WO2023191649A1 - Organosilica particles based on bridging polysilsesquioxanes for blocking ultraviolet rays - Google Patents
Organosilica particles based on bridging polysilsesquioxanes for blocking ultraviolet rays Download PDFInfo
- Publication number
- WO2023191649A1 WO2023191649A1 PCT/RS2023/000004 RS2023000004W WO2023191649A1 WO 2023191649 A1 WO2023191649 A1 WO 2023191649A1 RS 2023000004 W RS2023000004 W RS 2023000004W WO 2023191649 A1 WO2023191649 A1 WO 2023191649A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- organosilica
- organosilica particles
- component
- molecules
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 179
- 229920000734 polysilsesquioxane polymer Polymers 0.000 title claims abstract description 26
- 230000000903 blocking effect Effects 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 230000005855 radiation Effects 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000009472 formulation Methods 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 230000000475 sunscreen effect Effects 0.000 claims abstract description 16
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 230000008901 benefit Effects 0.000 claims abstract description 12
- 238000010276 construction Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims abstract description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-M 4-aminobenzoate Chemical compound NC1=CC=C(C([O-])=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-M 0.000 claims abstract description 5
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 5
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims abstract description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012965 benzophenone Substances 0.000 claims abstract description 5
- 229960000846 camphor Drugs 0.000 claims abstract description 5
- 229930008380 camphor Natural products 0.000 claims abstract description 5
- 229940114081 cinnamate Drugs 0.000 claims abstract description 5
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims abstract description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229960001860 salicylate Drugs 0.000 claims abstract description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 5
- WMJBVALTYVXGHW-UHFFFAOYSA-N 3,3-diphenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C(=CC(=O)O)C1=CC=CC=C1 WMJBVALTYVXGHW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003918 triazines Chemical class 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000003642 reactive oxygen metabolite Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 239000011782 vitamin Substances 0.000 claims description 5
- 235000013343 vitamin Nutrition 0.000 claims description 5
- 229940088594 vitamin Drugs 0.000 claims description 5
- 229930003231 vitamin Natural products 0.000 claims description 5
- MSFXUHUYNSYIDR-UHFFFAOYSA-N 4-[4,6-bis(4-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=NC(C=2C=CC(=CC=2)C(O)=O)=NC(C=2C=CC(=CC=2)C(O)=O)=N1 MSFXUHUYNSYIDR-UHFFFAOYSA-N 0.000 claims description 4
- 230000000843 anti-fungal effect Effects 0.000 claims description 4
- 229940121375 antifungal agent Drugs 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003102 growth factor Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- -1 triethoxysilyl Chemical group 0.000 claims description 4
- 239000002966 varnish Substances 0.000 claims description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000001282 organosilanes Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 230000029663 wound healing Effects 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- PTYGUPSTBTUWKH-UHFFFAOYSA-N 3-[[4,6-bis(3-carboxyanilino)-1,3,5-triazin-2-yl]amino]benzoic acid Chemical compound N1=C(N=C(N=C1NC=1C=C(C(=O)O)C=CC=1)NC=1C=C(C(=O)O)C=CC=1)NC=1C=C(C(=O)O)C=CC=1 PTYGUPSTBTUWKH-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910018540 Si C Inorganic materials 0.000 claims description 2
- 229910008051 Si-OH Inorganic materials 0.000 claims description 2
- 229910006358 Si—OH Inorganic materials 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 230000000699 topical effect Effects 0.000 claims description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims 1
- 244000046052 Phaseolus vulgaris Species 0.000 claims 1
- 229920002415 Pluronic P-123 Polymers 0.000 claims 1
- 229910020489 SiO3 Inorganic materials 0.000 claims 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 claims 1
- 239000004599 antimicrobial Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 230000004224 protection Effects 0.000 abstract description 37
- 230000006750 UV protection Effects 0.000 abstract description 9
- 230000009931 harmful effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 241000196324 Embryophyta Species 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000003389 potentiating effect Effects 0.000 abstract description 4
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 150000002605 large molecules Chemical class 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 238000012377 drug delivery Methods 0.000 abstract description 2
- 230000002000 scavenging effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000002537 cosmetic Substances 0.000 description 11
- 235000014692 zinc oxide Nutrition 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 10
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- 229960001296 zinc oxide Drugs 0.000 description 7
- 230000036541 health Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000001692 EU approved anti-caking agent Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000037368 penetrate the skin Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 206010072170 Skin wound Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032912 absorption of UV light Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- XVAMCHGMPYWHNL-UHFFFAOYSA-N bemotrizinol Chemical compound OC1=CC(OCC(CC)CCCC)=CC=C1C1=NC(C=2C=CC(OC)=CC=2)=NC(C=2C(=CC(OCC(CC)CCCC)=CC=2)O)=N1 XVAMCHGMPYWHNL-UHFFFAOYSA-N 0.000 description 1
- 229960004101 bemotrizinol Drugs 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 231100000040 eye damage Toxicity 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006950 reactive oxygen species formation Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 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
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- YYJNCOSWWOMZHX-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C([Si](OCC)(OCC)OCC)C=C1 YYJNCOSWWOMZHX-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Abstract
Organosilica particles based on bridging polysilsesquioxanes for blocking ultraviolet rays, which have the novelty of components C and D in different ratios, which are covalently cross-linked within the organosilica particles, whereby particles of different structures and morphologies for application in protection from UV rays. The role of component C is to ensure potent absorption of UV rays, while component D can have a partial UV-protective effect, but its primary role is constructive, i.e. enables the construction of organosilica desired structure. Component C is based on organo-bridged polysilsesquioxanes, based on the structure of different organic UV blockers, from which bridging organosilicate precursors can be made by chemical modification. This component can be based on derivatives of triazine, cinnamate, salicylate, anthranilate, p-aminobenzoate, camphor, benzimidazole, benzophenone, dibenzoylmethane, diphenylacrylate and other organic molecules that have the ability to absorb UV rays. Component D is a bridged silsesquioxane that can serve the purpose of a particle building component. In the case of porous organosilica particles, the material can be loaded with molecules that can play a role in additional UV protection or exhibit other benefits for application (ROS scavenging, skin nourishing, drug delivery etc.). These additional molecules can be adsorbed on the surface or entrapped inside the pores of the organosilica particles through the application of various large molecules, which are covalently bound to the organosilica particles and prevent their exit or enable slow release from the pores into the surrounding environment. In addition, the particles with enhanced porosity exhibit enhanced surface area and lower density, both of which could be beneficial for dispersing the particles and increasing the stability of particles in formulations. The new organosilica particles can be applied as an integral part of sunscreens, although a wider application is also possible as an integral part of any material in which protection from UV radiation would be important, e.g. UV-proof glasses, resins and paints, which would be of interest for the protection of materials and devices in the mechanical, construction, automotive, aviation and space industries, as well as in agriculture for the protection of plants from the harmful effects of UV radiation.
