CN115735002A - Composition comprising a metal oxide and a metal oxide - Google Patents
Composition comprising a metal oxide and a metal oxide Download PDFInfo
- Publication number
- CN115735002A CN115735002A CN202180046896.5A CN202180046896A CN115735002A CN 115735002 A CN115735002 A CN 115735002A CN 202180046896 A CN202180046896 A CN 202180046896A CN 115735002 A CN115735002 A CN 115735002A
- Authority
- CN
- China
- Prior art keywords
- composition
- carbon atoms
- quaternary ammonium
- chloride
- water
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 229910044991 metal oxide Inorganic materials 0.000 title description 4
- 150000004706 metal oxides Chemical class 0.000 title description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 150000002009 diols Chemical group 0.000 claims abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000003752 hydrotrope Substances 0.000 claims description 7
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 6
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 5
- 229940031723 1,2-octanediol Drugs 0.000 claims description 4
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 3
- 229960001950 benzethonium chloride Drugs 0.000 claims description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 claims 1
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- -1 aliphatic alcohols Chemical class 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical group [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001449 anionic compounds Chemical group 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 230000001332 colony forming effect Effects 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 239000006150 trypticase soy agar Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ORUDEUCNYHCHPB-OUUBHVDSSA-N (2r,3s,4s,5r,6r)-2-(hydroxymethyl)-6-tetradecoxyoxane-3,4,5-triol Chemical compound CCCCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O ORUDEUCNYHCHPB-OUUBHVDSSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- ZCPPLZJPPBIWRU-UHFFFAOYSA-M 1-hexadecyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCN1C=C[N+](C)=C1 ZCPPLZJPPBIWRU-UHFFFAOYSA-M 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- JDRSMPFHFNXQRB-CMTNHCDUSA-N Decyl beta-D-threo-hexopyranoside Chemical compound CCCCCCCCCCO[C@@H]1O[C@H](CO)C(O)[C@H](O)C1O JDRSMPFHFNXQRB-CMTNHCDUSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241001103617 Pseudomonas aeruginosa ATCC 15442 Species 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 description 1
- 229940073499 decyl glucoside Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- GCXZDAKFJKCPGK-UHFFFAOYSA-N heptane-1,2-diol Chemical compound CCCCCC(O)CO GCXZDAKFJKCPGK-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 1
- 229940048848 lauryl glucoside Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VMJQVRWCDVLJSI-UHFFFAOYSA-M tetraheptylazanium;chloride Chemical compound [Cl-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC VMJQVRWCDVLJSI-UHFFFAOYSA-M 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C11D2111/14—
Abstract
The present invention relates to a composition for cleaning food, in particular fruits and vegetables. A composition for cleaning food is disclosed comprising 0.1 to 2 wt% of a nonionic surfactant, an ortho glycol, and a quaternary ammonium salt, wherein the glycol has 7 to 14 carbon atoms. It also discloses a method of cleaning a food by diluting in water a composition comprising from 0.1 to 2% by weight of a nonionic surfactant, a vicinal diol having from 7 to 14 carbon atoms, and a quaternary ammonium salt, washing the food in a diluted mixture of the composition in water and then rinsing.
Description
The present invention relates to a composition for cleaning food, in particular fruits and vegetables.
WO 2018/044840 discloses a method of reducing microorganisms on food surfaces and hard surfaces. It discloses an antimicrobial composition comprising two cationic surfactants, and one of the cationic surfactants is a quaternary ammonium cation. It is further disclosed that the composition may have a second cationic surfactant, an antibiotic, and an aminopolycarboxylic acid.
Despite the prior art, there remains a need for improved compositions for cleaning foods such as fruits and vegetables. In particular, it would be desirable to have a composition that can clean uncut fruits or vegetables from bacteria, viruses, etc. without leaving any residue.
Accordingly, in a first aspect, there is provided a composition for cleaning food comprising from 0.1 to 2% by weight of a nonionic surfactant, an ortho glycol and a quaternary ammonium salt, wherein the glycol has from 7 to 14 carbon atoms.
Typically, consumers purchase food from the market and wash them with water before consumption. However, washing with water alone does not effectively remove microorganisms. One way to improve cleaning efficacy, particularly removal of microorganisms, is to use a cleaning composition comprising a surfactant and an antimicrobial agent. It is desirable to have improved cleaning compositions to provide enhanced antimicrobial efficacy.
