In any case, because conventional cosmetics containing ultraviolet absorbers have had one of the problems mentioned above, their use on the skin has been limited to certain types. Ta.
（ロ）一方、上記無機顔料を含有する化粧料の場合には
、皮膚に対する刺激等については問題はないが、本来的
に紫外線吸収効果を予定して化粧料に含有されたもので
はないため、紫外線を十分に遮蔽できず、紫外線の経皮
吸収を防止できないという欠点がある。(b) On the other hand, in the case of cosmetics containing the above-mentioned inorganic pigments, there is no problem with irritation to the skin, but since they are not originally included in cosmetics with the intention of having an ultraviolet absorption effect, The drawback is that it cannot sufficiently block ultraviolet rays and prevent transdermal absorption of ultraviolet rays.
特に、可視光線を遮蔽する領域の粒子径（粒子径が比較
的大きいもの）の無機顔料を含有する化粧料は、紫外部
での吸収が弱い。In particular, cosmetics containing inorganic pigments with a particle size in a region that blocks visible light (relatively large particle size) have weak absorption in the ultraviolet region.
これに対して、微粒子の二酸化チタンを配合した場合、
その光散乱効果により、紫外線の遮蔽効果は得られるが
、逆に上記光の散乱によって肌が白っぽく浮いた感じに
なる。しかも、肌への付着性が悪く、延展性に欠けるた
め、肌に厚ぼったく付着し、従っていわゆるメークアッ
プの状態が透明感のない仕上がりとなる。On the other hand, when fine particle titanium dioxide is blended,
Due to the light scattering effect, an effect of shielding ultraviolet rays can be obtained, but conversely, the scattering of the light makes the skin look whitish and floating. Moreover, since it has poor adhesion to the skin and lacks spreadability, it adheres thickly to the skin, resulting in a so-called make-up finish without transparency.
いずれにしても、従来では、紫外線の経皮吸収を防止し
、しかも皮膚に対する安全性や相溶性等の種々の条件を
充足する化粧料はほとんど開発されていなかったのであ
る。In any case, until now, few cosmetics have been developed that prevent transdermal absorption of ultraviolet rays and satisfy various conditions such as safety and compatibility with the skin.
本発明は、上述のような問題点をすべて解決するために
なされたもので、皮膚に有害な紫外線の吸収及び遮蔽効
果が良好で皮膚への紫外線の経皮吸収を防止し、しかも
、安全性、皮膚への付着力。The present invention was made to solve all of the above-mentioned problems, and has a good absorption and shielding effect of ultraviolet rays harmful to the skin, prevents transdermal absorption of ultraviolet rays into the skin, and is safe. , adhesion to the skin.
延展性に優れ、且つ使用感、透明感に優れた化粧料を提
供することを課題とするものである。The object of the present invention is to provide a cosmetic material that has excellent spreadability, and also has excellent feel on use and transparency.
（課題を解決するための手段）
本発明者等は、このような課題を解決するために鋭意研
究を行った結果、ある種の有機系紫外線吸収剤を、ある
種の無機系球状微粒子に内包せしめてマイクロカプセル
化し、これを化粧料に配合すると、上記課題がすべて解
決されることを見出し本発明を完成するに至った。(Means for Solving the Problems) As a result of intensive research to solve these problems, the present inventors have found that a certain kind of organic ultraviolet absorber is encapsulated in a certain kind of inorganic spherical fine particles. The present inventors have discovered that all of the above-mentioned problems can be solved by microcapsulating the product and incorporating it into cosmetics, leading to the completion of the present invention.
すなわち、本発明は、上記課題解決のために、紫外線吸
収剤内包マイクロカプセル、及びそのマイクロカプセル
の製造方法、並びにそのマイクロカプセルを含有する化
粧料としてなされたもので、マイクロカプセルとしての
特徴は、
一般式
式中ｍ個のＸ及びｎ個のＹは各々同−又は異なる炭素数
１〜２４のアルキル基、アルコキシ基、又はスルホン酸
基若しくはそのアルカリ金属塩を示し、且つｍ及びｎは
０〜３の整数を示す、ｋ＋１は１〜４の整数を示す）で
表されるベンゾフェノン誘導体を、シリカを主成分とす
る平均粒径が０゜１〜３０μｍの球状微粒子中に内包せ
しめたことにある。That is, the present invention has been made in order to solve the above-mentioned problems as ultraviolet absorber-containing microcapsules, a method for producing the microcapsules, and a cosmetic containing the microcapsules.The microcapsules have the following characteristics: In the general formula, m X's and n Y's each represent the same or different alkyl group, alkoxy group, or sulfonic acid group having 1 to 24 carbon atoms, or an alkali metal salt thereof, and m and n are 0 to The benzophenone derivative represented by the formula (k+1 is an integer of 3, k+1 is an integer of 1 to 4) is encapsulated in spherical fine particles whose main component is silica and has an average particle diameter of 0°1 to 30 μm. .
又、マイクロカプセルの製造方法としての特徴は、上記
化学構造を有するベンゾフェノン誘導体を、アルカリ金
属のケイ酸塩水溶液中に溶解し、その水溶液と、水及び
前記ベンゾフェノン誘導体に対する溶解度が５％以下の
有機溶媒とを混合して’ｌ／Ｖ１０乳濁液とし、次に前
記アルカリ金属のケイ酸塩及びベンゾフェノン誘導体の
アルカリ溶解物との中和反応により水不溶性沈澱を生成
しうる酸性水溶液を前記乳濁液と混合し、その後、必要
に応じて濾過、水洗、乾燥することにより、前記ベンゾ
フェノン誘導体を、シリカを主成分とする平均粒径が０
．１〜３０μｍの球状微粒子中に内包せしめて製造する
ことにある。The method for manufacturing microcapsules is characterized by dissolving a benzophenone derivative having the above chemical structure in an aqueous solution of an alkali metal silicate, and combining the aqueous solution with an organic compound having a solubility in water and the benzophenone derivative of 5% or less. The emulsion is mixed with a solvent to form a l/V10 emulsion, and then an acidic aqueous solution capable of producing a water-insoluble precipitate is added to the emulsion by neutralization reaction with an alkaline solution of the alkali metal silicate and benzophenone derivative. By mixing the benzophenone derivative with the liquid, and then filtering, washing with water, and drying as necessary, the benzophenone derivative is made into a material whose main component is silica and has an average particle size of 0.
．． It is produced by encapsulating it in spherical fine particles of 1 to 30 μm.
さらに、化粧料としての特徴は、上記のようなマイクロ
カプセルを含有せしめたことにある。Furthermore, its feature as a cosmetic is that it contains the above-mentioned microcapsules.
尚、上記一般式で表されるベンゾフェノン誘導体として
は、たとえば次のものが挙げられる。Incidentally, examples of the benzophenone derivative represented by the above general formula include the following.
（イ）２．２° −ジヒドロキシ−４−メトキシベンゾ
フェノン
（ロ）２−ヒドロキシ−４−メトキシベンゾフェノン
（ハ）２−ヒドロキシ−４−メトキシベンゾフェノン−
５−スルホン酸
（ニ）２，２°−ジヒドロキシ−４，４° −ジメトキ
シベンゾフェノン
（ホ）２，２°、４，４° −テトラヒドロキシベンゾ
フェノン
（へ）２．２”−ジヒドロキシ−４，４° −ジメトキ
シベンゾフェノン−５−スルホン酸ナトリウム
（））２．４−ジヒドロキシベンゾフェノン（チ）２−
ヒドロキシ−４−メトキシベンゾフェノン−５−スルホ
ン酸 ナトリウム
（す）２−ヒドロキシ−４−オクチロキシベンゾフェノ
ン
（ヌ）２−ヒドロキシ−４° −メトキシベンゾフェノ
ン
（ル）２−ヒドロキシベンゾフエノン
（ヲ）４−ヒドロキシベンゾフェノン
（ワ）２−ヒドロキシ−４−メチルベンゾフェノン
（力）２−ヒドロキシ−５−メチルベンゾフェノン
（ヨ）２．５−ジヒドロキシベンゾフェノン（り）２−
ヒドロキシ−５−メトキシベンゾフェノン
ただし、本発明におけるベンゾフェノン誘導体の種類は
上記（イ）〜（夕）に限定されるものではない。(a) 2.2°-dihydroxy-4-methoxybenzophenone (b) 2-hydroxy-4-methoxybenzophenone (c) 2-hydroxy-4-methoxybenzophenone
5-Sulfonic acid (d) 2,2°-dihydroxy-4,4°-dimethoxybenzophenone (e) 2,2°,4,4°-tetrahydroxybenzophenone (h)2,2”-dihydroxy-4,4 ° -Dimethoxybenzophenone-5-sodium sulfonate ()) 2.4-dihydroxybenzophenone (thi) 2-
Hydroxy-4-methoxybenzophenone-5-sulfonic acid Sodium 2-hydroxy-4-octyloxybenzophenone 2-hydroxy-4°-methoxybenzophenone 2-hydroxybenzophenone 4- Hydroxybenzophenone (wa) 2-Hydroxy-4-methylbenzophenone (power) 2-hydroxy-5-methylbenzophenone (y) 2.5-dihydroxybenzophenone (li) 2-
Hydroxy-5-methoxybenzophenone However, the types of benzophenone derivatives in the present invention are not limited to the above (a) to (b).
