CN113693954A - Antibacterial hand sanitizer - Google Patents
Antibacterial hand sanitizer Download PDFInfo
- Publication number
- CN113693954A CN113693954A CN202111035200.7A CN202111035200A CN113693954A CN 113693954 A CN113693954 A CN 113693954A CN 202111035200 A CN202111035200 A CN 202111035200A CN 113693954 A CN113693954 A CN 113693954A
- Authority
- CN
- China
- Prior art keywords
- hand sanitizer
- sodium
- acid
- tio2
- solution
- 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
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 17
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 9
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 9
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 15
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- -1 sodium tungstate trihydrate Chemical class 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000000645 desinfectant Substances 0.000 claims description 8
- 239000003906 humectant Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 235000005979 Citrus limon Nutrition 0.000 claims description 7
- 244000131522 Citrus pyriformis Species 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000005488 sandblasting Methods 0.000 claims description 6
- 235000019864 coconut oil Nutrition 0.000 claims description 5
- 239000003240 coconut oil Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 230000002457 bidirectional effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- FCLAPXQWWIRXCV-UHFFFAOYSA-J tetrachloroniobium Chemical compound Cl[Nb](Cl)(Cl)Cl FCLAPXQWWIRXCV-UHFFFAOYSA-J 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 238000005422 blasting Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 19
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 18
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 238000005202 decontamination Methods 0.000 abstract description 7
- 230000003588 decontaminative effect Effects 0.000 abstract description 7
- 241000588724 Escherichia coli Species 0.000 abstract description 5
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 abstract description 3
- 206010020751 Hypersensitivity Diseases 0.000 abstract description 2
- 208000026935 allergic disease Diseases 0.000 abstract description 2
- 230000007815 allergy Effects 0.000 abstract description 2
- 230000003385 bacteriostatic effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 230000000694 effects Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000006870 function Effects 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000249 desinfective effect Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000700605 Viruses Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910020935 Sn-Sb Inorganic materials 0.000 description 2
- 229910008757 Sn—Sb Inorganic materials 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 description 1
- 241001116389 Aloe Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000008454 Hyperhidrosis Diseases 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 229960002152 chlorhexidine acetate Drugs 0.000 description 1
- 229960005443 chloroxylenol Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005541 medical transmission Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 208000013460 sweaty Diseases 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- 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
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
-
- 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
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- 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
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9789—Magnoliopsida [dicotyledons]
-
- 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
- A61Q17/005—Antimicrobial preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/22—Inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- A61K2800/48—Thickener, Thickening system
-
- 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
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
-
- 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
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
-
- 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
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
Abstract
The invention provides an antibacterial hand sanitizer, which obtains high-efficiency foaming and decontamination performances by compounding an anionic surfactant, an amphoteric surfactant and a nonionic surfactant as a surfactant, takes hypochlorous acid as a sterilization raw material, has strong sterilization and decontamination capabilities of about 4.48 for 2 minutes of escherichia coli and staphylococcus aureus, and has the performances of skin care, skin moistening, antibacterial and bacteriostatic effects, allergy resistance, relaxation resistance and strong sterilization and decontamination capabilities.
Description
Technical Field
The invention belongs to the field of detergents, and particularly relates to an antibacterial hand sanitizer.
Background
The hand sanitizer is used as a novel hand cleaning product and replaces the soap which is commonly used in the past in public places such as hotels, catering departments, airports and the like. Compared with soap, the hand sanitizer has unique advantages, can avoid contacting hands, prevents secondary pollution sources caused by dirt, bacteria, viruses and the like after use or in the environment, is easy to store, and has less natural consumption. The soap has strong dependence on mechanical kneading in the smearing and using processes, is in a wet state for a long time when used in a public place, and is beneficial to breeding bacteria and viruses.
The hand sanitizer has the characteristics of flexible and changeable formula, strong plasticity, easiness in improvement, mild performance, no skin irritation, hard water resistance, rich foam, diversified components and easiness in processing, and hand sanitizer products on the market are various in types and can be roughly divided into the following components according to different purposes: (1) a common hand sanitizer: no special component is added, and the cleaning agent generally only has the function of removing dirt and grease on hands; (2) skin-care hand sanitizer: skin care ingredients such as pure glycerin and aloe are added into the hand sanitizer, so that the hand sanitizer has the function of moistening the skin while cleaning hands; (3) heavy oil stain type hand sanitizer: the soap is mainly suitable for workers engaged in industries such as machine repair, oil refining, automobile repair and the like, the hands of the workers are often stained with heavy oil stains, and common soap and liquid soap are difficult to clean; (4) disinfecting and sterilizing type hand sanitizer: in response to a plurality of public health problems at present, the effective sterilization components are added into the hand sanitizer, so that the disease transmission can be blocked; (5) water-free type
Liquid soap: alcohol is generally used as a main component, water washing is not needed, the use is simple and convenient, and the hand cleaning and disinfecting liquid is generally used for hand cleaning and disinfection under the condition of water shortage; (6) other functional hand washing solutions: the special function hand sanitizer is developed for different consumer groups, such as a lead-removing hand sanitizer, a compound function hand sanitizer and the like. The variety and functions of the hand sanitizer are so rich, and the hand sanitizer is proved to be easy to process, high in product plasticity and wide in market prospect again, and can play a more important role in preventing diseases.
