CN115024324B - Pesticide bactericide and preparation method thereof - Google Patents
Pesticide bactericide and preparation method thereof Download PDFInfo
- Publication number
- CN115024324B CN115024324B CN202210800273.9A CN202210800273A CN115024324B CN 115024324 B CN115024324 B CN 115024324B CN 202210800273 A CN202210800273 A CN 202210800273A CN 115024324 B CN115024324 B CN 115024324B
- Authority
- CN
- China
- Prior art keywords
- agent
- tricyclazole
- kasugamycin
- mass ratio
- thickener
- 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.)
- Active
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 46
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 22
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002562 thickening agent Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000080 wetting agent Substances 0.000 claims abstract description 56
- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 claims abstract description 55
- 239000002270 dispersing agent Substances 0.000 claims abstract description 47
- 239000004480 active ingredient Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000003755 preservative agent Substances 0.000 claims abstract description 34
- 230000002335 preservative effect Effects 0.000 claims abstract description 32
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 239000004615 ingredient Substances 0.000 claims abstract 3
- 239000002994 raw material Substances 0.000 claims description 38
- 238000010008 shearing Methods 0.000 claims description 37
- 239000011786 L-ascorbyl-6-palmitate Substances 0.000 claims description 36
- QAQJMLQRFWZOBN-LAUBAEHRSA-N L-ascorbyl-6-palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-LAUBAEHRSA-N 0.000 claims description 36
- 235000010385 ascorbyl palmitate Nutrition 0.000 claims description 36
- 238000012360 testing method Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000013530 defoamer Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000004806 packaging method and process Methods 0.000 claims description 17
- 229920005646 polycarboxylate Polymers 0.000 claims description 17
- 238000005070 sampling Methods 0.000 claims description 17
- 230000002528 anti-freeze Effects 0.000 claims description 14
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 13
- 239000004299 sodium benzoate Substances 0.000 claims description 13
- 235000010234 sodium benzoate Nutrition 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000230 xanthan gum Substances 0.000 claims description 12
- 229920001285 xanthan gum Polymers 0.000 claims description 12
- 229940082509 xanthan gum Drugs 0.000 claims description 12
- 235000010493 xanthan gum Nutrition 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 230000000855 fungicidal effect Effects 0.000 claims description 5
- 239000000417 fungicide Substances 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004302 potassium sorbate Substances 0.000 claims description 3
- 235000010241 potassium sorbate Nutrition 0.000 claims description 3
- 229940069338 potassium sorbate Drugs 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 240000005020 Acaciella glauca Species 0.000 claims 1
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 235000008582 Pinus sylvestris Nutrition 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000001839 pinus sylvestris Substances 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 29
- 235000009566 rice Nutrition 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 19
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 239000003814 drug Substances 0.000 description 20
- 241000219782 Sesbania Species 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 10
- 230000002421 anti-septic effect Effects 0.000 description 9
- 239000000375 suspending agent Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 8
- 230000002265 prevention Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000009885 systemic effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000857 drug effect Effects 0.000 description 3
- 239000004495 emulsifiable concentrate Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 2
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical group [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 2
- 230000008485 antagonism Effects 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000004562 water dispersible granule Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HLHOHTNONYACFD-UHFFFAOYSA-N 1-[4-[4-morpholin-4-yl-1-[1-(pyridine-3-carbonyl)piperidin-4-yl]pyrazolo[3,4-d]pyrimidin-6-yl]phenyl]-3-pyridin-4-ylurea Chemical compound C=1C=C(C=2N=C3N(C4CCN(CC4)C(=O)C=4C=NC=CC=4)N=CC3=C(N3CCOCC3)N=2)C=CC=1NC(=O)NC1=CC=NC=C1 HLHOHTNONYACFD-UHFFFAOYSA-N 0.000 description 1
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 1
- RTIXKCRFFJGDFG-UHFFFAOYSA-N Chrysin Natural products C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- FGUBFGWYEYFGRK-HNNXBMFYSA-N Pinocembrin Natural products Cc1cc(C)c2C(=O)C[C@H](Oc2c1)c3ccccc3 FGUBFGWYEYFGRK-HNNXBMFYSA-N 0.000 description 1
- 241001655322 Streptomycetales Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000037354 amino acid metabolism Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- URFCJEUYXNAHFI-ZDUSSCGKSA-N pinocembrin Chemical compound C1([C@@H]2CC(=O)C3=C(O)C=C(C=C3O2)O)=CC=CC=C1 URFCJEUYXNAHFI-ZDUSSCGKSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a pesticide bactericide, which comprises, by mass, 20-50% of an effective ingredient, 1-3% of a dispersing agent, 4-6% of a wetting agent, 2-3% of a thickening agent, 4-6% of an antifreezing agent, 0.2-0.4% of a preservative, 0.2-0.4% of a defoaming agent and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20. The pesticide bactericide provided by the invention has both protection and treatment effects, and has a good effect on preventing and treating rice blast.