The efficacy of such compositions is generally dependent on the amount of active (i.e., surfactant, antimicrobial, etc.) present in the composition. Low amounts of active can result in inadequate cleaning. While an excess of active leaves a residue of active on the food, which is not preferred by the consumer. Thus, it is also desirable that the cleaning composition provide enhanced antimicrobial efficacy without leaving residues on the food.
We have surprisingly found that reducing the amount of surfactant can provide better antimicrobial efficacy in compositions further comprising a glycol and a quaternary ammonium salt.
The composition comprises 0.1 to 2 wt% of a nonionic surfactant. Preferably, the surfactant is present at 0.5 to 1.8 wt%, more preferably 0.5 to 1.5 wt% of the composition.
Nonionic surfactants produce less foam than anionic surfactants. Nonionic surfactants are characterized by the presence of hydrophobic and organic hydrophilic groups and are typically prepared by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide.
Preferably, the nonionic surfactant comprises an alkoxylated alkanol, wherein the alkanol is from 9 to 20 carbon atoms and wherein the number of molecules of alkylene oxide (of 2 or 3 carbon atoms) is from 5 to 20. Among such materials, preference is given to using fatty alcohols in which the alkanol is from 9 to 11 or from 12 to 15 carbon atoms and which contain from 5 to 8 or from 5 to 9 alkoxy groups per mole.
Also preferred are paraffinic alcohols (e.g., nonionic surfactants from Huntsman or Sassol). Preferably, the nonionic surfactant is selected from alkoxylated linear alcohols, more preferably ethoxylated linear alcohols.
Examples of such compounds are those in which the alkanol is from 10 to 15 carbon atoms and contains about 5 to 12 oxirane groups per mole, e.g. Neodol TM Family, tergitol 15-S-7, and the like. These are the condensation products of mixtures of higher aliphatic alcohols having an average of from about 12 to 15 carbon atoms with about 9 moles of ethylene oxide. The higher alcohol is a primary alkanol.
Another sub-class of alkoxylated surfactants that may be used contains a precise alkyl chain length rather than the alkyl chain distribution of the alkoxylated surfactant.
Generally, these are referred to as narrow range alkoxylates. Examples of these include Neodol TM -1 series of surfactants.
Other useful nonionic surfactants are those available from BASF under the trademark Plurafac TM The business of marketing is well knownThe class of nonionic surfactants of (1) is represented. Plurafac TM Is the reaction product of a higher linear alcohol with a mixture of ethylene oxide and propylene oxide, containing a mixed chain of ethylene oxide and propylene oxide, terminated by hydroxyl groups. Examples include C13 to C15 fatty alcohols condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, C13 to C15 fatty alcohols condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, C13 to C15 fatty alcohols condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide or mixtures of any of the above.
Another group of nonionic surfactants can be Dobanol TM Commercially available as ethoxylated C fatty alcohols with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Preferably, the nonionic surfactant comprises an Alkyl Polyglycoside (APG). Alkyl polyglycosides are compounds having the formula: R1O (R2O) b (Z) a, wherein R1 is an alkyl group having from about 1 to about 30 carbon atoms; r2 is an alkylene group having 2 to 4 carbon atoms; z is a sugar residue having 5 or 6 carbon atoms; b is a number having a value of 0 to about 12; and a is a number (degree of polymerization) having a value of 1 to about 6. Due to the process by which they are synthesized, alkylpolyglycosides typically exist as mixtures of alkylpolyglycosides having different numbers of carbon atoms in the alkyl group and different degrees of polymerization. Thus, when referring to alkyl polyglycosides, alkyl groups are generally referred to as having a range of carbon atoms (e.g., C4/22 refers to a range of alkyl groups having from 4 to 22 carbon atoms) and the degree of polymerization generally refers to the average degree of polymerization of the mixture.
Preferably, the nonionic surfactant comprises an alkyl polyglucoside surfactant. Examples of such surfactants are decyl glucoside, lauryl glucoside, myristyl glucoside.
Other suitable nonionic surfactants are the monoalkanoic acids and the sorbitan esters of trialkanoic acids having from 10 to 20 carbon atoms condensed with ethylene oxide. Examples of such compounds are polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
Another example of a suitable nonionic surfactant is a polyethylene glycol derivative of hydrogenated castor oil.