Description
ORGANOSILICA PARTICLES BASED ON BRIDGING POLYSILSESQUIOXANES FOR
BLOCKING ULTRAVIOLET RAYS
Technical field
The invention relates to new organosilica particles composed entirely of covalently linked bridged polysilsesquioxanes as effective blockers for ultraviolet rays.
The invention relates to new organosilica particles used as a component of sunscreens, although broader application is also possible as a component of any material in which protection from UV radiation would be of importance, e.g., for the manufacture of UV-resistant glasses, resins and paints that would be of interest for the protection of materials and equipment in the engineering, construction, automotive, aviation and space industries, as well as in agricultural industries for the protection of crops from the harmful effects of UV radiation.
The invention focuses on different particle structures composed entirely of covalently bound bridged silsesquioxanes, where a mixture of bridged silsesquioxanes, including building silsesquioxane component (D) and UV-shielding silsesquioxane component (C) is used to produce efficient UV-shielding organosilica particles. Component C is based on organo-bridged polysilsesquioxanes, based on the structure of different organic UV blockers, from which bridging organosilicate precursors can be made by chemical modification. Component D can be different building units based on bridging organosilica precursors, e.g.: 4,4'- bis(triethoxy silyl)- 1,1 -biphenyl or l,4-bis(triethoxysilyl)benzene, which can also exhibit a partial benefit in UV protection.
The covalent linkages between the components prevent their leakage from the particles. The changes in components C and D, their ratios, and synthesis methodologies can yield a plethora of novel organosilica particles with different characteristics. Thus, the intensity and wavelength of the absorbed UV light can be finetuned, which can yield optimized organosilica particles for applications in different areas where UV-shielding is needed. Herein, an example of the synthesized organosilica particle is presented with absorption maximum in UVB region and thus containing potent ability for UV shielding of skin, with an estimated SPF = 30. The prepared organosilica particles constructed from 4, 4'-bis(triethoxysil)- 1,1 '-biphenyl as component D and a bridged silsesquioxane containing a triazine-based molecule as component C based in a ratio of 1:9.
Furthermore, the organosilica particles can be prepared in such a manner to contain a porous structure and high surface area. The surface and the pores can be utilized for storing different molecules and enabling their slow release from the particles, which may add additional benefit to the applications. These may include
storing and release of vitamins, minerals, skin conditioners, scavengers of reactive oxygen species (ROS), additional UV-shielding molecules, medication drugs, antimicrobial and antifungal molecules, growth factors and other molecules and biomolecules that may benefit the users or to enhance the characteristics of the product. In addition, the particles with enhanced porosity exhibit enhanced surface area and lower density, both of which could be beneficial for dispersing the particles and increasing the stability of particles in formulations.
The International Patent Classification (IPC) designation is: A61K8/27, B82Y30/00, A61K8/0279, A61Q19/00, C01G9/02 and A61K/585.
The invention relates to new organosilica particles based on covalently interlocked bridged polysilsesquioxanes as effective blockers for ultraviolet rays. The new organosilica particles show stable, effective and safe ability to block ultraviolet rays.
The UV radiation of the sun can cause skin and eye damage in humans and animals. In plants, UV radiation causes damage to the cell membrane, chloroplasts, mitochondria and DNA, resulting in reduced yield and crop quality.
Currently, TiCh and ZnO nanoparticles or organic blockers are used in the market to protect against UV solar radiation. However, there is a growing concern about the harmful effects of these UV protection ingredients on human health and the environment, especially after exposure to UV radiation, which causes the production of highly destructive reactive oxygen species (ROS), leading to the degradation of the surrounding materials, but also to the degradation of the UV blockers themselves, reducing their ability to protect against UV radiation.
Organosilica particles as a new material represent a safer alternative (both in terms of health and environmental protection) as active ingredients for protection against UV radiation than the active UV blockers in current use. The invention precisely solves the above-mentioned problem of the harmfulness of UV rays and with the invention proposes a construction of novel biocompatible organosilica particles that are capable of protecting against ultraviolet solar radiation through the absorption and scattering of UV rays, while the organosilica particles remain stable under the effect of UV radiation and with a possible wide protection spectrum (UV A + UVB + UVC).
Background art
For the first time, in our publication from 2018, the concept of using porous organosilica particles to protect against UVA and UVB radiation was described and proven (Knezevic et. al. ACS Appl. Mater. Interfaces 2018, 10, 20231-20236, DOI: 10.1021/acsami.8b04635). This publication describes a new application of organosilica particles, with a composition (based on a bridging benzene group) that was already known in the scientific literature. Our published results demonstrated a proof of concept that organosilica particles composed solely of covalently interlocked silsesquioxanes with bridging benzene groups have the ability to block UV radiation, with a maximum estimated protection factor (SPF) value of 18.2. In addition, surface functionalization with chelating ligands and zinc ions (important for skin wound healing, maintenance and protection against inflammation) also had a positive effect on the material's ability to protect against UV radiation. These materials also showed great stability when exposed to UV and visible light. The difference compared to the proposed invention is reflected in a different and new (unpublished) composition of organosilica particles, which in this invention are particularly adapted for protection against UV radiation. Organosilica particles based solely on bridging benzene are not covered by this invention. Therefore, the idea, structure (composition) and properties of organosilica particles that are included in this invention have not been published.
Patent application number WO2016189828A1 and titled Zinc oxide-containing composite particles, composition for blocking uv rays, and cosmetic material, published on December 1, 2016. describes zinc oxide nanoparticles as active components for blocking UV rays. The difference compared to the proposed invention is the new structure of organosilica particles.