Hypochlorous acid is the most effective disinfectant in a dilute solution containing chlorine, is prepared by an electrochemical method, is acidic electrolyzed water, is water with the pH of 5.0-6.5 and the effective chlorine concentration of 10-30mg/L, has strong oxidizing ability and the effect of quickly killing microorganisms, and is widely used in hand sanitizer.
For example, Shandong Shuda Biotechnology Co., Ltd CN 111481452A discloses a safety protection hand sanitizer and a preparation method thereof, which comprises the following components: the sodium hypochlorite aqueous solution is weakly acidic, 0-phenylphenol, polyhexamethylene guanidine hydrochloride, chloroxylenol, quaternary ammonium salt, chlorhexidine acetate, glycerol and a surfactant, wherein the weakly acidic sodium hypochlorite aqueous solution contains 50-100 mg/L of available chlorine, and the pH value ranges from 5-7. . The preparation method comprises the following specific steps: the method comprises the following steps: respectively diluting hydrochloric acid and sodium hypochlorite solution with water, and fully mixing; step two: fully reacting the solution in the step one in a reactor; step three: and D, adding the rest components into the weakly acidic sodium hypochlorite solution prepared in the step two, stirring and mixing uniformly by using a stirring device, and bottling and packaging. Compared with the prior art, the invention has the advantages that: the alcohol-free sterilization liquid is colorless and odorless, is safe and convenient to use, does not generate secondary biological pollution after sterilization, and has good sterilization and bacteriostasis effects.
Further, CN201110066196A, which is similar to the present invention, discloses a natural disinfecting detergent composition without preservatives, which has both disinfecting and cleaning functions, said composition comprising an electrolytic chloroxidizing agent, APG, for use in washing the offensive odor of tableware, kitchenware, vegetables, melons and fruits, textiles, or sweaty feet, sweat socks, the electrolytic chloroxidizing agent comprising hypochlorite ions and hypochlorous acid, obtained by electrolyzing a dilute solution of sodium chloride in a diaphragm-free electrolytic cell.
Disclosure of Invention
Based on the content, the invention provides the antibacterial hand sanitizer which takes hypochlorous acid as a sterilizing substance, has a very strong sterilizing effect on escherichia coli, staphylococcus aureus and candida albicans, is clean, environment-friendly, safe and good in decontamination effect, and is a safe and effective daily use article.
The invention also adopts a special anode to electrolyze sodium chloride to prepare the high-efficiency hypochlorous acid solution, the anode obviously improves the binding force between the base material and the active layer by designing the micro-arc oxidation intermediate layer, the metal oxide reinforced electrolysis has long service life, and the compounding of Ti-W-Ir-Nb-Rh is realized by preparing the (Ir-Nb-Rh) Ox active layer, so that the electrode with high catalytic activity, high corrosion resistance and high conductivity is obtained, the oxygen evolution and chlorine evolution potentials are reduced, the electrochemical conversion efficiency is improved, and the anode current efficiency is 85.3-94.2%.
An antibacterial hand sanitizer comprises an alpha-sodium olefin sulfonate AOS anionic surfactant, a cocamidopropyl betaine CAB-35 amphoteric surfactant, a cocofatty acid monoethanolamide CMEA nonionic surfactant, a glycerin humectant, sodium chloride inorganic salt, a polyacrylic acid PPA thickener, disodium ethylene diamine tetraacetate EDTA-2Na, a mica powder pearlescent additive, lemon essence and a hypochlorous acid deionized water solution, wherein the pH of the hand sanitizer is 5.75-6.75, and the viscosity is 2000-4000 mPa.S.
Further, the hand sanitizer comprises the following components:
alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetic acid EDTA-2 Na: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution: and (4) the balance.
Furthermore, the effective chlorine component in the hand sanitizer is 50-70 ppm.