Description
Technical Field
The invention relates to a pesticide bactericide and a preparation method thereof, belonging to the field of pesticide bactericides.
Background
The tricyclazole mainly inhibits the formation of the attached spore melanin, thereby inhibiting the germination of spores and the formation of attached spores, preventing the invasion of germs and reducing the generation of fungus spores, and mainly has the protection effect, so that the tricyclazole is a protective bactericide with strong systemic property, and the active ingredients can be rapidly absorbed by roots, stems and leaves of rice. Tricyclazole is a common agent for preventing and treating rice blast in rice production, and has been used for more than 30 years since the application of the last century in the 80 th year, and although the rice blast in part of areas is reported to be resistant, the large-area resistance generation is not reported, and the tricyclazole belongs to low-resistance risk pesticides. From the practical use, tricyclazole is a specific drug for preventing rice blast, is used before rice blast bacteria invade, has very excellent control effect on protection She Baomiao, but rice blast is a typical multi-cycle disease, can be infected and onset from a rice seedling stage to a grouting setting stage, and is difficult to strictly take the drug before rice blast bacteria infection in the rice planting process. If the rice blast fungus attached spore has completed melanin formation on rice plants and the conidium has invaded, the tricyclazole can prevent the disease from spreading, but the effect of preventing and treating the disease can not be achieved. Meanwhile, in the rice growth process, the weather such as storm, typhoon and the like is frequently encountered, so that the wound of rice leaves is possibly caused, germs can directly enter the rice body to feel diseases, the tricyclazole cannot achieve a prevention effect, and the disease prevention effect is poor. Lei Mei is a weak alkaline antibiotic produced by streptomycete, has strong systemic property, has a certain antibacterial activity on partial gram positive and negative bacteria and certain fungi, has strong penetrability, can be quickly absorbed by plants and transferred to the whole plant, mainly interferes with amino acid metabolism of a bacterial esterase system, affects protein synthesis, and has obvious treatment effect on rice blast. Therefore, after the rice blast is caused, the tricyclazole is compounded with the kasugamycin and other therapeutic agents to be used together, so that the novel leaf and the healthy seedling are well protected. Although both belong to systemic bactericides, the mechanism of action is different, and no report of cross resistance exists at present. The two active ingredients are mixed, so that on one hand, the service life of the medicament for preventing and treating rice blast can be prolonged, the risk of resistance occurrence is avoided or reduced, and on the other hand, the prevention and treatment spectrum of the medicament can be expanded.
The pure tricyclazole is white crystal with melting point 187-188 deg.C and vapor pressure 266.6448X 10-7 Pa at 25 deg.C. The solubility at 25 ℃ is: 1.6g/l water, 33% dichloromethane, 25% ethanol, 25% methanol, 10.4% acetone, 10.4% acetonitrile, 10.0% cyclohexanone, 4.2% benzene, 2.1% xylene, and >500 g/l chloroform. Stable property, difficult decomposition by water and light, and thermal stability. The kasugamycin is stable in acidic or neutral medium, is easy to damage and lose efficacy when meeting alkali, is insoluble in various organic solvents such as methanol, ethanol, propanol, benzene and the like, and is easy to dissolve in water. Because the tricyclazole belongs to a systemic bactericide, the particle size of the original medicine processed by the dosage form directly influences the absorption and utilization of the medicine, and finally influences the control effect of the product, and the smaller the particle size of the processed particles, the better the final drug effect of the product. In the existing pesticide formulation in the field, the product particles of the emulsifiable concentrate and the microemulsion are the finest, but the solubility of the tricyclazole raw material in the conventional organic solvent is not great because of the nature of the tricyclazole raw material, and a large amount of polar solvent is required to be added to process the tricyclazole raw material into the emulsifiable concentrate or the microemulsion, so that the environment is greatly damaged, the processing of the tricyclazole raw material into the emulsifiable concentrate or the microemulsion is not a reasonable formulation choice, and the processing of the tricyclazole raw material into solid wettable powder or granular preparation or a liquid suspension formulation is a reasonable choice. The suspending agent product adopts the wet sanding technology, and materials are repeatedly ground in a sealed grinding device, so that the particle size of the suspending agent product can be processed to be very fine, but the particle size of the suspending agent product can be processed to be 1-2 microns, and the absorption and utilization rate of crops can be greatly improved. However, as the solubility of the tricyclazole technical in water reaches 1.6g/L, the tricyclazole technical belongs to a variety with higher solubility in water, the processed suspending agent product can undergo Oryza in the storage process, so that the crystallization of the product is separated out, the aggregation of small particles is large, the particle size is large, the drug effect is reduced, and even the suspending agent product with high content can not be used because of the hardening of the material bottom caused by Oryza.