The composition comprises a vicinal diol. Vicinal diols have a pair of hydroxyl groups at the 1 and 2 positions of the carbon chain. The diol has 7 to 14 carbon atoms.
Preferably, the diol is selected from the group consisting of 1,2 heptanediol, 1,2 octanediol, 1,2 nonanediol, 1,2 decanediol, 1,2 dodecanediol, 1,2 tetradecanediol, and combinations thereof. Preferably, the diol has from 8 to 10 carbon atoms. The most preferred diol is 1,2-octanediol.
Preferably, the glycol is present at 0.01 to 3.0% by weight of the composition. More preferably, the glycol is present at 0.1 to 1.0% by weight of the composition, most preferably 0.3 to 0.8% by weight of the composition.
The composition comprises a quaternary ammonium salt. Preferably, the quaternary ammonium salt is present at 0.05 to 5.0 wt% of the composition. More preferably, the ammonium salt is present at 0.1 to 4.0 wt%, even more preferably 0.5 to 3.0 wt% of the composition.
The quaternary ammonium salt has the following general formula: R1R2R3R4N + X-, wherein R1 is C12 to C18 alkyl, R2, R3 and R4 are each independently C1 to C3 alkyl and X is an inorganic anion. R1 is preferably a C14 to C16 linear alkyl group, more preferably C16. R2, R3 and R4 are preferably methyl. The inorganic anion (X-) is preferably selected from the group consisting of halides, sulfates, bisulfates, or hydroxides.
For the purposes of the present invention, quaternary ammonium hydroxides are considered to be quaternary ammonium salts. More preferably the anion is a halide or sulfate, most preferably chloride or sulfate. Cetyltrimethylammonium chloride is a specific example of a suitable compound and is available in large commercial quantities.
Suitable quaternary ammonium cationic surfactants are of the class of benzalkonium halides, also known as alkyldimethylbenzyl ammonium halides. The most common type is benzalkonium chloride, also known as alkyldimethylbenzyl ammonium chloride (or ADBAC).
Examples of suitable quaternary ammonium include cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, stearyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecylpyridinium chloride, cetylpyridinium chloride, benzalkonium chloride, tetrabutylammonium chloride, tetraheptylammonium chloride, 1,3-decyl-2-methyl-imidazolium chloride, 1-hexadecyl-3-methyl-imidazolium chloride, didecyl-dimethyl-ammonium bromide, didecyl-dimethyl-ammonium chloride.
Preferably, the quaternary ammonium salt is selected from benzalkonium chloride, benzethonium chloride, cetearonium chloride, cetylpyridinium chloride and tetraethylammonium bromide and mixtures thereof. The most preferred quaternary ammonium salt is benzalkonium chloride.
Preferably, the composition comprises citrate. Preferably, the citrate salt is present at 0.5 to 5.0 wt% of the composition, more preferably 0.75 to 4 wt%, even more preferably 1.0 to 3.0 wt%, by weight of the composition. The preferred citrate is sodium citrate.
The composition may comprise a hydrotrope. Preferably, the hydrotrope is present at 0.1 to 5.0 wt% of the composition. More preferably, the hydrotrope is present at 1.0 to 3.0 wt%.
Hydrotropes are typically low molecular weight, water-soluble or water-miscible organic compounds such as C1 to C5 monohydric alcohols (e.g. ethanol and n-or isopropanol); c2 to C6 glycols (e.g., monopropylene glycol and dipropylene glycol); c3 to C9 triols (e.g., glycerol); polyethylene glycol having a weight average molecular weight (Mw) in the range of about 200 to 600; c1 to C3 alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylene, toluene, ethylbenzene, and isopropylbenzene (cumene) sulfonates).
Suitable hydrotropes include short carbon chain glycols such as ethylene glycol, monopropylene glycol, dipropylene glycol. The most preferred hydrotrope is 1,2-propanediol.
Preferably, the composition is an aqueous composition and comprises from 50 to 95 wt% water, more preferably from 60 to 90 wt%, even more preferably from 70 to 85 wt% water.
Preferably, the composition is in a single dose form. Single dose forms include compositions stored and packaged in sachets. In a single dose form, preferably, the composition is contained in a water-soluble pouch which dissolves on contact with water, thereby releasing the composition in water.