Further, the sodium hypochlorite aqueous solution is prepared by the following method:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, and a titanium alloy or stainless steel is used as a cathode:
(2) electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid to the bottom of the reaction tank;
(3) diluting and collecting hypochlorous acid disinfectant: effluent liquid is collected from the top of the electrolytic bath and then used and diluted with deionized water to obtain hypochlorous acid disinfectant water.
The preparation method of the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode comprises the following steps:
(a) pretreating a titanium plate or a titanium mesh substrate;
(b) preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: placing the pretreated substrate serving as an anode in an electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of sodium tungstate trihydrate, sodium hydroxide, sodium fluoride, sodium hexametaphosphate and deionized water;
electrolysis parameters: the bidirectional pulse voltage is 400V at positive pressure of 350-;
(c) preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, dissolving a certain amount of ammonium chlororhodate and chloroiridic acid in a mixed solution of isopropanol and hydrochloric acid in a ratio of 1:1, mixing the chloroiridic acid, the ammonium chlororhodate and niobium tetrachloride according to a molar ratio of (10-25) to (15-20) to (5-10) to obtain a precursor solution, coating the precursor solution on the surface of the TiO2-WO3 composite interlayer by brushing, drying at 60-70 ℃ for 3-5min, converting a muffle furnace, raising the temperature of the muffle furnace to 500 ℃ at a temperature of 5 ℃/min, keeping the temperature for 20-30min, naturally cooling, repeating the brushing process until the required loading capacity is reached, and then annealing at 500 ℃ for 1-1.5h at 450 ℃ to obtain the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
Further, the pretreatment comprises oil removal, sand blasting and washing, wherein the oil removal comprises the following steps: placing the substrate in 3-5wt.% Na2CO3Keeping the solution for 5-10min, and then 60-80oC, performing ultrasonic treatment for 1-3 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.1-0.15 MPa; the washing is deionized water washing.
Further, 13-17g/L of sodium tungstate trihydrate, 1.5-2.5g/L of sodium hydroxide, 2-3g/L of sodium fluoride, 4-5g/L of sodium hexametaphosphate and the balance of deionized water.
Further, the thickness of the TiO2-WO3 composite intermediate layer is 5-10 μm, and the thickness of the (Ir-Nb-Rh) Ox active layer is 12-15 μm.
Further, the loading amount in the step (c) is 2.2-2.5mg/cm2。
The hand sanitizer is a cleaning product designed for removing stains and bacteria on hands, and comprises necessary active ingredients, a sterilization ingredient and auxiliary ingredients.
Surfactant (b): the basic function is cleaning function, the hand sanitizer mainly cleans oil stains on hands, the surfactant can generate abundant foam, the surfactant can be dissolved in water under lower concentration, the surface tension of a solution system can be greatly reduced, a large number of micelles can be formed in the solution along with the fact that the surfactant reaches critical micelle concentration, the micelles can play roles of wetting, solubilizing, emulsifying and dispersing, and the oil stains are cleaned.
Humectant: for the market demand, not only simple cleansing and decontamination, but also the human feeling after cleansing is very important to avoid dryness and roughness of hands, so that there is a need for a moisturizing agent for improving the physical feeling, which is defined as a substance capable of retaining water in the horny layer of the skin or delaying and preventing the volatilization of water in the horny layer, and especially showing such a characteristic at low humidity, and the present invention employs glycerin having low volatility, high boiling point and strong hygroscopicity as a moisturizing agent.
Thickening agent: when the hand sanitizer is used, if the viscosity is too low, the hand sanitizer is very easy to slip away from hands, waste is caused, the dirt removing capability is also influenced, and the hand sanitizer is not easy to squeeze and wash due to too high viscosity adjustment. The hand sanitizer has proper viscosity, can enhance the sensory effect of consumers, and adopts sodium chloride and PPA (polyacrylic acid) as a thickening agent.
Complexing agent: the ordinary water contains Ca2+、Mg2+Some surfactants have poor hard water resistance, and the hard metal ions can form precipitates with the metal ions in the water to influence the performance of the detergent. The invention adopts EDTA-2Na as complexing agent, which can form a soluble ring structure in water to bind metal ions in the ring, thereby preventing the metal ions from forming precipitates and ensuring that the solution has good appearance.
Essence and pearl powder are used for improving the touch effect of the hand sanitizer, and the taste and the appearance required by customers can be selected according to requirements.