さらに、本発明の上記マイクロカプセルの製造方法にお
いて、アルカＩＪ ｍ属のケイ酸塩としては、たとえば
ＪＩＳＩ号ケイ酸ナトリウム、ＪＩＳ２号ケイ酸ナトリ
ウム、ＪＩＳａ号ケイ酸す） ＩＪウム、メタケイ酸ナ
トリウム、ケイ酸カリウム（Ｋｚｏ・ｎ５ｉｏｚ、ｎ＝
２〜３．８）等が例示される。Furthermore, in the method for producing microcapsules of the present invention, the silicates of the alkali group IJm include, for example, JISI sodium silicate, JIS No. 2 sodium silicate, JISa sodium silicate, sodium metasilicate, Potassium silicate (Kzo・n5ioz, n=
2 to 3.8), etc. are exemplified.
又、上記製造方法に用いる有機溶媒としては、ｎ−ヘキ
サン、デカン、オクタン等の脂肪族飽和炭化水素、又は
トルエン、ベンゼン、キシレン等の芳香族炭化水素、さ
らにはシクロヘキサン等の脂環式炭化水素等が挙げられ
る。In addition, the organic solvent used in the above production method includes aliphatic saturated hydrocarbons such as n-hexane, decane, and octane, aromatic hydrocarbons such as toluene, benzene, and xylene, and further alicyclic hydrocarbons such as cyclohexane. etc.
これら各溶媒は、勿論１種単独で、又は２種以上併用し
て使用することができる。Of course, each of these solvents can be used alone or in combination of two or more.
さらに、該製造方法に用いる乳化剤としては、好ましく
はＨＬＢ値が３．５〜６．０の範囲内にある非イオン界
面活性剤の使用ができる。代表的なものとして、たとえ
ばソルビタンセスキオレエート。Furthermore, as the emulsifier used in the production method, a nonionic surfactant preferably having an HLB value within the range of 3.5 to 6.0 can be used. A typical example is sorbitan sesquioleate.
ソルビタンモノオレエート、ポリオキシエチレンソルビ
タントリオレエート等がある。Examples include sorbitan monooleate and polyoxyethylene sorbitan trioleate.
さらに、該製造方法に用いる酸性水溶液としては、硫酸
イオンやリン酸イオン等、多価陰イオンを含有するもの
が好ましい。たとえば上記ベンゾフェノン誘導体が２，
４−ジヒドロキシベンゾフェノン、２，２°−ジヒドロ
キシ−４，４“ −ジメトキシベンゾフェノン、２，２
°、４，４゜テトラヒドロキシベンゾフェノンの等の場
合には、反応終了後のｐＨが５以下、とりわけ３以下で
ある酸性水溶液が好ましく、又、その濃度は高い程好ま
しい。Furthermore, the acidic aqueous solution used in the production method preferably contains polyvalent anions such as sulfate ions and phosphate ions. For example, the above benzophenone derivative is 2,
4-dihydroxybenzophenone, 2,2°-dihydroxy-4,4"-dimethoxybenzophenone, 2,2
In the case of 4,4° tetrahydroxybenzophenone, etc., an acidic aqueous solution whose pH after the reaction is 5 or less, especially 3 or less is preferable, and the higher the concentration, the more preferable it is.
ただし、上記アルカリ金属のケイ酸塩、有機溶媒、乳化
剤、酸性水溶液等の種類は上記のものに限定されない。However, the types of the alkali metal silicate, organic solvent, emulsifier, acidic aqueous solution, etc. are not limited to those mentioned above.
（作用）
（１）調製機構に関して
第１図は本発明のマイクロカプセルの微粒子生成過程を
示す説明図である。(Function) (1) Regarding the preparation mechanism, FIG. 1 is an explanatory diagram showing the process of producing microparticles of the microcapsules of the present invention.
先ず、ベンゾフェノン誘導体をアルカリ金属のケイ酸塩
水溶液中に溶解し、その水溶液と有機溶媒とを混合する
と、第１図（イ）に示すように、上記ベンゾフェノン誘
導体とアルカリ金属のケイ酸塩水溶液との混合液を分散
質１とし、有機溶媒を分散媒２とするＷ１０型乳濁液が
調整される。First, when a benzophenone derivative is dissolved in an aqueous solution of an alkali metal silicate and the aqueous solution is mixed with an organic solvent, as shown in FIG. A W10 type emulsion is prepared in which the mixed liquid is used as the dispersoid 1 and the organic solvent is used as the dispersion medium 2.
次に、この乳濁液を上記酸性水溶液と混合する。Next, this emulsion is mixed with the above acidic aqueous solution.
このとき、上記分散質１と酸性水溶液との界面において
次の化学反応が生ずる。At this time, the following chemical reaction occurs at the interface between the dispersoid 1 and the acidic aqueous solution.
（ａ） Ｓ ｉ ０３”−＋ ２ Ｈ”→Ｓ ｉ ０２
＋Ｈ２０（Ｓ １２０５’−＋ ２ Ｈ”−２Ｓ ｉ０
２＋８２０）及び
（ｂ） Ｒ−０−＋Ｈ“→Ｒ−○Ｈ
（ここでＲはベンゾフェノン骨格を示す）尚、この（ｂ
）の反応において、Ｒがたとえば２．４−ジヒドロキシ
ベンゾフェノンの場合は、本発明における界面の化学反
応は、 上記の反応式のように反応し、この２つの化学
反応が同時進行する共沈反応である。(a) S i 03”-+ 2 H”→S i 02
+H20(S 1205'-+ 2H"-2S i0
2+820) and (b) R-0-+H"→R-○H (here, R represents a benzophenone skeleton).
), when R is, for example, 2,4-dihydroxybenzophenone, the interfacial chemical reaction in the present invention is a coprecipitation reaction in which the two chemical reactions proceed simultaneously as shown in the above reaction formula. be.
しかしながら、反応速度の面で（ａ）の反応が（ｂ）の
反応より速く進行するため、先ず、上記界面においてシ
リカの薄膜３が形成され、その後時間の経過とともに、
界面反応が内水相の内側に進行し、ベンゾフェノン誘導
体の生成物４がシリカに内包された状態でマイクロカプ
セル５が製造されることとなるのである。However, in terms of reaction rate, the reaction (a) proceeds faster than the reaction (b), so first a thin silica film 3 is formed at the interface, and then as time passes,
The interfacial reaction proceeds inside the internal aqueous phase, and the microcapsules 5 are produced with the benzophenone derivative product 4 encapsulated in the silica.