Therefore, the kasugamycin and tricyclazole bactericidal composition is limited by the action condition, the component property and the production process, so that the bactericidal composition has poor compatibility and low stability, and the problem that the full play of the drug effect is difficult to realize is solved. Therefore, the combination and the compounding of different effective components are realized, and meanwhile, the limitations of the combination formula and the process are overcome, so that the stability of the bactericide is improved, and the pharmacodynamic action of the bactericidal composition can be enhanced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a pesticide bactericide and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
subject 1
The pesticide bactericide comprises, by mass, 20-50% of an effective component, 1-3% of a dispersing agent, 4-6% of a wetting agent, 2-3% of a thickening agent, 4-6% of an antifreezing agent, 0.2-0.4% of a preservative, 0.2-0.4% of an organosilicon antifoaming agent, 0-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20.
As some preferred embodiments of the present invention, the pesticide fungicide further comprises 0.1% -0.2% ascorbyl palmitate by mass%.
As some preferred embodiments of the present invention, the pesticide bactericide comprises 22% of an active ingredient, 2% of a dispersing agent, 5% of a wetting agent, 2.5% of a thickening agent, 5% of an antifreezing agent, 0.3% of a preservative, 0-0.3% of an organosilicon antifoaming agent, and the balance of water in mass percent; the active ingredients are 1 in mass ratio: kasugamycin and tricyclazole of 10.
As some preferred embodiments of the present invention, the wetting agent comprises at least one of methyl coco polyoxyethylene ether, sodium lauryl ether sulfate, L64 surfactant, and methacrylic acid maleic anhydride copolymer
As some preferred embodiments of the invention, the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:0.8-1.2.
As some preferred embodiments of the present invention, the thickener includes at least one of magnesium aluminum silicate, xanthan gum, polyvinyl alcohol, sesbania gum and white carbon black.
As some preferred embodiments of the present invention, the dispersant includes at least one of lignosulfonate, polycarboxylate, and polyoxyethylene ether phosphate.
As some preferred embodiments of the present invention, the antifreeze agent includes at least one of ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.
As some preferred embodiments of the present invention, the preservative comprises at least one of kathon, sodium benzoate, and potassium sorbate.
As some preferred embodiments of the present invention, the dispersant is a GY-D07 polycarboxylate dispersant; the antifreezing agent is glycol; the preservative is sodium benzoate.
Subject matter II
The invention provides a preparation method of a pesticide bactericide containing the technical subject one, which comprises the following steps:
A. the raw materials comprise, by mass, 20-50% of active ingredients, 1-3% of dispersing agents, 4-6% of wetting agents, 2-3% of thickening agents, 4-6% of antifreezing agents, 0.2-0.4% of preservatives, 0-0.4% of organosilicon antifoaming agents, 0-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
B. deionized tricyclazole, kasugamycin, wetting agent, dispersing agent and 50-70wt% of raw materialsMixing with water, shearing, and grinding to particle size DV 95 And (3) adding the rest deionized water, thickener, antifreezing agent, preservative, organic silicon defoamer and ascorbyl palmitate into the ground material, shearing and stirring, adjusting the pH value to 5.5-7.5, sampling and testing to be qualified, and filling, packaging and warehousing.