And (3) bactericide: because hypochlorous acid is uncharged and has a relatively low molecular weight, it can penetrate cell walls more rapidly than other bactericides or bacteriostats, and can perform oxidation reaction with organic matters (namely key components of microbial cells) more rapidly, so that the disinfection effect is more efficient, and only under the condition of low concentration, the hypochlorous acid can penetrate cell membranes by attacking physiologically-related molecules (such as ammonia, thioether, mercaptan, nucleotide and the like) to oxidize proteins, thereby achieving the aim of killing bacterial propagules, viruses, fungi, tubercle bacillus and bacterial spores.
With respect to the electrolytic process of the invention and the anodes used:
firstly: the surface pretreatment is carried out on the titanium substrate, the surface treatment comprises degreasing and sand blasting, wherein the degreasing step is an unnecessary treatment process, mainly because micro-arc oxidation is carried out subsequently, the voltage in the micro-arc oxidation process is large, and an obvious anodic electrochemical degreasing process can occur, so degreasing is optional, but the degreasing can influence the binding force of the micro-arc oxidation layer and the substrate to a certain extent.
Secondly, the intermediate layer has the functions of increasing the binding force between the titanium substrate and the active coating, resisting gas scouring and preventing the premature peeling of the coating, simultaneously, the intermediate layer prevents oxygen from diffusing and permeating to the substrate, slows down the forming speed of the non-conductive titanium oxide film between the substrate and the active coating, delays the passivation and inactivation of the substrate, and improves the service life of the oxide anode
Its life is long. The intermediate layer in the prior art is mainly SnO2, Sn-Sb oxide, Ir-Co oxide, Sn-Sb-Mn oxide, Sn-Ru-Mn oxide, Ru-Sn-Sb oxide, Ru-Sb-Mn oxide, Nb-Sn oxide and the like, and certainly, part of the intermediate layer is a titanium-based anodic oxide film, a titanium-based micro-arc oxide film is rarely used as the intermediate layer, and the anodic oxidation or micro-arc oxide film is used as the intermediate layer, so that the bonding force between the base material and the intermediate layer can be effectively improved, mainly because the oxide film is generated in situ, no obvious interface exists between the intermediate layer on the surface of the titanium base material and the base material, the transition is good, and the coating, electroplating or other deposition methods have obvious interfaces, when the interface is subjected to subsequent heat treatment on an active layer, certain thermal peeling or thermal stress accumulation inevitably occurs, in addition, compared with an anodic oxide film, the micro-arc oxide film is far higher than the micro-arc oxide film in corrosion resistance (salt spray resistance), hardness and service life, but the micro-arc oxide film has lower porosity in morphology, so that the bonding force between an active coating and a base material is reduced, the surface of the single titanium oxide micro-arc oxide film is rough, discharge residual holes with different sizes exist, the range of the holes is greatly changed, the porosity ranges from 2 wt.% to 8wt.%, wherein the main contribution of the porosity is a surface porous layer, the physicochemical contribution mainly lies in a transition layer, the bonding force mainly lies in a bottom dense layer, the hole absorption rate of the dense layer is lower than 1%, and the specific surface area of the micro-arc oxide slip film is 10.32m2(ii) in terms of/g. In contrast, the W element is added in the micro-arc oxidation film, higher porosity is shown, and the specific surface area is increased to 13.9 m2(g), the improvement of porosity and surface area is obviously improvedThe contact area with the active layer improves the bonding force of the active layer and the active layer, more active sites are provided in the process of composite synergistic activation, and the obtained TiO in the middle layer2About 50-55wt.%, the mass fraction of W is about 25-30wt.%, and the composition of Ti is greater due to Ti4+Participate in at least two main reactions, and W participates in at least one main reaction, the reaction formula is as follows:
Ti4++2OH-+2H2O→TiO2+2H2O+
Ti4++2WO4 2-+TiO2+2WO3。
namely, the TiO2-WO3 has the advantages of corrosion resistance, good conductivity and close combination with a titanium matrix.
Active layer: two or more components mixed in the electrode seek a synergistic effect to achieve close electronic connection between the components
The invention aims to improve the electrode activity, and is the main purpose of active layer research, the main active elements adopted by the invention are Ir, Nb and Rh, namely the main body of the coating is Ir, Nb and Rh elements, wherein Ir and Rh are main oxides and provide high catalytic activity and corrosion resistance, Nb is used for improving the particle morphology of the oxide on the surface of the coating, refining the crystal grains of the coating, increasing the microscopic area of the electrode, having larger roughness and improving the specific surface area of the surface activity, and further improving the catalytic activity of the coating.