Patent application W02018025610A1 entitled Zinc-oxide-containing composite particles, composition for uv shielding, and cosmetic published on February 8, 2018. also describes zinc oxide nanoparticles as active UV blocking components that are physically entrapped in organosilica particles which prevents the release of zinc. The difference compared to the proposed invention is that in the case of organosilica nanoparticles, the active component is an organic molecule (there is no presence of metal ions) which is an integral part of the particle bound by chemical bonds within the organosilica particle and they are all composed of organosilicas (on the basis of bridging polysilsesquioxanes).
Patent application W02001093812A1 entitled Cosmetic preparation, published on December 13, 2001. describes zinc oxide nanoparticles and titanium dioxide nanoparticles as active components for blocking UV rays that are physically trapped in the silicate particles. The difference compared to the proposed invention is reflected in the fact that organosilica particles have an active component, an organic molecule (there is no
presence of metal ions), which is again, as above, an integral part of the particle bound by chemical (covalent Si-O-Si) bonds within the organosilica particle (bonded, not physically trapped), whereby organosilica particles are composed of organosilicas (contain Si-C bond), i.e. based on bridging polysilsesquioxane.
Patent US20070183992 entitled Cosmetic composition comprising porous particles incorporating optically active substances, published on August 9, 2007. differs from the invention in that, in the case of the invention, the organosilica particles are not coated with a silicate shell (they are not organic and inorganic substances that are physically trapped inside a porous silicate shell as in the case of the patent application), but the active components are found throughout the entire structure of the particle bound by chemical bonds in the structure of the particle, which is entirely composed of polysilsesquioxanes and there are no distinct features such as core and shell.
Patent application US20030170280A1 entitled Dermatological composition published on September 11, 2003. talks about the preparation of porous silicon and silicate particles for protection against UV radiation. The difference compared to the invention is in the structure and composition of the new organosilica particles.
Patent US10183868B2 entitled Mesoporous zinc oxide powder and method for production thereof, published on December 31, 2015. talks about the preparation of mesoporous zinc oxides. The difference compared to the invention is reflected in the fact that the organosilica particles in this invention are composed entirely of polysilsesquioxanes.
Patent US9138395B2 entitled Sunscreen compositions having synergistic combination of UV filters published on September 22, 2015. talks about the preparation of a formulation for protection against UV radiation based on a mixture of different organic components. In relation to the invention, the patent does not mention making particles with chemical (covalent) bonds as in the case of organosilica particles.
Patent US10682294B2 entitled Controlling zinc oxide particle size for sunscreen applications published on March 9, 2017, describes zinc oxide particles, which is a different composition compared to organosilica particles.
Patent JP5597549B2 entitled Mesoporous zinc oxide powder and method for producing the same published on March 31, 2011, also only describes zinc particles, not organosilica particles.
Patent US20100003204A1 entitled Nanoparticle hybrid sunscreens published on July 2, 2009. The status of this patent is listed as "abandoned". It refers to spherical particles with a diameter between 0.2 and 10 micrometers, prepared by emulsion polymerization of tetra-alkoxysilanes or organotrialkoxysilanes or
organobridged trialkoxysilanes with a UV-absorbing chromophore monomer bearing two or more alkoxysilyl groups attached to the bridging chromophores. The synthesis of these particles takes place in anhydrous conditions in toxic solvents such as toluene and tetrahydrofuran, with the addition of formic acid as an acid catalyst. The difference compared to the invention is reflected in the composition of the particles, since the patent describes the use of silica precursors (Si(OMe4) on Fig 1) along with bridged silsesquioxane for the synthesis, while organosilica particles in this invention are constructed and composed entirely of bridged polysilsesquioxanes, including the use of building silsesquioxane component (D) and UV-shielding silsesquioxane component (C) to produce efficient UV-shielding organosilica particles. Furthermore, the synthesis methodology differs, since the invention uses mild synthesis conditions (room temperature) and as solvents methanol and water, with the addition of ammonia as a base catalyst and the presence of pore- templating species.
Patent DE102006025057A1 entitled Cosmetic sunscreen preparation with special texture published on July 2, 2009. The status of this patent is listed as "withdrawn". It refers to cosmetic formulations that contain molecules for UV protection in a formulation (in the form of a physical mixture) with liquid or pasty silicone oils or their mixtures, with the addition of other components. The difference compared to the invention is reflected in the composition, the method of synthesis and the nature of the formulation, since the invention describes organosilica particles that contain chemically (covalently) bound molecules for protection against UV radiation.
Patent US11389386B2 entitled Photochemically stable, non-leaching, bridged polysilsesquioxane based sunscreens published on January 30, 2017. The status of this patent is kept as "active". It refers to active particles (diameter 50 - 500 nm) for UV protection based on organobridged trialkoxysilanes (polysilsesquioxanes) that are prepared in the form of nanoparticles through oil/water microemulsion polymerization, sol-gel polymerization or a modified Stober process. The difference compared to the invention is reflected in the composition and to the method of particle synthesis. The patent also involves the use of bridged polysilsesquioxanes to incorporate covalently the UV-blocking molecules into the particles, however the patent claims (pages 11, 12) that the particle also: “comprise silicate comonomers in concentrations ranging from 0.001-95 mole % . Preferably , the silicate comonomers can copolymerize with the bridged compound monomers to form the bridged polysilsesquioxane-based sunscreen particles. The silicate comonomers may be selected from a group consisting of tetraalkoxysilane comonomers, sodium silicate comonomers , and organotrialkoxysilane comonomers”. In contrast, the invention herein relates to the particles that are produced solely from bridged polysilsesquioxane precursors, where a mixture of bridged silsesquioxanes, including building silsesquioxane component (D) and UV-shielding silsesquioxane component (C) is used to produce efficient UV-shielding organosilica particles. Therefore, the use of silica comonomers is not the subject of this
invention as the organosilica particles in this invention are composed entirely of polysilsesquioxanes. Furthermore, the particles in the patent are not porous to a significant extent as there is no mention of the porosity of the particles and the use of this feature for storing different molecules and enabling their slow release from the particles, which may add additional benefit to the applications, which is also one of the claims in this invention.