（２）内包されたベンゾフェノン誘導体の溶出防止上記
反応機構で得られたシリカを主成分とする球状微粒子中
にベンゾフェノン誘導体を内包せしめたマイクロカプセ
ルには、多量の付着水分が含まれているため、ベンゾフ
ェノン誘導体が変質しない程度に１００℃以上の高温で
乾燥することが好ましい。この操作によって、内包され
たベンゾフェノン誘導体の溶出が極力抑制されることと
なるのである。(2) Prevention of elution of encapsulated benzophenone derivatives Because the microcapsules in which benzophenone derivatives are encapsulated in spherical fine particles mainly composed of silica obtained by the above reaction mechanism contain a large amount of attached water, It is preferable to dry at a high temperature of 100° C. or higher to the extent that the benzophenone derivative does not change in quality. By this operation, elution of the encapsulated benzophenone derivative is suppressed as much as possible.
又、その後、必要に応じてシリコンオイル処理等の公知
の表面処理を行うことも可能であり、内包されたベンゾ
フェノン誘導体の溶出が抑制される。Further, after that, it is possible to perform a known surface treatment such as silicone oil treatment if necessary, and the elution of the encapsulated benzophenone derivative is suppressed.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
実施例１
本実施例は、本発明におけるベンゾフェノン誘導体の一
例である２、２°、４．４’ −テトラヒドロキシベン
ゾフェノンを内包するマイクロカプセルについての実施
例である。Example 1 This example concerns a microcapsule encapsulating 2,2°,4,4'-tetrahydroxybenzophenone, which is an example of the benzophenone derivative of the present invention.
すなわち、本実施例におけるマイクロカプセルは、シリ
カを主成分とする球状微粒子中に、下記式の２． ２’
、 ４． ４°−テトラヒドロキシベンゾフェノン
を１８．２２重量％内包して構成されたもので、その平
均粒子径は１．８μｍである。That is, the microcapsule in this example has 2. 2'
, 4. It is composed of 18.22% by weight of 4°-tetrahydroxybenzophenone, and its average particle diameter is 1.8 μm.
実施例２
本実施例は、本発明におけるベンゾフェノン誘導体の一
例である２、２゛ −ジヒドロキシ−４゜４゛ −ジメ
トキシベンゾフェノンを内包するマイクロカプセルにつ
いての実施例である。Example 2 This example concerns a microcapsule encapsulating 2,2'-dihydroxy-4'4'-dimethoxybenzophenone, which is an example of the benzophenone derivative of the present invention.
すなわち、本実施例におけるマイクロカプセルは、シリ
カを主成分とする球状微粒子中に、下記式の２，２“−
ジヒドロキシ−４，４“−ジメトキシベンゾフェノンを
２２．０４重量％内包して構成されたもので、その平均
粒子径は２．２μｍである。That is, the microcapsules in this example have 2,2"-
It is composed of 22.04% by weight of dihydroxy-4,4''-dimethoxybenzophenone, and its average particle diameter is 2.2 μm.
実施例３
本実施例は、本発明におけるベンゾフェノン誘導体の一
例である２、４−ジヒドロキシベンゾフェノンを内包す
るマイクロカプセルについての実施例である。Example 3 This example is about a microcapsule encapsulating 2,4-dihydroxybenzophenone, which is an example of the benzophenone derivative of the present invention.
すなわち、本実施例におけるマイクロカプセルは、シリ
カを主成分とする球状微粒子中に、上記式の２．４−ジ
ヒドロキシベンゾフェノンを１９．５重量％内包して構
成されたもので、その平均粒子径は３．１μｍである。That is, the microcapsules in this example were constructed by encapsulating 19.5% by weight of 2,4-dihydroxybenzophenone of the above formula in spherical fine particles mainly composed of silica, and the average particle diameter was It is 3.1 μm.
尚、本発明のマイクロカプセルの粒子径は上記各実施例
に限定されるものではなく、要は、そのマイクロカプセ
ルの外壁を構成する球状微粒子の平均粒子径が０．１〜
３０μｍに形成されていればよい。The particle size of the microcapsules of the present invention is not limited to the above-mentioned examples, and the point is that the average particle size of the spherical fine particles constituting the outer wall of the microcapsules is 0.1 to 0.1.
It is sufficient if the thickness is 30 μm.
参考例
上記実施例１〜３のマイクロカプセルについて紫外線吸
収スペクトルを測定し、且つすべり摩擦についての試験
を行った。Reference Example Ultraviolet absorption spectra were measured for the microcapsules of Examples 1 to 3 above, and a sliding friction test was conducted.
（１）紫外線吸収スペクトル
局方の白色ワセリン中に上記各実施例の試料粉末を２０
重量％加え、十分練り込んで分散させ、石英板の間に塗
布し、厚み１５μｍとしてその紫外線吸収スペクトルを
測定した。(1) Add 20% of the sample powder of each of the above examples to white petrolatum with ultraviolet absorption spectra.
% by weight was added, thoroughly kneaded and dispersed, and applied between quartz plates to a thickness of 15 μm, and its ultraviolet absorption spectrum was measured.
その結果、第３図に示すように、上記各実施例のマイク
ロカプセルは、内包するベンゾフェノン誘導体の紫外線
吸収スペクトルに相当する吸収スペクトルを示し、経皮
吸収との関係で問題となるＵＶ−Ａ若しくはＵＶ−Ｂ領
域の紫外線に対して十分な紫外線吸収能を示している。As a result, as shown in FIG. 3, the microcapsules of each of the above examples exhibited absorption spectra corresponding to the ultraviolet absorption spectra of the benzophenone derivatives contained therein, and UV-A or It shows sufficient ultraviolet absorption ability for ultraviolet rays in the UV-B region.
（２）すべり摩擦
上記各実施例の試料をガラス板の上に薄く塗布し、さら
にその上に２００ｇの分銅をのせた平らなガラス板に置
き、水平に引いたとき、滑っている時点での力の大きさ
を測定し、その相対値を第４図のように棒グラフで示し
た。(2) Sliding friction The samples of each of the above examples were applied thinly on a glass plate, and then placed on a flat glass plate with a weight of 200 g placed on it. The magnitude of the force was measured and its relative value was shown in a bar graph as shown in FIG.
その結果、一般の化粧料に含有されているタルク、セリ
サイト、ベンガラ、酸化チタンと比較してすべり摩擦が
小さいことが判明した。As a result, it was found that the sliding friction was lower than that of talc, sericite, red iron oxide, and titanium oxide contained in general cosmetics.
これは、マイクロカプセルが真球状を呈しているので、
上記タルク等に比べ、ローリング効果（転勤性）が良好
であるためと推定される。This is because the microcapsules have a true spherical shape.
This is presumed to be because it has a better rolling effect (transferability) than the above-mentioned talc and the like.
〔マイクロカプセルの製造方法の実施例〕実施例４
本実施例は、上記実施例１の２． ２’、 ４． ４
゜−テトラヒドロキシベンゾフエノンを内包するマイク
ロカプセルを製造する方法についての実施例である。[Example of method for producing microcapsules] Example 4 This example is based on 2. of Example 1 above. 2', 4. 4
This is an example of a method for producing microcapsules containing ゜-tetrahydroxybenzophenone.
先ず、２．２°、４．４” −テトラヒドロキシベンゾ
フェノン４．０５ｇを、１．５ｍｏｌ／βの１号ケイ酸
ナトリウム溶液９０ｍ７！に溶解し、この水溶液をソル
ビタンセスキオレエートとポリオキシエチレンソルビタ
ントリオレエートとの混合物（混合比４：１）の５％ト
ルエン溶液１５０艷に注ぎ、５分間ホモミキサーで乳化
し、Ｗ１０型乳濁液を調製する。First, 4.05 g of 2.2°, 4.4"-tetrahydroxybenzophenone was dissolved in 90 m7 of 1.5 mol/β sodium silicate solution No. 1, and this aqueous solution was dissolved in sorbitan sesquioleate and polyoxyethylene sorbitan. The mixture with trioleate (mixing ratio 4:1) was poured into 150 g of a 5% toluene solution and emulsified in a homomixer for 5 minutes to prepare a W10 type emulsion.
次に、この乳濁液を１．２ｍｏｌ＃！硫酸アンモニウム
、 ０．８８ｍｏｌ＃リン酸２水素ナトリウム及び０．
７２ｍｏｌ／βリン酸との混合水溶液４５０ ｒｒｔｉ
！中に注入し、１時間攪拌し１晩静置する。その後、遠
心分離により固液分離した後、濾過、水洗し、１２０℃
で乾燥を行う。Next, add 1.2 mol of this emulsion! Ammonium sulfate, 0.88 mol #sodium dihydrogen phosphate and 0.88 mol #sodium dihydrogen phosphate.