The (Ir-Nb-Rh) Ox solid solution can not be completely dissolved, and part of the (Ir-Nb-Rh) Ox solid solution can be precipitated by IrOX and RuO2, so that the microcosmic specific surface area and active sites of the anode can be increased, the chlorine precipitation efficiency is improved, a large number of micropores and gaps are formed on the surface of the electrode, obvious crystal clusters are precipitated from the gaps, the microcosmic specific surface area is increased, the current density is small, the service life of the electrode is prolonged, and the coating has the advantages of flat surface, compact crystallization, shallow depth of the cracks, narrow width and fine cracks.
The process of electrolyzing hypochlorous acid adopts a diaphragm-free electrolytic bath, the reaction bath at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, a titanium alloy or stainless steel is used as a cathode, the anode is used for chlorine evolution reaction, namely the chlorine ions lose electrons to formForming chlorine molecules, and reacting the chlorine with water to generate hypochlorous acid, chloride ions and a small part of chlorate ions. Meanwhile, oxygen is separated out after water molecules at the anode are electrolyzed, the oxygen evolution reaction is a side reaction, the oxygen evolution reaction is avoided as much as possible, the chlorine evolution reaction is dominant in the competition of the chlorine evolution reaction and the oxygen evolution reaction, but when the concentration of the sodium chloride electrolyte is too low, ionized chloride ions cannot meet the electrolysis speed of an electrolytic cell, so that water electrolysis is started, oxygen is separated out, the oxygen precipitation of the oxygen can obviously reduce the oxygen defect of the anode active oxide, the catalytic layer is inactivated, and the current density is: the current density of the invention is 100-2The available chlorine increases with the increase of the current density, the pH value shifts slowly to neutral, the chlorine evolution potential decreases significantly, as in example 3, the chlorine evolution potential is 0.98V, which is lower than that of example 2, after the current density is increased, and in addition, the current efficiency decreases with the increase of the current density, mainly due to the decrease of the current efficiency caused by the oxygen evolution competition reaction.
The pH of the effluent of the invention is 2.5-4, within the range, the hypochlorous acid can not be stored almost, the available chlorine of the obtained effluent is almost zero within about 20-30 days, therefore, the newly obtained effluent must be diluted to 6.5-7, the effluent obtained in the example 2 is diluted to pH =6.75 by deionized water, the content of the available chlorine is tested under the conditions of light shielding and sealing for different time, the initial content of the available chlorine is 62mg/L, the storage rate of the available chlorine is 97% after 120 days, the storage effect is excellent, the sterilization effect of the available chlorine stored in the sealed light shielding on escherichia coli and staphylococcus aureus is tested, the ORP value is 1040mV, the available chlorine is about 60 mg/L, and the sterilization effect is almost 100% within 3 min.
The beneficial technical effects are as follows:
(1) the efficient foaming and decontamination performances are obtained by compounding anionic surfactant, amphoteric surfactant and nonionic surfactant into the surfactant.
(2) The hand sanitizer has the effects of skin care, skin moistening, antibiosis, bacteriostasis, allergy resistance, relaxation and strong sterilization and decontamination capability, the sterilization efficiency of escherichia coli and staphylococcus aureus in 1min is 99.99%, and the sterilization log value in 2min is 4.48 (99.99668%).
(3) The TiO2-WO3 intermediate layer is prepared on the surface of the titanium substrate through in-situ oxidation, the bonding force between the titanium substrate and the active layer is effectively improved, the specific surface area of the intermediate layer is high, the microcosmic contact specific surface area is provided for coating the active layer, and the stability between the intermediate layer and the active layer is further improved.
(4) By coating the solid solution active component mainly containing Ir, Nb and Rh on the surface of the intermediate layer, the catalytic activity of electrolysis is obviously improved, coating crystal grains are refined, the obtained coating has the advantages of smooth surface, compact crystallization, shallow depth and width of cracks, fine cracks, improved catalytic activity and stability and prolonged service life.
(5) The hypochlorous acid prepared by electrolyzing sodium chloride has low chlorine evolution potential, high current efficiency, high effective chlorine concentration and excellent sterilization effect.
The specific implementation mode is as follows:
all the hypochlorous acid preparation processes in the embodiments 1 to 3 of the invention are as follows:
a preparation method of a disinfectant is characterized in that hypochlorous acid is used as the disinfectant, and the preparation method comprises the following steps:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, a titanium alloy or stainless steel is used as a cathode, and the polar distance between the cathode and the anode is 3.5 mm.
(2) Electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid into the bottom of the reaction tank, wherein the pH value of the mixed solution is 0.9, the mixed solution inlet speed is 1.5L/h, and the current density is 125mA/cm2。
(3) Diluting and collecting hypochlorous acid disinfectant: the effluent was collected from the top of the cell and then used and diluted with deionized water.