Disclosure of invention
The invention is about new organosilica particles composed of covalently bound bridged polysilsesquioxane as effective blockers for ultraviolet rays.
The new organosilica particles are stable, efficient and safer in blocking UV rays. Current solutions are based on the use of TiCh and ZnO nanoparticles, however, there is growing concern about the harmful effects and effectiveness of these solutions.
Organosilica particles, as a new material, represent a safer alternative (both in terms of health and environmental protection) to active ingredients for protection against UV radiation that are currently in use. The invention solves this problem through the construction of new biocompatible organosilica particles that are capable of protecting against ultraviolet solar radiation by absorbing and scattering UV rays, while the organosilica particles are stable under the effect of UV radiation and with a possible wide spectrum of protection (UVA + UVB + UVC).
The main purpose of the invention is that the new organosilica particles can be used as an integral component of sunscreens, although broader application is also possible as an integral component of any material where protection from UV radiation is important.
According to current scientific knowledge, organosilica particles are safe for the environment and human health, without the ability to penetrate the skin.
Various types of silica particles, most commonly classified as synthetic amorphous silica (SAS), can be found in formulations since the 1950s as stabilizers and thickeners in various industry segments due to their high surface area and high water absorption capacity. In cosmetic products, SAS materials are considered health-safe additives, and they are most often used as abrasives, adsorbents, anti-caking agents, volumizers, coloring agents, and as thickening agents.
In terms of internal composition, organosilica particles differ significantly from SAS materials, however, the outer surface of organosilica particles and SAS materials is similar in structure, as a result of which a similar interaction with biomolecules is expected and therefore good biocompatibility of organosilica particles. Also, due to the similar characteristics of the outer surface with SAS materials, the application of organosilica particles as UV blockers would provide a significant contribution to the improvement of product characteristics, for which SAS materials are currently used (abrasive agents, adsorbents, anti-caking agents, for increasing volume, coloring and as thickening agents...).
The invention relates to the composition of organosilica particles, which contain bridged polysilsesquioxane components C and D in different ratios, which are covalently cross-linked within the organosilica particles, whereby particles of different porous structures and morphology (spherical, cylindrical or bean-shaped) can be obtained for use in protection against UV rays. The role of component C is to ensure potent absorption of UV rays, while component D can have a partial UV-protective effect, but its primary role is constructive, i.e. enables the construction of organosilica desired structure.
In the case of porous organosilica particles, the pores can be filled with molecules that can play a role in additional UV protection or other benefits for the application. These additional molecules adsorbed on the surface or entrapped inside the pores of the organosilica particles through the application of various large molecules, which are covalently bound to the organosilica particles and prevent their leakage from the pores or enable their gradual release into the surrounding environment. In addition, the particles with enhanced porosity exhibit enhanced surface area and lower density, both of which could be beneficial for dispersing the particles and increasing the stability of particles in formulations.
Brief Description of Drawings
• Figure 1 shows UV VIS spectrum of ethanolic suspension (2 mg/mL) of organosilica particles-component D (contains only component D)
• Figure 2 shows UV VIS spectrum of ethanolic suspension (0.05 mg/mL) of organosilica particles-CD (contains components C and D)
• Figure 3 shows Assumed structure of an organosilica particle
• Figure 4 shows Scanning electron microscope images of particles
• Figure 5 shows Distribution of hydrodynamic diameter of particles in aqueous suspension
• Figure 6 shows Zeta potential of an organosilica particle
• Figure 7 shows BET isotherm and BJH pore size distribution for of organosilica particles-CD
• Figure 8 shows Component A- 4,4',4"-s-triazine-2,4,6-triyl-tribenzoic acid = TTBA and Component B - (3-aminopropyl)triethoxysilane = AP-TES
• Figure 9 shows Component C-4,4',4"-s-Triazine-2,4,6-triyl-tribenzamide- propyltriethoxysilane = TTTBA-TES
• Figure 10 shows Component D-4,4'-Bis(triethoxysilyl)- 1,1 '-biphenyl - BPH-TES
Best Mode for Carrying Out of the Invention
The invention is about new organosilica particles, composed of bridging polysilsesquioxanes, which have the ability to block ultraviolet rays. Unlike the previous TiO2 and ZnO nanoparticles or organic blockers, the invention offers a more efficient and safer solution that does not lead to decomposition of UV blockers and formation of reactive oxygen species (ROS), which are harmful for the human health and the environment.
The invention solves this problem through the construction of new biocompatible organosilica particles that are capable of protecting against ultraviolet solar radiation by absorbing and scattering UV rays, while the organosilica particles are stable under the effect of UV radiation and with a possible wide spectrum of protection (UVA + UVB + UVC).
The primary purpose of the invention would be that the new organosilica particles can be applied as an integral part of sun creams, although a wider application is also possible as an integral part of any material in which protection from UV radiation would be important, e.g. for the preparation of UV-proof glasses, resins and paints, which would be of interest for the protection of materials and devices in the mechanical, construction, automotive, aviation and space industries, as well as in agriculture for the protection of plants from the harmful effects of UV radiation.
According to current scientific knowledge, organosilica particles are safe for the environment and human health, without the ability to penetrate the skin.
The invention relates to the composition of organosilica particles, which contain bridged polysilsesquioxane components C and D in different ratios, which are covalently cross-linked within the organosilica particle, whereby particles of different porous structure and morphology (spherical, cylindrical or bean-shaped) can be obtained for use in protection against UV rays. The role of component C is to ensure potent absorption of UV rays, while component D can have a partial UV-protective effect, but its primary role is constructive, i.e. enables the construction of organosilica desired structure.
Component C is based on organo-bridged polysilsesquioxanes, based on the structure of different organic UV blockers, from which bridging organosilicate precursors can be made by chemical modification. This component can be based on derivatives of triazine, cinnamate, salicylate, anthranilate, p-aminobenzoate, camphor, benzimidazole, benzophenone, dibenzoylmethane, diphenylacrylate and other organic molecules that have the ability to absorb UV rays. Herein, characteristics of a novel material are provided, which is obtained from the component C that is based on 1,3,5-triazine derivative-bridged polysilsesquioxane (compound which is analogous to bemotrizinol, a UV-absorbing molecule approved for use in sunscreens). Other examples of
component C based on functionalized 1,3,5-triazine could include: 4,4',4"-(l,3,5-Triazine-2,4,6-triyl)tribenzoic acid), 4',4",,4""'-(l,3,5-Triazine-2,4,6-triyl)tris(([l,r-biphenyl]-4-carboxylic acid)), 3,3',3"-((l,3,5-Triazine- 2,4,6-triyl)tris(azanediyl))tribenzoic acid)).