As a preferred embodiment of the present invention, the shearing is shearing at a rotational speed of 10000r/min to 14000r/min for 20 to 30min; the grinding temperature is 15-25 ℃.
As a preferred embodiment of the invention, a preparation method of the pesticide bactericide containing the technical subject one comprises the following steps:
A. the raw materials comprise, by mass, 20-50% of active ingredients, 1-3% of dispersing agents, 4-6% of wetting agents, 2-3% of thickening agents, 4-6% of antifreezing agents, 0.2-0.4% of preservative, 0-0.4% of organosilicon antifoaming agents, 0.1-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 50-70wt% deionized water in the raw materials, shearing, and grinding to particle size DV 95 Adding preservative and organic silicon defoamer into the ground material, shearing and stirring to obtain mixed ground material;
C. mixing the rest deionized water, the antifreezing agent and the thickener, and stirring to obtain a thickener solution;
D. homogenizing the mixed and ground material, adding thickener solution and ascorbyl palmitate while homogenizing, adjusting pH to 5.5-7.5, sampling, testing, filling, packaging, and warehousing.
As a preferred embodiment of the present invention, the shearing is shearing at a rotational speed of 10000r/min to 14000r/min for 20 to 30min; the grinding temperature is 15-25 ℃; homogenizing under 20-30MPa for 20-35min.
As a preferred embodiment of the present invention, the pH adjustment is performed using citric acid, malic acid or tartaric acid.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
1. the kasugamycin and the tricyclazole are compounded, so that the invention has the functions of protection and treatment, and has better effect on preventing and treating rice blast. The two compound sterilization mechanisms are different, and the respective sterilization advantages and the complementary effects can be comprehensively exerted. The results of mycelium growth rate measurement show that kasugamycin and tricyclazole have certain inhibitory activity on rice blast fungi, the EC50 value of the kasugamycin is 2.73 mg/L, and the EC50 value of the tricyclazole is 22.65 mg/L.
2. The kasugamycin original drug contains impurities which are easy to be decomposed by microorganisms to cause deterioration, and the preservative is added to delay deterioration but can not prevent deterioration, so the inventor explores to add ascorbyl palmitate to improve the oxidation resistance, but the suspension rate of pesticide bactericide products can not be ensured by adding ascorbyl palmitate, and the L64 surfactant and methacrylic acid maleic anhydride copolymer are compounded and cooperated, so that the suspension rate of pesticide bactericide products can be maintained, the traditional organic silicon defoamer can be replaced, and the foaming performance is reduced.
3. The L64 surfactant and the methacrylic acid maleic anhydride copolymer can also form good synergistic effect with GY-D07 polycarboxylate dispersant, and can effectively inhibit the crystallization phenomenon of the product caused by Oryza curing in the storage process. The GY-D07 polycarboxylate dispersant belongs to water-soluble carboxylate high polymer salt, has a unique amphiphilic structure, is firmly adsorbed on the surfaces of original drug particles by means of self anchoring groups in a pesticide suspension system, effectively reduces the interfacial free energy of the original drug particles, reduces the merging trend among the pesticide particles, simultaneously ionizes the dispersant, forms an electric double layer on the surfaces of the original drug particles, and stably suspends and disperses the dispersed original drug particles in the suspension system by means of steric hindrance formed by the electric double layer and the high polymer. The L64 surfactant is a block copolymer surfactant of EO and PO, and has the surface active effects of emulsification, dispersion, wetting and the like.
4. The invention improves the compatibility of the system by precisely controlling and regulating the adding mode of the thickening agent and other auxiliary agents, thereby reducing the collision probability of particles, prolonging the sedimentation time of the particles, keeping the storage stability and improving the suspension rate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
All the substances in the formula can be purchased from the market, and the polycarboxylate is GY-D07 polycarboxylate dispersant and is purchased from China chemical group company; l64 surfactant, available from Zhejiang chemical Co., ltd; the methacrylic acid maleic anhydride copolymer was purchased from the Guangzhou Weber technologies Co., ltd, the average molecular weight was 6000, and the white carbon black was purchased from the Jinan Kasong chemical Co., ltd; the silicone defoamer was purchased from chemical industry limited in guangzhou, model FTRT AF1551; the following effective components of kasugamycin and tricyclazole are kasugamycin original medicine and tricyclazole original medicine. The grinding temperatures are controlled between 15 and 25 ℃.