The preparation method of the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode is as follows.
(a) Pre-treating a titanium plate or titanium mesh substrate: the pretreatment comprises oil removal, sand blasting and washing, wherein the oil removal comprises the following steps: placing the substrate in 4wt.% Na2CO3Keeping the solution for 7.5min,then 70oC, performing ultrasonic treatment for 2 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.125 MPa; the washing is deionized water washing.
(b) Preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: the pretreated substrate is used as an anode and placed in electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of 15g/L sodium tungstate trihydrate, 2g/L sodium hydroxide, 2.5g/L sodium fluoride, 4.5g/L sodium hexametaphosphate and the balance of deionized water.
Electrolysis parameters: bidirectional pulse voltage, positive voltage 375V, negative voltage 40V, duty ratio 35%, frequency 750Hz, positive-negative pulse ratio 1:1, time 6 min.
(c) Preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, dissolving certain amounts of ammonium chlororhodate and chloroiridic acid in a mixed solution of isopropanol and hydrochloric acid in a ratio of 1:1, mixing the chloroiridic acid, the ammonium chlororhodate and niobium tetrachloride according to a molar ratio of (17.5) to (7.5) to obtain a precursor solution, coating the precursor solution on the surface of a TiO2-WO3 composite intermediate layer by brushing, drying at 70 ℃ for 5min, converting a muffle furnace, raising the temperature of the muffle furnace to 475 ℃ at 5 ℃/min, keeping the temperature for 25min, naturally cooling, and repeating the brushing process until the required temperature reaches 2.35mg/cm2Carrying out annealing at 475 ℃ for 1.25h to obtain the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
Example 1
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5 wt.%;
glycerin humectant: 1 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 5.75.
Example 2
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 6.2.
Example 3
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 6.75.
The hand sanitizer obtained in example 2 was tested for foamability, and the foam rate was 372% and the foam was reduced by 5 to 7% at 0 to 3min, and then was maintained stable, and the foam stability was reduced by 43% after 1 hour, according to GB/T13173.6 "determination of foaming power of detergent", and the viscosity was 3752 mPa · S. The sterilization efficiency for escherichia coli and staphylococcus aureus is 99.8% within 1min, and the sterilization log value within 5min is 4.48 (99.99668%).
While the invention has been described in conjunction with specific embodiments thereof, it will be understood by those skilled in the art that many modifications and variations may be made to the invention. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit and scope of the invention.
Claims (9)
1. An antibacterial hand sanitizer is characterized by comprising alpha-alkenyl sodium sulfonate AOS anionic surfactant, cocamidopropyl betaine CAB-35 amphoteric surfactant, cocofatty acid monoethanolamide CMEA nonionic surfactant, a glycerin humectant, sodium chloride inorganic salt, polyacrylic acid PPA thickener, disodium ethylene diamine tetraacetate EDTA-2Na complexing agent, mica powder pearlescent additive, lemon essence and hypochlorous acid deionized water solution, wherein the pH of the hand sanitizer is 5.75-6.75, and the viscosity is 2000-4000 mPa.S.
2. The antimicrobial hand sanitizer according to claim 1, wherein the hand sanitizer comprises the following composition:
alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution: and (4) the balance.
3. The antibacterial hand sanitizer according to claim 1, wherein the active chlorine component in the hand sanitizer is 50 to 70 ppm.
4. An antibacterial hand sanitizer according to claim 1 wherein said aqueous hypochlorous acid solution is prepared by:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, and a titanium alloy or stainless steel is used as a cathode:
(2) electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid to the bottom of the reaction tank;
(3) diluting and collecting hypochlorous acid disinfectant: effluent liquid is collected from the top of the electrolytic bath and then used and diluted with deionized water to obtain hypochlorous acid disinfectant water.