72 mol/mixed aqueous solution with β phosphoric acid 450 rrti
! Pour into the solution, stir for 1 hour, and let stand overnight. After that, solid-liquid separation was performed by centrifugation, followed by filtration, washing with water, and heating at 120°C.
Dry with .
これによって、シリカを主成分とする球状微粒子中に２
．２’、４．４” −テトラヒドロキシベンゾフェノン
を１８．２２重量％内包する平均粒子径１．８μｍのマ
イクロカプセル１９．７ｇを得た。As a result, 2
．． 19.7 g of microcapsules containing 18.22% by weight of 2',4.4''-tetrahydroxybenzophenone and having an average particle diameter of 1.8 μm were obtained.
尚、本実施例のマイクロカプセルを、走査電子顕微鏡で
観察したところ、第２図のように真球状を呈しているこ
とを確認した。When the microcapsules of this example were observed using a scanning electron microscope, it was confirmed that they had a true spherical shape as shown in FIG.
実施例５
本実施例は、本発明におけるベンゾフェノン誘導体の一
例である２、２′ −ジヒドロキシ−４゜４° −ジメ
トキシベンゾフェノンを内包するマイクロカプセルを製
造する方法についての実施例である。Example 5 This example describes a method for producing microcapsules containing 2,2'-dihydroxy-4°4°-dimethoxybenzophenone, which is an example of the benzophenone derivative of the present invention.
先ず、２，２°−ジヒドロキシ−４，４′−ジメトキシ
ベンゾフェノン１３．５ｇを、１．５ｍｏｌ／ ｊ！の
１号ケイ酸ナトリウム溶液２２５ｒｎ！、に溶解し、こ
の水溶液をソルビタンセスキオレエートとポリオキシエ
チレンソルビタントリオレエートとの混合物（混合比３
：１）の４％ベンゼン溶液４００−に注ぎ、５分間ホモ
ミキサーで乳化し、Ｗ１０型乳濁液を調製する。First, 13.5 g of 2,2°-dihydroxy-4,4'-dimethoxybenzophenone was added to 1.5 mol/j! No. 1 sodium silicate solution 225rn! , and this aqueous solution was mixed with a mixture of sorbitan sesquioleate and polyoxyethylene sorbitan trioleate (mixing ratio 3).
: Pour into the 4% benzene solution of 1) and emulsify with a homomixer for 5 minutes to prepare a W10 type emulsion.
次に、この乳濁液を１．５ ｍｏｌ＃！硫酸アンモニウ
ム、 ０．７５ｍｏｌ＃！リン酸２水素ナトリウム及び
０．７５ｍｏｌ／ｊ！ＩＪン酸との混合水溶液１２０Ｏ
ｒｎｌ中に注入し、１時間攪拌し１２時間静置する。そ
の後、上記実施例４と同様の操作を行い、シリカを主成
分とする球状微粒子中に２．２°−ジヒドロキシ−４，
４゜−ジメトキシベンゾフェノンを２２．０４重量％内
包する平均粒子径２．２μｍのマイクロカプセル５０．
７ｇを得た。Next, add this emulsion to 1.5 mol#! Ammonium sulfate, 0.75mol#! Sodium dihydrogen phosphate and 0.75 mol/j! Mixed aqueous solution with IJ acid 120O
rnl, stirred for 1 hour and left to stand for 12 hours. Thereafter, the same operation as in Example 4 was performed, and 2.2°-dihydroxy-4, 2.2°-dihydroxy-4,
Microcapsules with an average particle diameter of 2.2 μm containing 22.04% by weight of 4°-dimethoxybenzophenone 50.
7g was obtained.
実施例６
本実施例は、本発明におけるベンゾフェノン誘導体の一
例である２、４−ジヒドロキシベンゾフェノンを内包す
るマイクロカプセルを製造する方法についての実施例で
ある。Example 6 This example describes a method for manufacturing microcapsules containing 2,4-dihydroxybenzophenone, which is an example of the benzophenone derivative of the present invention.
先ｆ、２．４−ジヒドロキシベンゾフェノン１０．０ｇ
を、１．５＋ｔ＋ｏ ｌ／ ｊ！の１号ケイ酸ナトリウ
ム溶液２００ ｍｎに溶解し、この水溶液をソルビタン
モノオレエートとポリオキシエチレンソルビタンモノオ
レエートとの混合物（混合比６：１）の５％ｎ−へキサ
ン溶液３５０ｍ１に注ぎ、３分間ホモミキサーで乳化し
、Ｗ１０型乳濁液を調製する。F, 2,4-dihydroxybenzophenone 10.0g
, 1.5+t+o l/j! This aqueous solution was poured into 350 ml of a 5% n-hexane solution of a mixture of sorbitan monooleate and polyoxyethylene sorbitan monooleate (mixing ratio 6:1). Emulsify with a homomixer for 3 minutes to prepare a W10 type emulsion.
次に、この乳濁液を１．２ ｍｏｌ＃！ ！Ｊン酸２水
素ナトリウムと１．８ｍｏｌ／ｊ２ ｔＪン酸との混合
水溶液１００〇−中に注入し、１時間攪拌し１晩静置す
る。その後、上記実施例４と同様の操作を行い、シリカ
を主成分とする球状微粒子中に２．４−ジヒドロキシベ
ンゾフェノンを１９．５２重量％内包する平均粒子径３
．１μｍのマイクロカプセル４５．２ｇを得た。Next, add this emulsion to 1.2 mol#! ! The mixture was poured into 1,000 ml of a mixed aqueous solution of sodium dihydrogen chloride and 1.8 mol/j2 t phosphoric acid, stirred for 1 hour, and left to stand overnight. Thereafter, the same operation as in Example 4 was carried out, and the average particle size was 3, which contained 19.52% by weight of 2,4-dihydroxybenzophenone in spherical fine particles mainly composed of silica.
．． 45.2 g of 1 μm microcapsules were obtained.
上記のようなマイクロカプセルは、皮膚に対する紫外線
の悪影響を防止する目的で化粧料、医薬品等に配合する
ことができる。Microcapsules as described above can be incorporated into cosmetics, pharmaceuticals, etc. for the purpose of preventing the harmful effects of ultraviolet rays on the skin.
本発明のマイクロカプセルの化粧料への配合料は、化粧
料の種類によっても異なるが、一般にはベンゾフェノン
誘導体として０．１〜２０重量％、とりわけ０．５〜１
０重量％になるようにするのが好ましい。The content of the microcapsules of the present invention in cosmetics varies depending on the type of cosmetic, but generally 0.1 to 20% by weight, particularly 0.5 to 1% by weight, as a benzophenone derivative.
Preferably, the content is 0% by weight.
本発明の化粧料は、上記のようなマイクロカプセルを常
法により公知の化粧料基剤に配合し、クリーム、溶液、
スティック、乳液、ファンデーション、軟膏等の種々の
剤型にすることにより調製される。The cosmetics of the present invention can be prepared by blending the microcapsules described above into a known cosmetic base using a conventional method, and then preparing creams, solutions, etc.
It can be prepared in various dosage forms such as sticks, emulsions, foundations, and ointments.
すなわち、上記のようなマイクロカプセルを化粧料基剤
に合わせて選択使用することにより、オイル基剤の化粧
油、多量にオイル基剤を配合する油性クリーム、油性乳
液、水を多量に配合する弱油性クリームや弱油性乳液、
水ベースの化粧水等の基礎化粧品から油剤を基剤とする
ファンデーションやリップスティック等の各種メーキャ
ップ化粧料に至るまで、紫外線吸収効果を有するあらゆ
る形態の化粧料を製造することが可能となる。In other words, by selectively using the microcapsules mentioned above according to the cosmetic base, oil-based cosmetic oils, oil-based creams containing a large amount of oil base, oil-based emulsions, and weak cosmetics containing a large amount of water can be used. Oily creams and weakly oily emulsions,
It becomes possible to produce all types of cosmetics that have ultraviolet absorption effects, from basic cosmetics such as water-based lotions to various makeup cosmetics such as oil-based foundations and lipsticks.