Component D can be different building units based on bridging organosilica precursors. Examples: 4,4'-bis(triethoxysilyl)-l , 1 '-biphenyl, 1 ,4-bis(triethoxysilyl)benzene, 1 ,2-bis(triethoxysilyl)ethane, 1 ,2- bis(triethoxysilyl)ethylene, which they can also play a partial role in UV protection, as in the case of the use of precursors with significant absorption in the UVC region: 4,4'-bis(triethoxysil)-l,l'-biphenyl or 1,4- bis(triethoxysil)benzene.
In order to beter understand the innovative structure of the organosilica particle of the invention, we will observe the ability of the organosilica particle to block UV rays, by measuring the UV/VIS spectrum of this material. An example in Figure 1 is the UV/VIS spectrum of an organosilica material composed exclusively of component D (4,4'- bis (triethoxysil)- 1,1 '-biphenyl) (without component C) which shows a high ability to absorb UV rays in the area below 300 nm, which is partially covered by the UVB region, but the maximum absorption is in the UVC region.
Therefore, this material would have the greatest application potential for the preparation of glasses or coatings for protection against cosmic UVC radiation. Since UVC radiation does not reach the earth, a possible application of this material would be in protection against UV radiation in space, for use on visors on space suits or for glasses on spacecrafts. Porous organosilica particles based on this component D (4,4'- bis(triethoxysil)-l,l'-biphenyl) are already known in the literature, but their potential application for protection against UVC radiation has not been considered, which is a novelty within the scope of this invention.
Figure 2 shows the UV/VIS spectrum of the ethanolic suspension of the newly synthesized organosilica particles, which, in addition to the same component D (4,4'-bis(triethoxysil)-l,l'-biphenyl), also contain a triazine-based component C. It is noticeable that the maximum absorption of UV light is shifted to the area between 290 to 320 nm, which is the desired characteristic in the case of protection against UVB rays of solar radiation.
In the case of this example, organosilica particles contain component D (4,4'-bis(triethoxysil)-l,l'- biphenyl) and component C based on triazine at a ratio of 1 :9. Spectrophotometric measurements can be used to estimate the approximate value of the sun protection factor (SPF), which in the case of this material is 30. The SPF value indicates the amount of solar energy (UV radiation) required to produce sunburns on protected skin relative to the amount of solar energy required to produce sunburn on unprotected skin. The UV absorption efficiency and SPF of organosilica particles can be significantly increased by increasing the proportion of
component C in the material. This kind of material would have a greater application for protection against harmful UV radiation on the surface of the earth. For example, as an active ingredient in sunscreens, in formulations to protect plants and animals, for the production of UV-resistant glass in the automotive, aviation and construction industries, and for use in greenhouses. It can also be used to prepare emulsions, paints, varnishes, resins and other coatings for use on surfaces that need to be protected from the sun's UVB radiation.
Partial UVA protection is also provided by these materials, which is evident from the material's significant UV absorption in the 320 to 400 nm region. It is also possible to significantly increase the absorption in the UVA range and thereby increase the protection against this radiation in case of need, if additional organic components were used in the composition of organosilica particles that have significant absorption in the UVA range.
Figure 3 shows the simplified structure of the new organosilica particles, while Figure 4 shows the image of the obtained organosilica particles with the help of a scanning electron microscope.
The surface of organosilica particles is typically dominated by silanol (Si-OH) and silica bonds (Si- O-Si). In the interior of the organosilica particle, there are organic groups (components C and D) that are chemically (covalently) bound via Si-O-Si bonds, and there is no possibility of their exit from the interior under standard ambient conditions. The surface of organosilica particles does not differ in structure from silicate particles, which are regularly applied in cosmetic preparations, which would indicate that their interactions with the skin do not differ significantly and it is expected that organosilica particles are bicompatible, as in the case of related silica particles. The surface of organosilica particles can also be additionally modified with various organosilicates, which can additionally favorably affect the ability to protect against UV radiation, biocompatibility of organosilica particles, miscibility with various components in formulations for cosmetic preparations, paints, varnishes, or for optimizing the preparation of UV-proof glasses.
Figure 4 shows organosilica particles containing component D (4,4'-bis(triethoxysil)-l,T-biphenyl) and component C based on triazine in a ratio of 1 :9. It is noticeable that spherical particles were obtained with their diameter in the range of 200-500 nm. The size of organosilica particles and their morphology can be modified by changes in the synthesis conditions.
Figure 5 shows the distribution of the hydrodynamic diameter of the suspension of particles in water for 5 measurements of the same sample containing component D (4,4'-bis(triethoxysil)-l,l'-biphenyl) and component C based on triazine in a ratio of 1 : 9. The result indicates that individual particles (which according to SEM measurements are 200 to 500 nm in size) cannot be detected, but it is indicative that individual organosilica particles are organized (agglomerated) in the aqueous environment into larger particles, which
have a hydrodynamic diameter of about 1 micrometer . This result is particularly suitable in the case of the preparation of cosmetic preparations for protection against solar UV radiation, because such large particles have no possibilily of passing through the skin. The particle's ability to agglomerate can also be influenced by surface modification of organosilica particles with appropriate organosilanes.
Figure 6 shows the measurement of the surface charge of an organosilica particle (zeta potential), which confirms that the surface is negatively charged (zeta potential below -20 mV), which is characteristic of the as synthesized silica particles, with silanol groups present on the surface that are deprotonated in aqueous environment. Therefore, the surface charge of these organosilica particles is very similar to the charge of silica particles (SAS materials), which are standardly used in cosmetic and other preparations (paints, varnishes...), and a similar interaction of these particles with other components of the formulation and with skin.