5. The antibacterial hand sanitizer of claim 4, wherein the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode is prepared by the following method:
(a) pretreating a titanium plate or a titanium mesh substrate;
(b) preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: placing the pretreated substrate serving as an anode in an electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of sodium tungstate trihydrate, sodium hydroxide, sodium fluoride, sodium hexametaphosphate and deionized water;
electrolysis parameters: the bidirectional pulse voltage is 400V at positive pressure of 350-;
(c) preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, and dissolving certain amounts of ammonium chlororhodate and chloroiridic acid inIn a mixed solution of isopropanol and hydrochloric acid with the ratio of 1:1, mixing chloroiridic acid, ammonium chlororhodate and niobium tetrachloride according to the molar ratio of (10-25) to (15-20) to (5-10) to obtain a precursor solution, coating the precursor solution on the surface of a TiO2-WO3 composite intermediate layer by brushing, drying at the temperature of 60-70 ℃ for 3-5min, converting a muffle furnace, raising the temperature of the muffle furnace to 500 ℃ at the temperature of 450 ℃ at the programmed temperature of 5 ℃/min, keeping the temperature for 20-30min, naturally cooling, repeatedly brushing until the required loading capacity is reached, annealing at the temperature of 500 ℃ for 1-1.5h at the temperature of 450 ℃ to obtain a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
6. An antibacterial hand sanitizer according to claim 5 wherein said pretreatment comprises degreasing, blasting and rinsing, said degreasing: placing the substrate in 3-5wt.% Na2CO3Keeping the solution for 5-10min, and then 60-80oC, performing ultrasonic treatment for 1-3 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.1-0.15 MPa; the washing is deionized water washing.
7. The antibacterial hand sanitizer of claim 5, wherein the sodium tungstate trihydrate is 13-17g/L, the sodium hydroxide is 1.5-2.5g/L, the sodium fluoride is 2-3g/L, the sodium hexametaphosphate is 4-5g/L, and the balance is deionized water.
8. The antibacterial hand sanitizer according to claim 5, wherein the TiO2-WO3 composite intermediate layer has a thickness of 5-10 μm, and the (Ir-Nb-Rh) Ox active layer has a thickness of 12-15 μm.
9. The antibacterial hand sanitizer of claim 5, wherein the loading in the step (c) is 2.2-2.5mg/cm2。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111035200.7A CN113693954B (en) | 2021-09-05 | 2021-09-05 | Antibacterial hand sanitizer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111035200.7A CN113693954B (en) | 2021-09-05 | 2021-09-05 | Antibacterial hand sanitizer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113693954A true CN113693954A (en) | 2021-11-26 |
CN113693954B CN113693954B (en) | 2024-02-20 |
Family
ID=78660065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111035200.7A Active CN113693954B (en) | 2021-09-05 | 2021-09-05 | Antibacterial hand sanitizer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113693954B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377454A (en) * | 1980-05-09 | 1983-03-22 | Occidental Chemical Corporation | Noble metal-coated cathode |
US4468416A (en) * | 1981-05-19 | 1984-08-28 | Permelec Electrode Ltd. | Electrolytic electrodes having high durability and process for the production of same |
US5587058A (en) * | 1995-09-21 | 1996-12-24 | Karpov Institute Of Physical Chemicstry | Electrode and method of preparation thereof |
CN1433270A (en) * | 1999-12-10 | 2003-07-30 | 花王株式会社 | Microbicide compositions |
EP2055807A1 (en) * | 2007-10-31 | 2009-05-06 | Daiki Ataka Engineering Co., Ltd. | Oxygen Evolution Electrode |
CN102839387A (en) * | 2012-09-20 | 2012-12-26 | 福州大学 | Titanium anode having Ru-Ir-Ti ternary coating with embedded structure and preparation method thereof |
CN111188052A (en) * | 2020-02-27 | 2020-05-22 | 上海广锋生物科技有限公司 | Preparation method of high-performance hypochlorous acid |
CN111437206A (en) * | 2020-05-27 | 2020-07-24 | 珠海纳金科技有限公司 | Antibacterial and disinfectant hand sanitizer containing nano-silver and preparation method thereof |
CN113072138A (en) * | 2021-03-22 | 2021-07-06 | 浙江大学 | Preparation method of long-life DSA electrode capable of being used for frequently reversing cathode and anode |
-
2021
- 2021-09-05 CN CN202111035200.7A patent/CN113693954B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377454A (en) * | 1980-05-09 | 1983-03-22 | Occidental Chemical Corporation | Noble metal-coated cathode |
US4468416A (en) * | 1981-05-19 | 1984-08-28 | Permelec Electrode Ltd. | Electrolytic electrodes having high durability and process for the production of same |