次に、本発明の化粧料の実施例について説明する。Next, examples of the cosmetics of the present invention will be described.
実施例７
本実施例は、本発明のマイクロカプセルをいわゆるパウ
ダーファンデーションに配合した化粧料についての実施
例である。Example 7 This example is about a cosmetic composition containing the microcapsules of the present invention in a so-called powder foundation.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ 実施例１の
マイクロカプセル ３０．０■ タルク
残量■ マイカ
３０．０■ 雲母チタン １
．０■ 酸化チタン ８．０■
ベンガラ ０．７■ 黄酸
化鉄 １．８■ 黒酸化鉄
０．２■ 結晶セルロース
０．２０ メチルポリシロキサン
４．００ 流動パラフィン
３．００ スクワラン ４．０
０ 香料 適量０ 防腐剤
、酸化防止剤 微量本実施例の化粧料を製
造する場合には、上記■〜■をヘンシェルミキサーでよ
くかきまぜながらこれにその他の成分を混合したものを
均一に加え、粉砕機で処理し、圧縮成形することによっ
て製造される。Ingredients Weight %■ Microcapsules of Example 1 30.0■ Talc
Remaining amount ■ Mica
30.0■ Mica titanium 1
．． 0■ Titanium oxide 8.0■
Red iron oxide 0.7■ Yellow iron oxide 1.8■ Black iron oxide
0.2■ Crystalline cellulose
0.20 Methylpolysiloxane
4.00 Liquid paraffin
3.00 Squalane 4.0
0 Fragrance: Appropriate amount: 0 Preservatives, Antioxidants: Very small amount When producing the cosmetics of this example, mix the above ■ to ■ with a Henschel mixer and add the other ingredients evenly thereto, and grind. Manufactured by machine processing and compression molding.
本実施例の化粧料は、透明感、密着性があり、肌に薄く
均一に付着することが可能であった。The cosmetic of this example had transparency and adhesion, and was able to adhere thinly and uniformly to the skin.
又、紫外線遮蔽効果が極めて大であることが認められた
。In addition, it was recognized that the ultraviolet rays shielding effect was extremely high.
しかも、従来の無機顔料を配合した化粧料のように、白
っぽさが浮き出ることもない。What's more, unlike cosmetics containing conventional inorganic pigments, there is no whitish appearance.
さらに、ソフトな使用感が得られるとともに、化粧持続
性も良好であった。Furthermore, a soft feeling of use was obtained, and makeup durability was also good.
実施例８
本実施例は、本発明のマイクロカプセルをＷ１０型乳化
型ファンデーションに配合した化粧料についての実施例
である。Example 8 This example is about a cosmetic composition in which the microcapsules of the present invention are blended into a W10 type emulsified foundation.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ 実施例２の
マイクロカプセル １０．０■ 実施例３のマイク
ロカプセル １０．０■ 二酸化チタン
８゜０■ カオリン
２．０■ タルク
５，０■ 固形パラフィン ５，０■
ラノリン １０．０■ 流
動パラフィン ２７．０■ ソルビタ
ンセスキオレエート ５．００ 精製水
残量０ 香料
適量０ 防腐剤、酸化防止剤 微
量本実施例の化粧料を製造するには、先ず、■〜■を混
合し、粉砕機で処理して粉末を得る。次にこの粉末に上
記■の一部と■を加え、ホモミキサーで均一に分散させ
、■を除く他の成分を加熱溶解してこれに加え、７０℃
に保つ（油相）。その後、■を７０℃に加熱し、油相に
加えホモミキサーで均一に乳化分散させ、乳化後に掻き
混ぜながら４０℃まで冷却する。Ingredients Weight %■ Microcapsules of Example 2 10.0■ Microcapsules of Example 3 10.0■ Titanium dioxide
8゜0■ Kaolin
2.0 ■ Talc
5,0■ Solid paraffin 5,0■
Lanolin 10.0■ Liquid paraffin 27.0■ Sorbitan sesquioleate 5.00 Purified water
0 remaining fragrance
Appropriate amount: 0 Preservative, antioxidant: Very small amount To produce the cosmetic of this example, first, ① to ③ are mixed and processed in a pulverizer to obtain a powder. Next, add a part of the above and ■ to this powder, disperse it uniformly with a homomixer, heat and dissolve the other ingredients except for ■, and add it to this.
(oil phase). Thereafter, (2) is heated to 70°C, added to the oil phase, and uniformly emulsified and dispersed using a homomixer. After emulsification, the mixture is cooled to 40°C while stirring.
本実施例の化粧料は、紫外線遮蔽効果が大で有り、使用
感、透明感が優れている。The cosmetic of this example has a large ultraviolet shielding effect, and has excellent usability and transparency.
又、白さの浮き防止効果も優れており、化粧持続性も良
好であった。In addition, the effect of preventing whiteness from floating was excellent, and the makeup retention was also good.
実施例９
本実施例は、本発明のマイクロカプセルをＷ１０型クリ
ームに配合した化粧料についての実施例である。Example 9 This example is about a cosmetic composition in which the microcapsules of the present invention are blended into a W10 type cream.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ ミクロクリ
スタリンワックス １１．０■ ミツロウ
４．０■ ワセリン
６．０■ 固形パラフィン
５．０■ スクワラン ３
０．０■ ヘキサデシルアジピン酸エステル １０．０
■ グリセリン千ノオレイン酸エステル３．０■ ポリ
オキシエチレン（２０）
ソルビタンオレエート１．０
■ プロピレングリコール ２．５■ 実
施例１のマイクロカプセル １０．００ 精製水
残量０ 香料
適量０ 防腐剤、酸化防止剤
微量本実施例の化粧料を製造するには、先ず、■に
■及び＠を加え、加熱して８０℃に保つ（水相）。Ingredients Weight%■ Microcrystalline wax 11.0■ Beeswax
4.0 ■ Vaseline
6.0■ Solid paraffin
5.0 ■ Squalane 3
0.0■ Hexadecyl adipate ester 10.0
■ Glycerin oleate 3.0 ■ Polyoxyethylene (20) Sorbitan oleate 1.0 ■ Propylene glycol 2.5 ■ Microcapsules from Example 1 10.00 Purified water
0 remaining fragrance
Appropriate amount 0 preservatives, antioxidants
To produce a small amount of the cosmetic of this example, first add ■ and @ to ■, heat and keep at 80°C (aqueous phase).
又、他の成分を混合し、加熱分解して８０℃に保つ（油
相）。ホモミキサーで水相中の■を均一に分散させた後
、油相に水相を加え、ホモミキサーで均一に乳化し、そ
の乳化後に冷却しながら掻き混ぜることによって上記化
粧料が製造される。Also, other components are mixed, heated and decomposed and kept at 80°C (oil phase). After uniformly dispersing (1) in the aqueous phase using a homomixer, the aqueous phase is added to the oil phase, uniformly emulsified using a homomixer, and after the emulsification, the above cosmetic is produced by stirring while cooling.
本実施例の化粧料は、紫外線遮蔽効果に優れ、従来の化
粧料と比べて安全性が高い。The cosmetic of this example has an excellent ultraviolet shielding effect and is safer than conventional cosmetics.
又、肌に均一に薄く付着し、密着性があり、しかも使用
感、透明感が優れている。In addition, it adheres to the skin in a thin and uniform manner, has good adhesion, and has excellent usability and transparency.
又、白さの浮き防止効果も優れており、化粧持続性も良
好であった。In addition, the effect of preventing whiteness from floating was excellent, and the makeup retention was also good.