Example 1
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.2% of organosilicon defoamer and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is an L64 surfactant; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic and organic silicon defoamer into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, filling, packaging and warehousing.
Example 2
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 20% of active ingredients, 3% of dispersing agent sodium lignin sulfonate, 4% of wetting agent, 2% of thickener, 4% of antifreeze, 0.4% of preservative kathon and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3; the wetting agent is prepared from the following components in percentage by mass: 1:1 methyl cocoyl polyoxyethylene ether, sodium lauryl ether sulfate and maleic anhydride methacrylate copolymer; the thickener is aluminum magnesium silicate; the antifreezing agent is propylene glycol and glycerol with the mass ratio of 1:1;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 50wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent and antiseptic into the ground material, shearing at 10000r/min for 30min, stirring, adjusting pH to 7.5 with tartaric acid, sampling, testing, packaging, and warehousing.
Example 3
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.2% of organosilicon defoamer, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is an L64 surfactant; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic, organosilicon defoamer and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, filling, packaging, and warehousing.
Example 4
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.2% of organosilicon defoamer, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is methacrylic acid maleic anhydride copolymer; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic, organosilicon defoamer and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, filling, packaging, and warehousing.
Example 5
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.2% of organosilicon defoamer, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is an L64 surfactant and methacrylic acid maleic anhydride copolymer with a mass ratio of 1:1; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Less than or equal to 5.0 mu m, adding the rest deionized water, thickener, antifreezing agent, preservative and organic silicon defoaming agent into the ground materialShearing agent and ascorbyl palmitate for 25min at 12000r/min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, packaging, and warehousing.
Example 6
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 20% of active ingredients, 3% of dispersing agent sodium lignin sulfonate, 4% of wetting agent, 2% of thickener aluminum magnesium silicate, 4% of antifreeze, 0.4% of preservative pinocembrin, 0.2% of organosilicon defoamer, 0.1% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-3; the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1.2; the method comprises the steps of carrying out a first treatment on the surface of the The antifreezing agent is propylene glycol and glycerol with the mass ratio of 1:1;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest 40wt% deionized water, thickener, antifreezing agent, antiseptic, organosilicon defoamer and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, and packaging.
Example 7
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 50% of active ingredients, 1% of dispersing agent tristyrylphenol polyoxyethylene ether phosphate, 6% of wetting agent, 3% of thickening agent, 6% of antifreeze, 0.2% of preservative potassium sorbate, 0.4% of organosilicon defoamer, 0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-20; the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:0.8; the mass ratio of the thickener is 1:1:1, magnesium aluminum silicate, polyvinyl alcohol and white carbon black;
B. tricyclazole, kasugamycin,Mixing wetting agent, dispersant and 60wt% deionized water in the raw materials, shearing at 12000r/min for 25min, and grinding to particle size DV 95 Adding the rest 40wt% deionized water, thickener, antifreezing agent, antiseptic, organosilicon defoamer and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, and packaging.
Example 8
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is an L64 surfactant; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, packaging, and warehousing.
Example 9
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is methacrylic acid maleic anhydride copolymer; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, packaging, and warehousing.
Example 10
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is an L64 surfactant and methacrylic acid maleic anhydride copolymer with a mass ratio of 1:1; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding the rest deionized water, thickener, antifreezing agent, antiseptic and ascorbyl palmitate into the ground material, shearing at 12000r/min for 25min, stirring, adjusting pH to 6.0 with citric acid, sampling, testing, packaging, and warehousing.
Example 11
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding preservative and organosilicon defoamer into the ground material, shearing for 25min at the rotation speed of 12000r/min, and stirring to obtain mixed ground material;
C. mixing the rest deionized water, the antifreezing agent and the thickener, and stirring to obtain a thickener solution;
D. homogenizing the mixed and ground materials under the pressure of 25MPa for 30min, adding thickener solution and ascorbyl palmitate while homogenizing, adjusting pH to 6.0, sampling, testing, and packaging.