In a second aspect, there is provided a method for cleaning a foodstuff by diluting a composition according to the first aspect in water, washing the foodstuff in a diluted mixture of the composition in water, and then rinsing.
Preferably, the composition is present in water in a ratio of 1:5 to 1: and (5) diluting by 200.
The diluted composition is used to wash the edible items and it is preferred that the edible items are not cut prior to being placed in the wash composition. Preferably, the edible items are left in the wash composition for 5 minutes to 2 hours before being removed, optionally rinsed and drained.
Alternatively, the composition may be packaged in a bottle with a spray head. In this case, the consumer sprays the composition directly onto the food and wipes it with a paper towel or piece of cloth.
Examples
The following formulations were prepared for cleaning fruits and vegetables.
TABLE 1
Composition (I) | Preparation A | Preparation 1 |
1,2 octanediol | 0.5 | 0.5 |
Benzalkonium chloride | 1 | 1 |
Nonionic surfactant | 3 | 1.5 |
Citric acid sodium salt | 2 | 2 |
1,2-propanediol | 2 | 2 |
Water (W) | To 100 | To 100 |
Formulation 1 is a composition according to the invention, whereas formulation a is a comparative formulation.
Test methods for assessing antimicrobial efficacy:
antimicrobial efficacy was tested according to the European Suspension Test (EST) or EN 1276B.
The following bacteria were tested:
escherichia coli ATCC 10536 (gram-negative)
Pseudomonas aeruginosa ATCC 15442 (gram negative)
A24 hour bacterial growth or culture was taken and bacterial cells were suspended in solution to obtain 10 based on a 620nm Optical Density (OD) calibration plot 8 Colony forming units per ml (CFU/ml) (E.coli at 620nm at 0.8OD, P.aeruginosa at 620nm at 0.5 OD).
To test the formulation, it was diluted to the desired concentration in water at 37 ℃.
8 milliliters (ml) of the diluted formulation was mixed with 1ml of the test bacterial culture (with 1ml of 0.3% or 3.0% (w/v) BSA or bovine serum albumin (protein, also known as soil load) premixed contact time was monitored by a stopwatch.
After the specified contact time, 1ml of the above mixture (total volume 10 ml) was immediately neutralized with a suitable buffer solution containing the neutralizing agent specified in the protocol.
The neutralized buffer solution was diluted to obtain countable bacterial counts and seeded on tryptic soy agar in duplicate to obtain 30 to 300 bacterial colonies that were statistically valid on a single plate.
In the case of the control, 1ml of the test culture was mixed with 1ml of 0.3% BSA, and 1ml of 3.0% BSA was added to 8ml of hard water, serially diluted and inoculated on TSA. Plates were incubated at 37 ℃ for 48 hours and residual colonies were counted.
The reduction of bacteria was calculated as Log colony forming units/ml (Log CFU/ml). The log of the "control" or input level of bacteria was calculated, and similarly the log of the number of bacteria remaining in the sample containing the test formulation was calculated. Log reduction was calculated by subtracting the residual bacteria of each formulation from the input values. Higher values mean more reduction of bacteria.
The test results are summarized in the following table:
TABLE 2
Testing | Preparation A | Preparation 1 |
(Log 10) reduction of E.coli | 3.72 | >5.3 |
(Log 10) reduction of Pseudomonas aeruginosa | 0.46 | 1.01 |
Table 2 shows that composition 1 is more effective in removing bacteria than formulation a.
As is evident from the examples, the use of lower amounts of nonionic surfactant means better cleaning of the food product, contrary to expectations.
Claims (11)
1. A composition for cleaning food comprising 0.1 to 2 wt% of a nonionic surfactant, a vicinal diol, and a quaternary ammonium salt, wherein the diol has from 7 to 14 carbon atoms.
2. The composition of claim 1 or 2, wherein the glycol is present at 0.01 to 3.0% by weight of the composition.
3. The composition of any preceding claim, wherein the diol has from 7 to 10 carbon atoms.
4. The composition of any one of the preceding claims, wherein the diol is 1,2-octanediol.
5. The composition of any preceding claim, wherein the quaternary ammonium salt is present at 0.05 to 5.0 wt% of the composition.