実施例１０
本実施例は、本発明のマイクロカプセルを０／Ｗ型クリ
ームに配合した化粧料についての実施例である。Example 10 This example is about a cosmetic composition in which the microcapsules of the present invention are blended into an O/W type cream.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ ミツロウ
１０．０■ セチルアル
コール ５．０■ 水添ラノリン
８．０■ スクワラン
３２．５■ グリセリンモノステアリン
酸エステル２．０■ ポリオキシエチレン（２０）ソル
ビタンモノラウリン酸エステル ２．０■ １
．３−ブチレングリコール ５．０■ 実施例
２のマイクロカプセル １０．０■ 精製水
残量■ 香料
適量０ 防腐剤、酸化防止剤
微量本実施例の化粧料を製造するには、先ず、■に■
及び■を加え、加熱して７０℃に保つ（水相）。Ingredients Weight%■ Beeswax 10.0■ Cetyl alcohol 5.0■ Hydrogenated lanolin
8.0 ■ Squalane
32.5 ■ Glycerin monostearate 2.0 ■ Polyoxyethylene (20) Sorbitan monolaurate 2.0 ■ 1
．． 3-Butylene glycol 5.0 ■ Microcapsules of Example 2 10.0 ■ Purified water
Remaining amount ■ Fragrance
Appropriate amount 0 preservatives, antioxidants
To produce the cosmetic of this example in a small amount, first,
Add and (2), heat and keep at 70°C (aqueous phase).
又、他の成分を混合し、加熱溶解して７０℃に保つ（油
相）。ホモミキサーで水相中の■を均一に分散させた後
、水相に油相を加え、ホモミキサーで均一に乳化し、そ
の乳化後に冷却しながら掻き混ぜることによって上記化
粧料が製造される。Also, other ingredients are mixed, heated and dissolved and kept at 70°C (oil phase). After uniformly dispersing (1) in the aqueous phase using a homomixer, the oil phase is added to the aqueous phase, uniformly emulsified using a homomixer, and after the emulsification, the above cosmetic is produced by stirring while cooling.
本実施例の化Ｍ料は、紫外線遮蔽効果に優れ、従来の化
粧料と比べて安全性が高い。The chemical composition of this example has an excellent ultraviolet shielding effect and is safer than conventional cosmetics.
又、肌に均一に薄く付着し、密着性があり、しかも使用
感、透明感が優れている。In addition, it adheres to the skin in a thin and uniform manner, has good adhesion, and has excellent usability and transparency.
又、白さの浮き防止効果も優れており、化粧持続性も良
好であった。In addition, the effect of preventing whiteness from floating was excellent, and the makeup retention was also good.
実施例１１
本実施例は、本発明のマイクロカプセルを乳液に配合し
た化粧料についての実施例である。Example 11 This example is about a cosmetic composition containing the microcapsules of the present invention in a milky lotion.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ ステアリ
ン酸 ２．５■ セチルアルコー
ル １．５■ ワセリン
５．０■ 流動パラフィン
１０．０■ ポリオキシエチレン（１０）モ
ノオレイン酸エステル ２．０■
ポリエチレングリコール１５００ ３．０■ ト
リエタノールアミン ２．０■ カルボ
キシビニルポリマー ０，１５■ 実施例３
のマイクロカプセル １０．０■ 精製水
残量■ 香料
適量■ 防腐剤、酸化防止剤
微量本実施例の化粧料を製造するには、先ず、■
に■乃至■を加え、加熱溶解して８０℃に保つ（水相）
。又、他の成分を混合し、加熱溶解して８０℃に保つ（
油相）。ホモミキサーで水相中の■を均一に分散させた
後、水相に油相を加え、ホモミキサーで均一に乳化し、
その乳化後に掻き混ぜながら３０℃まで冷却することに
よって上記化粧料が製造される。Ingredients Weight%■ Stearic acid 2.5■ Cetyl alcohol 1.5■ Vaseline
5.0 ■ Liquid paraffin
10.0■ Polyoxyethylene (10) monooleic acid ester 2.0■
Polyethylene glycol 1500 3.0■ Triethanolamine 2.0■ Carboxyvinyl polymer 0.15■ Example 3
Microcapsules 10.0 ■ Purified water
Remaining amount ■ Fragrance
Appropriate amount ■ Preservatives, antioxidants
To produce the cosmetic of this example in a small amount, first,
Add ■ to ■, heat and dissolve and keep at 80℃ (water phase)
. Also, mix other ingredients, heat and melt and keep at 80℃ (
oil phase). After uniformly dispersing ■ in the aqueous phase with a homomixer, add the oil phase to the aqueous phase and uniformly emulsify with a homomixer.
After the emulsification, the above cosmetic is produced by cooling to 30° C. while stirring.
本実施例の化粧料は、紫外線遮蔽効果に優れ、従来の化
粧料と比べて安全性が高い。The cosmetic of this example has an excellent ultraviolet shielding effect and is safer than conventional cosmetics.
又、肌に均一に薄く付着し、密着性があり、しかも使用
感、透明感が優れている。In addition, it adheres to the skin in a thin and uniform manner, has good adhesion, and has excellent usability and transparency.
又、白さの浮き防止効果も優れており、化粧持続性も良
好であった。In addition, the effect of preventing whiteness from floating was excellent, and the makeup retention was also good.
実施例１２
本実施例は、本発明のマイクロカプセルをリップクリー
ムに配合した化粧料についての実施例である。Example 12 This example is about a cosmetic composition containing the microcapsules of the present invention in a lip balm.
すなわち、本実施例の化粧料の組成は次のとおりである
。That is, the composition of the cosmetic of this example is as follows.
成分 重量％■ 実施例２の
マイクロカプセル ３．０■ 実施例３のマイクロ
カプセル ４．０■ キャンデリラロウ
２，９■ セレシン
１４．９■ レジナー ４．
８■ オクチルドデカノール ７．０■ ジ
イソステアリルアレート ３５．５■ トリー２
−エチルヘキサン酸
グリセリン ２２．２■ ジオクタン
酸ネオペンチルグリ
コール ５．６［相］ 香料
適量■ 防腐剤、酸化防
止剤 微量本実施例の化粧料を製造するに
は、先ず、■。Ingredients Weight %■ Microcapsules of Example 2 3.0■ Microcapsules of Example 3 4.0■ Candelilla wax
2,9■ Ceresin
14.9 ■ Regina 4.
8■ Octyldodecanol 7.0■ Diisostearylalate 35.5■ Tory 2
- Glycerin ethylhexanoate 22.2 ■ Neopentyl glycol dioctoate 5.6 [Phase] Perfume Appropriate amount ■ Preservative, antioxidant Small amount To manufacture the cosmetics of this example, first, prepare ■.
■を■の一部に加え、３本ローラで処理し、顔料部とす
る。次に、他の成分を混合し、加熱溶解した後、上記顔
料部を加え、ホモミキサーで均一に分散させる。そして
、分散後に型に流し込んで急冷し、スティック状になっ
たものを容器に差し込み、フレーミングを行う。このよ
うにして上記化粧料が製造されることとなる。Add ■ to part of ■ and process with three rollers to form a pigment part. Next, the other components are mixed and heated and dissolved, then the pigment part is added and uniformly dispersed using a homomixer. After dispersion, it is poured into molds and rapidly cooled, and the stick-shaped mixture is inserted into a container for framing. In this way, the above cosmetic is manufactured.
本実施例の化粧料は、紫外線遮蔽効果に優れ、従来の化
粧料と比べて安全性が高い。The cosmetic of this example has an excellent ultraviolet shielding effect and is safer than conventional cosmetics.
又、唇に薄く均一に付着し、しかも使用感、透明感が優
れている。In addition, it adheres thinly and evenly to the lips, and has an excellent feeling of use and transparency.
さらに、化粧持続性も良好であった。Furthermore, the makeup durability was also good.
（発明の効果）
（イ）炊上のように、本発明のマイクロカプセルは、紫
外線吸収剤であるベンゾフェノン誘導体を、シリカを成
分とする平均粒径が０．１〜３０μｍの球状微粒子中に
内包せしめて構成したものなるため、紫外線吸収剤が直
接皮膚に接触することがなく、従って皮膚への刺激が軽
減されることとなり、その安全性が従来の紫外線吸収剤
に比べて大幅に高められることになるという顕著な効果
がある。(Effects of the Invention) (A) As described above, the microcapsules of the present invention encapsulate a benzophenone derivative, which is an ultraviolet absorber, in spherical fine particles containing silica and having an average particle size of 0.1 to 30 μm. At the very least, the ultraviolet absorber does not come into direct contact with the skin, thus reducing skin irritation and greatly increasing its safety compared to conventional ultraviolet absorbers. It has a remarkable effect of becoming.