Comparative example 1
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding preservative, organosilicon defoamer and ascorbyl palmitate into the ground material, shearing for 25min at the rotating speed of 12000r/min, and stirring to obtain mixed ground material;
C. mixing the rest deionized water, the antifreezing agent and the thickener, and stirring to obtain a thickener solution;
D. homogenizing the mixed and ground materials under the pressure of 25MPa for 30min, adding thickener solution while homogenizing, adjusting pH to 6.0, sampling, testing, filling, packaging, and warehousing.
Comparative example 2
A preparation method of a pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 22% of active ingredients, 2% of GY-D07 polycarboxylate dispersant, 5% of wetting agent, 2.5% of thickener, 5% of antifreeze glycol, 0.3% of preservative sodium benzoate, 0.15% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1-10; the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1; the mass ratio of the thickener is 1:0.4 xanthan gum and sesbania gum;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 60wt% deionized water in the raw materials, shearing for 25min at a rotation speed of 12000r/min, and grinding to obtain a particle size DV 95 Adding preservative and organosilicon defoamer into the ground material, shearing for 25min at the rotation speed of 12000r/min, and stirring to obtain mixed ground material;
C. mixing the rest deionized water, the antifreezing agent and the thickener, and stirring to obtain a thickener solution;
D. mixing the mixed grinding material, the thickener solution and the ascorbyl palmitate, homogenizing under the pressure of 25MPa for 30min, adjusting the pH value to 6.0, sampling, testing, filling, packaging and warehousing.
The bactericides of examples 1 to 11 and comparative examples 1 to 2 were tested for their suspension property, heat storage stability, long-lasting foamability and the like. The suspension rate is measured by referring to GB/T14825-2006 method for measuring suspension rate of pesticides, and the decomposition rate is measured by referring to GB/T19136-2003 standard for thermal storage stability of pesticides. Referring to a method for measuring the persistent foamability of a GB T28137-2011 pesticide, standard hard water specified in GB/T28137-2011 standard (the standard hard water specified in GB/T28137-2011 is calculated by calcium carbonate, 342 mg/L) is diluted for 250 times, and then a 250ml measuring cylinder with a plug is used for measuring the foamability for 1 min;
the pesticidal bactericides of examples 1 to 11 and comparative examples 1 to 2 of the present invention were used for actual sterilization to control rice blast, and the amount of the active ingredient was 198ga.i./hm 2 The pesticide application method is spraying, pesticide field efficacy test is carried out, and the results are shown in table 1.
TABLE 1
Because of space limitation, only the specific content of the efficacy test of the pesticide bactericide obtained in example 5 is shown, and the efficacy test methods of other examples are the same. The pesticide bactericide of the embodiment 5 of the invention is used for actually sterilizing and controlling rice blast, and is used for pesticide field efficacy test, and the specific contents of the test are as follows:
protocol docket number 2017-eight source bacteria-1, sample sealing number wing 2017280, test year 2017, test site: yunnan, test unit: the application method of the plant protection college of Yunnan agricultural university is as follows: spraying, and applying at the beginning of onset.
The dosage and treatment number of the medicine are shown in Table 2-1.
TABLE 2-1 test design of reagents for test
4.1 Meteorological and soil data
Gusts of rain on the day of the first application (day 9 and 11), breeze, air temperature of 20-28 ℃ and air humidity of 86%; the day of the second application (day 18 of 9 months) is slightly rainy, the temperature is 20-28 ℃, the air humidity is 85%, and the wind is slight. No rain was observed within 5 hours after the two doses. The test period is mainly rainy days, the highest daily air temperature is 30 ℃, and the lowest daily air temperature is 19 ℃. See Table 2-2 for details of the weather data.
TABLE 2 Meteorological data Table during test period
/>
5. Results and analysis
Test results list 2-3 of field efficacy test for controlling rice blast using a test agent 22% Chunlei tricyclazole suspension (example 2 agent). As can be seen from tables 2 to 3, every 667m 2 50ml, 55 ml and 60 ml of 22% kasugamycin and tricyclazole suspending agent and 100 ml of 2% kasugamycin water aqua and 20 g of 75% tricyclazole water dispersible granule are used for preventing and treating rice blast, and the prevention effect of 8 days after the first administration is 67.19%, 74.51%, 81.76%, 69.82% and 68.96% respectively. The prevention effect 7 days after the second administration is 70.61%, 82.44%, 90.17%, 73.21% and 77.73% respectively. The statistical analysis of the prevention effect 7 days after the second medicine shows that the prevention effect difference of 3 doses of 22% kasugamy-tricyclazole suspending agent on rice blast is very obvious, namely, the prevention effect is very obviously improved along with the increase of the dosage, and the treatment of 55 ml of 22% kasugamy-tricyclazole suspending agent is very obviously different from 100 ml of a control medicament 2% kasugamycin aqua and 75% tricyclazole suspending agent20 g of the azole water dispersible granule has no significant difference in control effect (tables 2-3).