6. The composition according to any preceding claims, wherein the quaternary ammonium salt is selected from benzalkonium chloride, benzethonium chloride, cetearonium chloride, cetylpyridinium chloride and tetraethylammonium bromide, and mixtures thereof.
7. The composition of any one of the preceding claims, comprising citrate.
8. The composition of any preceding claim, comprising a hydrotrope.
9. The composition according to any one of the preceding claims, in single dose form.
10. A method for cleaning food by: diluting a composition comprising 0.1 to 2% by weight of a nonionic surfactant, a vicinal diol having 7 to 14 carbon atoms, and a quaternary ammonium salt in water, washing the foodstuff in a diluted mixture of the composition in water, and then rinsing.
11. The method of claim 12, wherein the composition is present in water in a ratio of 1:5 to 1: and (5) diluting by 200.
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IN202021028469 | 2020-07-03 | ||
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EP20192326 | 2020-08-24 | ||
PCT/EP2021/066363 WO2022002607A1 (en) | 2020-07-03 | 2021-06-17 | Composition |
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CN (1) | CN115735002A (en) |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10162648A1 (en) * | 2001-12-20 | 2003-07-10 | Henkel Kgaa | Sprayable aqueous liquid cleansing agent, e.g. for washing-up liquid or fruit/vegetable rinser, comprises alkylether sulfate, secondary alkane sulfonate and amphoteric surfactant |
WO2008135085A1 (en) * | 2007-05-04 | 2008-11-13 | Symrise Gmbh & Co. Kg | Synergistic active preparations comprising 1,2-decanediol and further antimicrobial active compounds |
WO2011002929A1 (en) * | 2009-06-30 | 2011-01-06 | The Trustees Of Columbia University In The City Of New York | Antimicrobial/preservative compositions comprising botanicals |
WO2018044840A1 (en) * | 2016-08-31 | 2018-03-08 | Cryovac, Inc. | Synergistic cationic surfactants resulting in microbial inhibition on food surfaces and hard surfaces |
CN108192748A (en) * | 2017-12-28 | 2018-06-22 | 泉州市晋江恒安卫生科技有限公司 | A kind of impregnated wipe and preparation method thereof |
CN108699494A (en) * | 2016-02-23 | 2018-10-23 | 荷兰联合利华有限公司 | Disinfection water-based composition and method for handling base material |
EP3418361A1 (en) * | 2017-06-21 | 2018-12-26 | The Procter & Gamble Company | Solvent containing hard surface cleaning compositions |
-
2021
- 2021-06-17 EP EP21732328.6A patent/EP4176034A1/en active Pending
- 2021-06-17 CN CN202180046896.5A patent/CN115735002A/en active Pending
- 2021-06-17 WO PCT/EP2021/066363 patent/WO2022002607A1/en active Application Filing
- 2021-06-17 BR BR112022025034A patent/BR112022025034A2/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10162648A1 (en) * | 2001-12-20 | 2003-07-10 | Henkel Kgaa | Sprayable aqueous liquid cleansing agent, e.g. for washing-up liquid or fruit/vegetable rinser, comprises alkylether sulfate, secondary alkane sulfonate and amphoteric surfactant |
WO2008135085A1 (en) * | 2007-05-04 | 2008-11-13 | Symrise Gmbh & Co. Kg | Synergistic active preparations comprising 1,2-decanediol and further antimicrobial active compounds |
WO2011002929A1 (en) * | 2009-06-30 | 2011-01-06 | The Trustees Of Columbia University In The City Of New York | Antimicrobial/preservative compositions comprising botanicals |
CN108699494A (en) * | 2016-02-23 | 2018-10-23 | 荷兰联合利华有限公司 | Disinfection water-based composition and method for handling base material |
WO2018044840A1 (en) * | 2016-08-31 | 2018-03-08 | Cryovac, Inc. | Synergistic cationic surfactants resulting in microbial inhibition on food surfaces and hard surfaces |
EP3418361A1 (en) * | 2017-06-21 | 2018-12-26 | The Procter & Gamble Company | Solvent containing hard surface cleaning compositions |
CN108192748A (en) * | 2017-12-28 | 2018-06-22 | 泉州市晋江恒安卫生科技有限公司 | A kind of impregnated wipe and preparation method thereof |
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WO2022002607A1 (en) | 2022-01-06 |
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