Due to the similar characteristics of the outer surface with SAS materials, the application of organosilica particles as UV blockers would provide a significant contribution to the improvement of product characteristics, for which SAS materials are currently used (abrasive agents, adsorbents, anti-caking agents for increasing volume, coloring and as a thickening agent...).
The surface charge can also be modified into neutral or positive values by functionalization with organosilanes, depending on the desired application and the required miscibility in the formulation.
Figure 7 shows the results of the nitrogen sorption measurements which indicates the porous nature of the particles. The BET isotherm and BJH pore size distribution reveal predominantly microporous (pore diameter < 2 nm) nature of the material, with a portion of the pores in the mesoporous region (notable peak at 2.5 nm in the BJH graph). The prepared organosilica particles exhibit high surface area of 247 g/cm3 and average pore diameter of 1.7 nm. The amount of porosity and surface area can be influenced by modifications in the synthetic procedure, by changing the components C and D and their ratio.
In the case of porous organosilica particles, the material can be loaded with molecules that can play a role in additional UV protection or exhibit other benefits for application (ROS scavenging, skin nourishing, drug delivery etc.). These additional molecules can be adsorbed on the surface or entrapped inside the pores of the organosilica particles through the application of various large molecules, which are covalently bound to the organosilica particles and prevent their exit from the pores or enable their slow release into the surrounding environment. The loaded molecules can benefit the application, such as entrapping additional UV blocking molecules in the pores, enabling topical delivery of drugs, such as growth factors for wound healing, delivery of antimicrobial and antifungal molecules, vitamins and other molecules. In addition, the particles with
enhanced porosity exhibit enhanced surface area and lower density, both of which could be beneficial for dispersing the particles and increasing the stability of particles in formulations.
A more detailed insight into the preparation of the organosilica particle requires that component C is obtained in the reaction of components A and B. Component A is given in Figure 8 under the name 4,4',4"-s- triazine-2,4,6-triyl-tribenzoic acid - TTBA, while component B is given in Figure 8 under the name (3- aminopropyl)triethoxysilane = AP-TES. They are mixed in a ratio of 1:3 (or at least in the ratio 1:2), in acetonitrile as a solvent in the presence of dicyclohexylcarbodiimide (DCC) as a catalyst.
To obtain organosilica particles, component C (Figure 9) is mixed with component D (Figure 10), in a solution of surfactant (cetyltrimethylammonium bromide) in a mixture of water and ethanol as a solvent, with the presence of ammonia as a catalyst. In the case of the presented result, a mixture of components C and D was used in a ratio of 1:9, but by applying a higher proportion of component C, organosilica particles with stronger UV protection can be expected.
Industrial applicability
The primary purpose of the invention would be that the new organosilica particles can be applied as an integral part of sunscreens, although a wider application is also possible as an integral part of any material in which protection from UV radiation would be important, e.g. for the preparation and improvement of the physico-chemical characteristics of UV-proof glasses, resins and paints, which would be of interest for the protection of materials and devices in the mechanical, construction, automotive, aviation and space industries, as well as in agriculture for the protection of plants from the harmful effects of UV radiation.
Furthermore, the surface and the pores of organosilica particles can be applied for storing molecules and enabling their release from the particles, which may yield an additional benefit to the applications. These may include storing and release of drugs, antimicrobial and antifungal molecules, vitamins, minerals, skin conditioners, growth factors, scavengers of reactive oxygen species (ROS), additional UV-shielding molecules, and other molecules and biomolecules that may be of benefit for the application.
Claims
1. Organosilica particles formulation based on bridging polysilsesquioxanes for applications in blocking ultraviolet rays (UVA, UVB and UVC) of the general formula (I) Formula I: H-(O-SiO2-l-SiO2)n-(O-SiO2-H-SiO3)1n
Wherein C is a UV-absorbing organic moiety, wherein C is selected from a group consisting of triazine, cinnamate, salicylate, anthranilate, p-aminobenzoate, camphor, benzimidazole, benzophenone, dibenzoylmethane and diphenylacrylate and D is an organic moiety that facilitates particle formation with aditional UV absorbing capabilities; n, m > 0 And structural formula:
(I) are indicated by the fact that the external surface of the as-synthesized material contains silanol (Si-OH) groups. The Internal structure is composed of bridged silsesquioxanes, where the bridging organic components C and D are chemically, covalently bound to the particles via Si-C bonds, while covalent silicate bonds (Si-O-Si) exist between the individual bridging silsesquioxane moieties.
2. Claim 2 depends on Claim 1. Organosilica particles formulation according to claim 1, characterized in that component C is based on organic UV blockers, from which bridged silsesquioxane precursors are synthesized in chemical reactions between a parent UV-shielding organic molecule (component A), e.g. 4, 4', 4"- s-triazine-2,4,6-triyl-tribenzoic acid or other molecules based on derivatives of triazine, cinnamate, salicylate,
anthranilate, p-aminobenzoate, camphor, benzimidazole, benzophenone, dibenzoylmethane, diphenylaciylate and other organic molecules that have the ability to absorb UV rays) and two or more equivalents of a component A, e.g. (3-aminopropyl)triethoxysilane, (3-isocyanatopropyl)triethoxysilane, (3- Glycidyloxypropyl)trimethoxysilane or other suitable organoalkoxysilane reagent to produce a covalent bond with the component B, with or without a presence of a catalyst, in anhydrous conditions.
3. Claim 3 depends on Claims 1 and 2. Organosilica particles formulation according to claim 1, characterized in that component C is based on derivatives of triazine, cinnamate, salicylate, anthranilate, p- aminobenzoate, camphor, benzimidazole, benzophenone, dibenzoylmethane, diphenylacrylate and other structural analogues of these classes of organic molecules that have the ability to absorb UV rays. In case of the component C that is based on 1,3,5-triazine derivative-bridged polysilsesquioxane, the reactants to produce the component C could include: 4,4',4"-(l,3,5-Triazine-2,4,6-triyl)tribenzoic acid), 4',4"',4""'-(l,3,5-Triazine- 2,4,6-triyI)tris(([I,r-biphenyI]-4-carboxylic acid)), 3,3',3"-((l,3,5-Triazine-2,4,6- triyl)tris(azanediyl))tribenzoic acid)) and other structural analogues of 1,3,5-triazine.