よって、このようなマイクロカプセルを含有した化粧料
においても、皮膚に対する刺激緩和効果が得られるとい
う利点がある。Therefore, cosmetics containing such microcapsules also have the advantage of providing an effect of alleviating irritation to the skin.
（ロ）又、マイクロカプセル自体が粉体であるので、従
来の紫外線吸収剤の配合が困難であった化粧料基剤に対
しても容易に配合することが可能になるという効果があ
る。(b) Furthermore, since the microcapsule itself is a powder, it has the effect that it can be easily incorporated into cosmetic bases, which have been difficult to incorporate conventional ultraviolet absorbers.
（ハ）さらに、マイクロカプセルが真球状の粉体である
ため、このようなマイクロカプセルを含有した化粧料の
延展性は、無機顔料を含有した従来の化粧料に比べて非
常に良好で有り、肌に対して厚ぼったく付着することな
く薄く均一に付着し、肌に負担をかけることがないとい
う効果がある。(c) Furthermore, since the microcapsules are spherical powders, the spreadability of cosmetics containing such microcapsules is much better than that of conventional cosmetics containing inorganic pigments; It is effective in that it does not adhere thickly to the skin, but adheres thinly and evenly, and does not put a burden on the skin.
（ニ）しかも、このような化粧料においては、含有され
ているマイクロカプセルの外壁を構成する球状微粒子が
、化粧料基剤中の油溶剤と光の屈折率が略等しいシリカ
で構成されているため、従来の酸化チタンを含有する化
粧料のように光の散乱に基づき肌が白く浮き出たような
印象を与えることがないという利点がある。(d) Moreover, in such cosmetics, the spherical fine particles that make up the outer wall of the microcapsules contained therein are composed of silica, which has approximately the same optical refractive index as the oil solvent in the cosmetic base. Therefore, it has the advantage that it does not give the impression that the skin stands out due to light scattering, unlike conventional cosmetics containing titanium oxide.
（ホ）又、上記のような化粧料は透明感に優れ、プレス
充填性に優れ、化粧持続性が良好であるという利点があ
る。(e) Cosmetics such as those described above also have the advantage of being excellent in transparency, press-filling properties, and long-lasting makeup.
（へ）さらに、本発明の製造方法においては、ベンゾフ
ェノン誘導体を、アルカリ金属のケイ酸塩水溶液中に溶
解し、その水溶液と有機溶媒とを混合してＷ１０型乳濁
液とし、次に前記アルカリ金属のケイ酸塩及びベンゾフ
ェノン誘導体のアルカリ溶解物との中和反応により水不
溶性沈殿を生成しうる酸性水溶液を前記乳濁液と混合し
てマイクロカプセルを製造する方法なるため、前記ベン
ゾフェノン誘導体は、シリカを主成分とする球状微粒子
中に内包されてマイクロカプセルが製造できることとな
る。(f) Furthermore, in the production method of the present invention, a benzophenone derivative is dissolved in an aqueous solution of an alkali metal silicate, the aqueous solution and an organic solvent are mixed to form a W10 emulsion, and then the alkali The benzophenone derivative is a method of manufacturing microcapsules by mixing the emulsion with an acidic aqueous solution capable of producing a water-insoluble precipitate through a neutralization reaction with an alkaline solution of the metal silicate and the benzophenone derivative. Microcapsules can be manufactured by being encapsulated in spherical fine particles containing silica as a main component.
特に、界面における次の共沈反応
（ａ） Ｓ ｌ ０３’−＋ ２ Ｈ”→Ｓ ｉ ０２
＋Ｈ２０（Ｓ ｉ ２０５２−＋ ２ Ｈ＋→２Ｓ１０
゜＋Ｈ２０）及び
（ｂ） Ｒ−０−＋Ｈ＋→Ｒ−ＯＨ（ここでＲはベ
ンゾフェノン骨格を示す）において、上記（ａ）の反応
が（ｂ）の反応より速く進行するため、ベンゾフェノン
誘導体が球状微粒子中に確実に内包され、従ってマイク
ロカプセルの製造が確実に行えるという効果がある。In particular, the following coprecipitation reaction at the interface (a) S l 03′−+ 2 H”→S i 02
+H20(S i 2052-+ 2 H+→2S10
゜+H20) and (b) R-0-+H+→R-OH (where R represents a benzophenone skeleton), the reaction in (a) proceeds faster than the reaction in (b), so the benzophenone derivative becomes spherical. It has the effect that it is reliably encapsulated in fine particles, and therefore, microcapsules can be manufactured reliably.
第１図はマイクロカプセルの製造過程を示す説明図。
第２図は一実施例のマイクロカプセルの走査電子顕微鏡
による拡大写真。
第３図は一実施例のマイクロカプセルの紫外線吸収スペ
クトルのチャート図。
第４図は一実施例のマイクロカプセルのすべり摩擦試験
のグラフを示す。
第２図FIG. 1 is an explanatory diagram showing the manufacturing process of microcapsules. FIG. 2 is an enlarged photograph of the microcapsule of one example taken by a scanning electron microscope. FIG. 3 is a chart of the ultraviolet absorption spectrum of the microcapsules of one example. FIG. 4 shows a graph of the sliding friction test of the microcapsule of one example. Figure 2
Claims (1)
数１〜２４のアルキル基、アルコキシ基又はスルホン酸
基若しくはそのアルカリ金属塩を示し、且つｍ及びｎは
０〜３の整数を示し、ｋ＋ｌは１〜４の整数を示す）で
表されるベンゾフェノン誘導体を、シリカを主成分とす
る平均粒径が０．１〜３０μｍの球状微粒子中に内包せ
しめたことを特徴とする紫外線吸収剤内包マイクロカプ
セル。 ２、一般式 ▲数式、化学式、表等があります▼ （式中ｍ個のＸ及びｎ個のＹは各々同一又は異なる炭素
数１〜２４のアルキル基、アルコキシ基、又はスルホン
酸基若しくはそのアルカリ金属塩を示し、且つｍ及びｎ
は０〜３の整数を示し、ｋ＋ｌは１〜４の整数を示す）
で表されるベンゾフェノン誘導体を、アルカリ金属のケ
イ酸塩水溶液中に溶解し、その水溶液と、水及び前記ベ
ンゾフェノン誘導体に対する溶解度が５％以下の有機溶
媒とを混合してＷ／Ｏ型乳濁液とし、次に前記アルカリ
金属のケイ酸塩及びベンゾフェノン誘導体のアルカリ溶
解物との中和反応により水不溶性沈澱を生成しうる酸性
水溶液を前記乳濁液と混合し、その後、必要に応じて濾
過、水洗、乾燥することにより、前記ベンゾフェノン誘
導体を、シリカを主成分とする平均粒径が０．１〜３０
μｍの球状微粒子中に内包せしめて製造することを特徴
とする紫外線吸収剤内包マイクロカプセルの製造方法。 ３、一般式 ▲数式、化学式、表等があります▼ （式中ｍ個のＸ及びｎ個のＹは各々同一又は異なる炭素
数１〜２４のアルキル基、アルコキシ基、又はスルホン
酸基若しくはそのアルカリ金属塩を示し、且つｍ及びｎ
は０〜３の整数を示し、ｋ＋ｌは１〜４の整数を示す）
で表されるベンゾフェノン誘導体を、シリカを主成分と
する平均粒径が０．１〜３０μｍの球状微粒子中に内包
せしめたマイクロカプセルを含有してなることを特徴と
する化粧料。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. An acid group or an alkali metal salt thereof, m and n are integers of 0 to 3, and k+l is an integer of 1 to 4), with an average particle size mainly composed of silica. 1. A microcapsule containing an ultraviolet absorber, characterized in that it is encapsulated in spherical fine particles of 0.1 to 30 μm. 2. General formulas ▲ Numerical formulas, chemical formulas, tables, etc. indicates a metal salt, and m and n
represents an integer from 0 to 3, and k+l represents an integer from 1 to 4)
The benzophenone derivative represented by is dissolved in an aqueous alkali metal silicate solution, and the aqueous solution is mixed with water and an organic solvent having a solubility of 5% or less for the benzophenone derivative to form a W/O emulsion. Next, an acidic aqueous solution capable of producing a water-insoluble precipitate by a neutralization reaction with the alkaline solution of the alkali metal silicate and benzophenone derivative is mixed with the emulsion, and then, if necessary, filtration, By washing with water and drying, the benzophenone derivative has an average particle size of 0.1 to 30
A method for producing ultraviolet absorber-containing microcapsules, which is produced by encapsulating them in μm-sized spherical fine particles. 3. General formulas ▲ Numerical formulas, chemical formulas, tables, etc. indicates a metal salt, and m and n
represents an integer from 0 to 3, and k+l represents an integer from 1 to 4)
A cosmetic comprising microcapsules in which a benzophenone derivative represented by the following formula is encapsulated in spherical fine particles having an average particle size of 0.1 to 30 μm and mainly composed of silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15047288A JP2686484B2 (en) | 1988-06-17 | 1988-06-17 | Ultraviolet absorbent-containing microcapsules, method for producing the same, and cosmetics containing the microcapsules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15047288A JP2686484B2 (en) | 1988-06-17 | 1988-06-17 | Ultraviolet absorbent-containing microcapsules, method for producing the same, and cosmetics containing the microcapsules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH022867A true JPH022867A (en) | 1990-01-08 |