Table 2-3 results of field efficacy test of 22% Chunlei-tricyclazole suspension for controlling rice blast
7-day second drug investigation
From the results, the 22% spring thunder and tricyclazole suspending agent (the medicament of the example 2) of the test medicament has better control effect on rice blast, and each 667m 2 The control effect on rice blast can reach 82.44% -90.17% when 55-60 ml is used twice consecutively. The dosage of the test agent is safe to rice, has no phytotoxicity and no adverse effect on environment, and is suitable for large-area popularization and use.
According to the invention, after the kasugamycin and the tricyclazole are mixed, no antagonism is generated, and a formula screening test result shows that after the kasugamycin and the tricyclazole are mixed within the range of 1:3-1:20, no antagonism is generated. Wherein, after the two components are mixed according to the proportion of 1:6, 1:8, 1:10, 1:12 and 1:14, the SR values are respectively 1.60, 1.65, 1.62, 1.55 and 1.60, which shows that the synergistic effect is achieved.
According to the invention, the result of mycelium growth rate measurement shows that kasugamycin and tricyclazole have certain inhibitory activity on rice blast fungi, the EC50 value of kasugamycin is 2.73 mg/L, and the EC50 value of tricyclazole is 22.65 mg/L.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. The pesticide bactericide is characterized by comprising, by mass, 20-50% of an effective ingredient, 1-3% of a dispersing agent, 4-6% of a wetting agent, 2-3% of a thickening agent, 4-6% of an antifreezing agent, 0.2-0.4% of a preservative, 0-0.4% of an organosilicon antifoaming agent, 0.1-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1;
the preparation method of the pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 20-50% of active ingredients, 1-3% of dispersing agents, 4-6% of wetting agents, 2-3% of thickening agents, 4-6% of antifreezing agents, 0.2-0.4% of preservatives, 0-0.4% of organosilicon antifoaming agents, 0.1-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 50-70wt% deionized water in the raw materials, shearing, and grinding to particle size DV 95 And (3) adding the rest deionized water, thickener, antifreezing agent, preservative, organic silicon defoamer and ascorbyl palmitate into the ground material, shearing and stirring, adjusting the pH value to 5.5-7.5, sampling and testing to be qualified, and filling, packaging and warehousing.
2. The pesticide bactericide is characterized by comprising, by mass, 20-50% of an effective ingredient, 1-3% of a dispersing agent, 4-6% of a wetting agent, 2-3% of a thickening agent, 4-6% of an antifreezing agent, 0.2-0.4% of a preservative, 0-0.4% of an organosilicon antifoaming agent, 0.1-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
the wetting agent is L64 surfactant and methacrylic acid maleic anhydride copolymer with the mass ratio of 1:1;
the preparation method of the pesticide bactericide comprises the following steps:
A. the raw materials comprise, by mass, 20-50% of active ingredients, 1-3% of dispersing agents, 4-6% of wetting agents, 2-3% of thickening agents, 4-6% of antifreezing agents, 0.2-0.4% of preservative, 0-0.4% of organosilicon antifoaming agents, 0.1-0.2% of ascorbyl palmitate and the balance of water; the active ingredients comprise kasugamycin and tricyclazole with the mass ratio of 1:3-1:20;
B. mixing tricyclazole, kasugamycin, wetting agent, dispersing agent and 50-70wt% deionized water in the raw materials, shearing, and grinding to particle size DV 95 Adding preservative and organic silicon defoamer into the ground material, shearing and stirring to obtain mixed ground material;
C. mixing the rest deionized water, the antifreezing agent and the thickener, and stirring to obtain a thickener solution;
D. homogenizing the mixed and ground material, adding thickener solution and ascorbyl palmitate while homogenizing, adjusting pH to 5.5-7.5, sampling, testing, filling, packaging, and warehousing.