4. Claim 4 depends on Claims 1-3. Organosilica particles formulation according to claim 1, characterized in that component D is 4,4'-bis(triethoxysilyl)-l,l'-biphenyl, l,4-bis(triethoxysilyl)benzene, 1,2- bis(triethoxysilyl)ethane, l,2-bis(triethoxysyl)ethylene or other bridged silsesquioxanes that facilitate particle formation.
5. Claim 5 depends on Claims 1-4. Organosilica particles formulation according to claim 1, characterized in that said organosilica particles are porous with the pore diameter in the range 1-50 nm, and their morphology is spherical, or in the form of cylinders or beans.
6. Claim 6 depends on Claims 1-5. The application of the organosilica particles as claimed in claims 1-5 as components for sunscreen formulation comprising: a. the sunscreen composition according to claims 1-5, wherein the sunscreen composition is present in an amount effective to absorb UV radiation; and b. a pharmaceutically-acceptable sunscreen carrier.
7. Claim 7 depends on Claims 1 -5. The application of the surface and the pores of organosilica particles as claimed in claims 1-5 for storing molecules and enabling their release from the particles, which may yield an additional benefit to the applications. These may include entrapping additional UV-shielding molecules in the pores, storing and release of drugs, antibacterial or antifungal molecules, biomolecules, vitamins, minerals, skin conditioners, scavengers of reactive oxygen species (ROS), and other molecules that may benefit the
application, such as for medicinal application in terms of topical delivery of drugs, such as growth factors for wound healing or vitamins, antimicrobials and other molecules.
8. Claim 8 depends on Claims 1-5. The application of the organosilica particles formulations as claimed in claims 1-5 for UV-resistant glasses in the automotive, aviation, space and construction industries, and in agriculture industry for the use in greenhouses.
9. Claim 9 depends on Claims 1-5. The application of the organosilica particles formulations as claimed in claims 1-5 for the preparation of UV-proof emulsions, paints, varnishes, resins and other coatings for use on surfaces that need to be protected from the UV radiation.
10. The organosilica particles formulations according to Claims 1-5, wherein the porosity is obtained by using surfactants or other substances such as cetyltrimethylammonium bromide, sodium dodecyl sulfate, Pluronic P123, and other charged or not charged surfactants and substances that serve as templates for the pores during the synthesis of the organosilica particles.
11. The organosilica particles formulations according to Claims 1-5, wherein they are prepared by sol gel polymerization or modified Stober polymerization of bridged silsesquioxane precursors in the presence of pore templating surfactants or substances.
12. The organosilica particles formulations according to Claims 1-5, wherein they are characterized in that the maximum and intensity of UV absorption of the obtained organosilica particles can be modified by changing the components C and D and their ratio.
13. The organosilica particles formulations according to Claims 1-5, wherein they are characterized in that the obtained particle diameter is 50-1000 nm and their size can be modified by applying changes in the synthesis conditions.
14. The organosilica particles formulations according to Claims 1-5, wherein they are characterized in that the organosilica particles are organized in the aqueous environment into larger particles, whereby the ability to organize is affected by the surface modification of the particle itself with organosilanes.
15. The organosilica particles formulations according to Claims 1-5, wherein they are characterized in that the as synthesized organosilica particles are negatively charged, whereby the surface charge can be modified into more positive, negative or neutral values by surface modifications and functionalization, depending on the desired application and the required miscibility in the formulation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RSP-2022/0316 | 2022-03-28 | ||
| RS20220316A RS20220316A1 (en) | 2022-03-28 | 2022-03-28 | Organosilica particles based on bridging polysixesquioxanes for blocking ultraviolet rays |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023191649A1 true WO2023191649A1 (en) | 2023-10-05 |
Family
ID=86378616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/RS2023/000004 WO2023191649A1 (en) | 2022-03-28 | 2023-03-28 | Organosilica particles based on bridging polysilsesquioxanes for blocking ultraviolet rays |
Country Status (2)
| Country | Link |
|---|---|
| RS (1) | RS20220316A1 (en) |
| WO (1) | WO2023191649A1 (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001093812A1 (en) | 2000-06-05 | 2001-12-13 | Showa Denko K.K. | Cosmetic preparation |
| US20030170280A1 (en) | 2000-08-18 | 2003-09-11 | Canham Leigh T | Dermatological composition |
| US20070183992A1 (en) | 2003-08-05 | 2007-08-09 | L'oréal | Cosmetic composition comprising porous particles incorporating optically active substances |
| US20070249854A1 (en) * | 2004-04-30 | 2007-10-25 | Young-Baek Kim | Poly(Silsesquioxane) Spherical Particle Containing Ultraviolet Light-Absorbing Group and Manufacturing Method Thereof |
| DE102006025057A1 (en) | 2006-05-24 | 2007-11-29 | Beiersdorf Ag | Cosmetic sunscreen preparation with special texture |
| US20100003204A1 (en) | 2008-07-02 | 2010-01-07 | Energy Materials Corporation | Nanoparticle hybrid sunscreens |
| US20130109824A1 (en) * | 2010-07-15 | 2013-05-02 | Nano And Micro Technologies Co., Ltd. | Ultraviolet absorbing poly (organic oxidized silicon) particles having improved ultraviolet stability, and method for preparing same |
| JP5597549B2 (en) | 2008-01-11 | 2014-10-01 | アンタリア リミテッド | Mesoporous zinc oxide powder and method for producing the same |
| US9138395B2 (en) | 2012-12-19 | 2015-09-22 | L'oreal | Sunscreen compositions having synergistic combination of UV filters |
| WO2016189828A1 (en) | 2015-05-28 | 2016-12-01 | 日本板硝子株式会社 | Zinc oxide-containing composite particles, composition for blocking uv rays, and cosmetic material |