| JP2686484B2 JP2686484B2 (en) | 1997-12-08 |
Family
ID=15497651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15047288A Expired - Fee Related JP2686484B2 (en) | 1988-06-17 | 1988-06-17 | Ultraviolet absorbent-containing microcapsules, method for producing the same, and cosmetics containing the microcapsules |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2686484B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0839518A3 (en) * | 1996-11-04 | 2000-06-07 | L'Oreal S.A. | Cosmetic powder composition comprising a sunscreen |
| US6147305A (en) * | 1997-06-30 | 2000-11-14 | Nec Corporation | Insulated mounting structure with a hard insert |
| WO2000072806A3 (en) * | 1999-05-26 | 2001-05-31 | Sol Gel Technologies Ltd | Sunscreen composition containing sol-gel microcapsules |
| US6468509B2 (en) | 1998-12-18 | 2002-10-22 | Sol-Gel Technologies Ltd. | Sunscreen composition containing sol-gel microcapsules |
| WO2005016303A3 (en) * | 2003-08-04 | 2005-05-06 | Schering Plough Healthcare | Emulsion composition |
| WO2008107347A2 (en) * | 2007-03-07 | 2008-09-12 | Basf Se | Use of amines and amides for the stabilization of organic micronized uv absorbers |
| US7758888B2 (en) | 2000-04-21 | 2010-07-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
| US7923030B2 (en) | 2003-03-14 | 2011-04-12 | Sol-Gel Technologies, Inc. | Agent-encapsulating micro- and nanoparticles, methods for preparation of same and products containing same |
| US8110284B2 (en) | 2003-07-31 | 2012-02-07 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
| EP2431088A1 (en) | 2005-08-02 | 2012-03-21 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
| EP2545776A2 (en) | 2007-02-01 | 2013-01-16 | Sol-Gel Technologies Ltd. | Method for preparing particles comprising metal oxide coating and particles with metal oxide coating |
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| FR2982148A1 (en) * | 2011-11-07 | 2013-05-10 | Oreal | SOLID SOLID COMPOSITION BASED ON LIPOPHILIC ORGANIC UV FILTER AND HYDROPHOBIC SILICA AEROGEL PARTICLES |
| US9687465B2 (en) | 2012-11-27 | 2017-06-27 | Sol-Gel Technologies Ltd. | Compositions for the treatment of rosacea |
| US10285926B2 (en) | 2015-06-29 | 2019-05-14 | The Procter & Gamble Company | Superabsorbent polymers and starch powders for use in skin care compositions |
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| US9549891B2 (en) | 2012-03-19 | 2017-01-24 | The Procter & Gamble Company | Superabsorbent polymers and sunscreen actives for use in skin care compositions |
| CN107138104B (en) * | 2017-05-22 | 2019-10-29 | 天津晶润锐拓科技发展有限公司 | A kind of preparation method of the microcapsules of common cladding hindered amines stabilizer, Hinered phenols stabilizer and organic dyestuff |
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1988
- 1988-06-17 JP JP15047288A patent/JP2686484B2/en not_active Expired - Fee Related
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| EP0839518A3 (en) * | 1996-11-04 | 2000-06-07 | L'Oreal S.A. | Cosmetic powder composition comprising a sunscreen |
| US6147305A (en) * | 1997-06-30 | 2000-11-14 | Nec Corporation | Insulated mounting structure with a hard insert |
| US6468509B2 (en) | 1998-12-18 | 2002-10-22 | Sol-Gel Technologies Ltd. | Sunscreen composition containing sol-gel microcapsules |
| WO2000072806A3 (en) * | 1999-05-26 | 2001-05-31 | Sol Gel Technologies Ltd | Sunscreen composition containing sol-gel microcapsules |
| JP2003500428A (en) * | 1999-05-26 | 2003-01-07 | ゾル−ゲル テクノロジーズ エルティーディー． | Sunscreen composition containing sol-gel microcapsules |
| JP4671509B2 (en) * | 1999-05-26 | 2011-04-20 | ゾル−ゲル テクノロジーズ エルティーディー． | Sunscreen composition comprising sol-gel microcapsules |
| US7758888B2 (en) | 2000-04-21 | 2010-07-20 | Sol-Gel Technologies Ltd. | Composition exhibiting enhanced formulation stability and delivery of topical active ingredients |
| US8425940B2 (en) | 2003-03-14 | 2013-04-23 | Sol-Gel Technologies Ltd. | Agent-encapsulating micro-and nanoparticles, methods for preparation of same and products containing same |
| US7923030B2 (en) | 2003-03-14 | 2011-04-12 | Sol-Gel Technologies, Inc. | Agent-encapsulating micro- and nanoparticles, methods for preparation of same and products containing same |
| US8110284B2 (en) | 2003-07-31 | 2012-02-07 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
| WO2005016303A3 (en) * | 2003-08-04 | 2005-05-06 | Schering Plough Healthcare | Emulsion composition |
| US9868103B2 (en) | 2005-08-02 | 2018-01-16 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
| EP2431088A1 (en) | 2005-08-02 | 2012-03-21 | Sol-Gel Technologies Ltd. | Metal oxide coating of water insoluble ingredients |
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| US8435559B2 (en) | 2006-06-27 | 2013-05-07 | Dow Corning Corporation | Microcapsules from emulsion polymerization of tetraalkoxysilane |
| EP2545776A2 (en) | 2007-02-01 | 2013-01-16 | Sol-Gel Technologies Ltd. | Method for preparing particles comprising metal oxide coating and particles with metal oxide coating |
| WO2008107347A3 (en) * | 2007-03-07 | 2009-05-07 | Ciba Holding Inc | Use of amines and amides for the stabilization of organic micronized uv absorbers |
| WO2008107347A2 (en) * | 2007-03-07 | 2008-09-12 | Basf Se | Use of amines and amides for the stabilization of organic micronized uv absorbers |
| FR2982148A1 (en) * | 2011-11-07 | 2013-05-10 | Oreal | SOLID SOLID COMPOSITION BASED ON LIPOPHILIC ORGANIC UV FILTER AND HYDROPHOBIC SILICA AEROGEL PARTICLES |
| WO2013068236A1 (en) * | 2011-11-07 | 2013-05-16 | L'oreal | Solid anti-sun composition based on lipophilic organic uv screening agent and aerogel particles of hydrophobic silica |
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| US10285926B2 (en) | 2015-06-29 | 2019-05-14 | The Procter & Gamble Company | Superabsorbent polymers and starch powders for use in skin care compositions |
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| Publication number | Publication date |
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| JP2686484B2 (en) | 1997-12-08 |
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