US5587058A (en) * | 1995-09-21 | 1996-12-24 | Karpov Institute Of Physical Chemicstry | Electrode and method of preparation thereof |
CN1433270A (en) * | 1999-12-10 | 2003-07-30 | 花王株式会社 | Microbicide compositions |
EP2055807A1 (en) * | 2007-10-31 | 2009-05-06 | Daiki Ataka Engineering Co., Ltd. | Oxygen Evolution Electrode |
CN102839387A (en) * | 2012-09-20 | 2012-12-26 | 福州大学 | Titanium anode having Ru-Ir-Ti ternary coating with embedded structure and preparation method thereof |
CN111188052A (en) * | 2020-02-27 | 2020-05-22 | 上海广锋生物科技有限公司 | Preparation method of high-performance hypochlorous acid |
CN111437206A (en) * | 2020-05-27 | 2020-07-24 | 珠海纳金科技有限公司 | Antibacterial and disinfectant hand sanitizer containing nano-silver and preparation method thereof |
CN113072138A (en) * | 2021-03-22 | 2021-07-06 | 浙江大学 | Preparation method of long-life DSA electrode capable of being used for frequently reversing cathode and anode |
Non-Patent Citations (3)
Title |
---|
BAUMANM,N;CREMERS,C: "Supported IrxRu1-xO2 Anode Catalysts for PEM-Water Electrolysis", FUEL CELLS, vol. 17, no. 2, pages 259 - 267, XP055748695, DOI: 10.1002/fuce.201500212 * |
胡新发;刘全兵;廖世军;: "钛基涂层不溶性阳极的开发与研究进展", 材料保护, no. 08, pages 41 - 45 * |
霍淑利: "纳米TiO2-Ti基IrO2涂层钛阳极的制备及其性能研究", 《中国优秀硕士学位论文全文数据库(电子期刊)》, pages 014 - 384 * |
Also Published As
Publication number | Publication date |
---|---|
CN113693954B (en) | 2024-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2219684B1 (en) | Device for for cleaning floor surfaces with electrolysed water by means of oxidative radicals produced by diamond electrodes | |
EP1899081A1 (en) | Method for cleaning, sterilising and disinfecting dishes and other kitchen utensils and cleaning device | |
WO2001066682A1 (en) | Cleaning solution, and method and apparatus for cleaning using the same | |
WO1999037414A1 (en) | Washing process and washing unit | |
US20130125316A1 (en) | System and a Method for Washing, Cleaning, Disinfecting and Sanitizing Laundry Using Electrolytic Cell Having Boron-Doped Diamond Electrode | |
CN110055548A (en) | Electrolysis ozone electrode and preparation method thereof and electrolysis ozone water die set | |
KR20130049031A (en) | Germicidal sterilizer composition for hypochlrous acid solution and method for manufacturing sterilized water using the same | |
JP2004204328A (en) | Method of producing hypochlorous acid solution, and utilizing method thereof | |
CN104828910A (en) | Manufacturing method and uses of acid oxidation potential water | |
Qin et al. | An experimental study of an NaClO generator for anti-microbial applications in the food industry | |
CN113215596B (en) | System suitable for hypochlorous acid sterilizing water in industrial production | |
JP6656823B2 (en) | Raw material for producing electrolytic water, electrolytic solution using the same, electrolytic water produced from the electrolytic solution, and method for producing the electrolytic solution and electrolytic water | |
CN113693954B (en) | Antibacterial hand sanitizer | |
CN113749982B (en) | Preparation method of antibacterial hand sanitizer | |
CN113181096A (en) | Plant extract no-clean hand sanitizer and preparation method thereof | |
KR101362966B1 (en) | Electrodes structure for high concentration hypochlrous acid solution from soidum chloride solution and method for manufacturing sterilized water using the same | |
JP5678000B2 (en) | Washing water production method | |
CN109294750A (en) | Antibacterial cleaning nanometer water of one kind and preparation method thereof | |
CN104787856A (en) | Device for sterilization, disinfection, stain removal and odor elimination of ionized water | |
CN210275775U (en) | Multipurpose plasma sterilizer | |
US20220153613A1 (en) | Ultra-high alkaline electrolyzed water generation system | |
CN204918094U (en) | Ion water degerming disinfection decontamination ware suitable for public place | |
Umimoto et al. | Development of device producing electrolyzed water for home care | |
WO2018105098A1 (en) | Electrolyzed water production starting material and electrolytic solution using same, and methods for producing said production starting material, said electrolytic solution and said electrlyzed water | |
CN112956491A (en) | Application of acidic electrolyzed oxidizing water in disinfection and sterilization of central kitchen environment |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20240124 Address after: No.10, Huimin 1st Road, No.6 Industrial Zone, Guanlan street, Longhua District, Shenzhen, Guangdong 518000 Applicant after: SWASHES PRODUCTS CO.,LTD. Country or region after: China Address before: College of chemistry and material engineering Jiangnan University No. 1800 214122 Jiangsu city of Wuxi Province Li Lake Avenue Applicant before: Liang Lianzhi Country or region before: China |
|
TA01 | Transfer of patent application right | ||
GR01 | Patent grant | ||
GR01 | Patent grant |