| WO2018025610A1 (en) | 2016-08-04 | 2018-02-08 | 日本板硝子株式会社 | Zinc-oxide-containing composite particles, composition for uv shielding, and cosmetic |
| US10183868B2 (en) | 2008-01-11 | 2019-01-22 | Antaria Limited | Mesoporous zinc oxide powder and method for production thereof |
| US10682294B2 (en) | 2015-09-03 | 2020-06-16 | International Business Machines Corporation | Controlling zinc oxide particle size for sunscreen applications |
| US11389386B2 (en) | 2016-01-29 | 2022-07-19 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Photochemically stable, non-leaching, bridged polysilsesquioxane based sunscreens |
-
2022
- 2022-03-28 RS RS20220316A patent/RS20220316A1/en unknown
-
2023
- 2023-03-28 WO PCT/RS2023/000004 patent/WO2023191649A1/en unknown
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001093812A1 (en) | 2000-06-05 | 2001-12-13 | Showa Denko K.K. | Cosmetic preparation |
| US20030170280A1 (en) | 2000-08-18 | 2003-09-11 | Canham Leigh T | Dermatological composition |
| US20070183992A1 (en) | 2003-08-05 | 2007-08-09 | L'oréal | Cosmetic composition comprising porous particles incorporating optically active substances |
| US20070249854A1 (en) * | 2004-04-30 | 2007-10-25 | Young-Baek Kim | Poly(Silsesquioxane) Spherical Particle Containing Ultraviolet Light-Absorbing Group and Manufacturing Method Thereof |
| DE102006025057A1 (en) | 2006-05-24 | 2007-11-29 | Beiersdorf Ag | Cosmetic sunscreen preparation with special texture |
| US10183868B2 (en) | 2008-01-11 | 2019-01-22 | Antaria Limited | Mesoporous zinc oxide powder and method for production thereof |
| JP5597549B2 (en) | 2008-01-11 | 2014-10-01 | アンタリア リミテッド | Mesoporous zinc oxide powder and method for producing the same |
| US20100003204A1 (en) | 2008-07-02 | 2010-01-07 | Energy Materials Corporation | Nanoparticle hybrid sunscreens |
| US20130109824A1 (en) * | 2010-07-15 | 2013-05-02 | Nano And Micro Technologies Co., Ltd. | Ultraviolet absorbing poly (organic oxidized silicon) particles having improved ultraviolet stability, and method for preparing same |
| US9138395B2 (en) | 2012-12-19 | 2015-09-22 | L'oreal | Sunscreen compositions having synergistic combination of UV filters |
| WO2016189828A1 (en) | 2015-05-28 | 2016-12-01 | 日本板硝子株式会社 | Zinc oxide-containing composite particles, composition for blocking uv rays, and cosmetic material |
| US10682294B2 (en) | 2015-09-03 | 2020-06-16 | International Business Machines Corporation | Controlling zinc oxide particle size for sunscreen applications |
| US11389386B2 (en) | 2016-01-29 | 2022-07-19 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Photochemically stable, non-leaching, bridged polysilsesquioxane based sunscreens |
| WO2018025610A1 (en) | 2016-08-04 | 2018-02-08 | 日本板硝子株式会社 | Zinc-oxide-containing composite particles, composition for uv shielding, and cosmetic |
Non-Patent Citations (1)
| Title |
|---|
| KNEZEVIC, ACS APPL. MATER. INTERFACES, vol. 10, 2018, pages 20231 - 20236 |
Also Published As
| Publication number | Publication date |
|---|---|
| RS20220316A1 (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0973493B1 (en) | Sunscreens for protection from sun radiation | |
| US20100003204A1 (en) | Nanoparticle hybrid sunscreens | |
| US20090258072A1 (en) | Large ultraviolet attenuating pigments | |
| JP4890251B2 (en) | Metal oxide dispersion method | |
| KR101404965B1 (en) | Mesoporous composite powder containing metallic oxides and the method for preparing thereof | |
| ES2304985T3 (en) | A PARTICLE THAT UNDERSTANDS A HOSPEDADORA NETWORK AND A GUEST, ITS PREPARATION AND USE IN COMPOSITIONS OF IDENTIFICATION OF ULTRAVIOLET LIGHT. | |
| CN116261553A (en) | Zinc oxide particles, photostable UV filters, and methods of use thereof | |
| KR101835214B1 (en) | Uv blocking composition, cosmetic composition and method of preparing uv blocking composition | |
| JP2018514509A (en) | UV protection compositions and their use | |
| Kidsaneepoiboon et al. | Organic–inorganic hybrid polysilsesquioxane nanospheres as UVA/UVB absorber and fragrance carrier | |
| KR20170052727A (en) | Open Porous Inorganic-Polymer Hybrid Microspheres and Method Thereof, and Cosmetic Formulations Containing Them | |
| CN112867542A (en) | Topical photon barriers comprising bismuth oxide colloids | |
| CN101948127B (en) | Industrial preparation method of non-oxidative cerium oxide nanoparticles | |
| WO2023191649A1 (en) | Organosilica particles based on bridging polysilsesquioxanes for blocking ultraviolet rays | |
| Suh | Use of natural halloysite as a functional cosmetics carrier | |
| Lee et al. | Systematic modulation of mesoporous silica particles with avobenzone and benzene-containing organosilica results in remarkable enhancement of UV protection efficiency | |
| KR101095992B1 (en) | Method for Preparing Fullerene-Silica Nanocomplex Using Microemulsion and Composition for UV Blcoking Containing Fullerene-Silica Nanocomplex Thereof | |
| EP3426224B1 (en) | Physical solar filter consisting of substituted hydroxyapatite in an organic matrix | |
| SI22859A (en) | Sterically stabilised dispersion of hybrid inorganic-organic material in oil as preparation for protection from uv rays and procedure of preparation | |
| KR100611647B1 (en) | Silica coating method of TiO2 as ultraviolet shielding material to prevent photocatalytic activity and to disperse at solution | |
| KR101229509B1 (en) | Cosmetic Compositions Comprising Functional Material―Incorporating Zeolites | |
| JP2020186180A (en) | Composite powder and cosmetic using the same | |
| KR101116596B1 (en) | Hybrid powder of halloysite nanotube-light scattering nanoparticle, method for preparing the same and cosmetic composition comprising the same for uv protection | |
| KR101055025B1 (en) | Medium-porous inorganic composite powder carrying metal oxide in pores and cosmetic composition for ozone blocking containing same | |
| WIWANTHANEE et al. | Preparation of Composites of Citrus Flavonoids and Various Porous Silica Materials and their Performance as Ultraviolet Absorbers for Sunscreens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23723678 Country of ref document: EP Kind code of ref document: A1 |