3. A pesticide fungicide according to claim 1 or claim 2, in which the thickener comprises at least one of magnesium aluminium silicate, xanthan gum, polyvinyl alcohol, sesbania gum and white carbon black.
4. A pesticide fungicide according to claim 1 or claim 2, in which the dispersant comprises at least one of a lignosulfonate, a polycarboxylate and a polyoxyethylene ether phosphate.
5. A pesticide fungicide according to claim 1 or 2, in which the antifreeze comprises at least one of ethylene glycol, propylene glycol, glycerol, polyethylene glycol.
6. A pesticide fungicide according to claim 1 or claim 2, in which the preservative comprises at least one of pinus sylvestris, sodium benzoate and potassium sorbate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210800273.9A CN115024324B (en) | 2022-07-08 | 2022-07-08 | Pesticide bactericide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210800273.9A CN115024324B (en) | 2022-07-08 | 2022-07-08 | Pesticide bactericide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115024324A CN115024324A (en) | 2022-09-09 |
| CN115024324B true CN115024324B (en) | 2024-01-23 |
Family
ID=83129075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210800273.9A Active CN115024324B (en) | 2022-07-08 | 2022-07-08 | Pesticide bactericide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115024324B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102057921A (en) * | 2010-12-14 | 2011-05-18 | 江苏省绿盾植保农药实验有限公司 | Fungicide containing tricyclazole and kasugamycin |
| CN111903689A (en) * | 2020-07-31 | 2020-11-10 | 上海悦联生物科技有限公司 | Bactericide containing picoxystrobin and propiconazole and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9247742B2 (en) * | 2012-12-31 | 2016-02-02 | Dow Agrosciences Llc | Synergistic fungicidal compositions |
-
2022
- 2022-07-08 CN CN202210800273.9A patent/CN115024324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102057921A (en) * | 2010-12-14 | 2011-05-18 | 江苏省绿盾植保农药实验有限公司 | Fungicide containing tricyclazole and kasugamycin |
| CN111903689A (en) * | 2020-07-31 | 2020-11-10 | 上海悦联生物科技有限公司 | Bactericide containing picoxystrobin and propiconazole and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 22％春雷霉素•三环唑悬浮剂对稻瘟病的田间防效试验;任家琼;《植物医生》;第33卷(第4期);第74-77页 * |
| 沈晋良 主编.《农药加工与管理》.中国农业出版社,2002,第104-108页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115024324A (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111567531A (en) | Seed coating agent for spring rape and application thereof | |
| CN115024324B (en) | Pesticide bactericide and preparation method thereof | |
| CN103493831A (en) | Insecticide composition with insecticides of pyriminostrobin and tetronic acid | |
| CN114467928B (en) | Suspending agent containing dimethomorph and cyazofamid and preparation method thereof | |
| CN111165498A (en) | Bactericidal composition containing Dichlorobentiazox and fluorophenyletheramide, and application and preparation method thereof | |
| CN111685117B (en) | Bactericidal composition containing metrafenone and flutolanil and application thereof | |
| CN104798796B (en) | A kind of bactericidal composition containing benzo alkene fluorine bacterium azoles and application thereof | |
| CN107691456B (en) | Bactericidal composition containing fluoxastrobin and shenqinmycin | |
| CN114097787A (en) | Compound weeding composition containing tembotrione and ametryn and application thereof | |
| CN109169675B (en) | Bactericidal composition containing fluxapyroxad and oxine-copper | |
| CN107926951B (en) | Bactericidal composition containing terpene alcohol and trifloxystrobin and application thereof | |
| CN111280170A (en) | Bactericidal composition and application thereof | |
| CN107711868B (en) | Bactericidal composition containing prochloraz and biological antibacterial substance HSAF and application thereof | |
| CN110583669B (en) | Bactericidal composition for melon diseases | |
| CN111955464B (en) | Sterilization composition containing chlorofluoromethrin | |
| CN109479886A (en) | A kind of pesticide and preparation method containing prothioconazoles and probenazole | |
| CN114391545B (en) | Pesticide composition containing bixafen and copper quinolinate and application thereof | |
| CN104397019B (en) | Bactericidal composition containing boscalid and sulfur | |
| CN111955473B (en) | Sterilization composition containing thiophanate methyl and application thereof | |
| CN113907083B (en) | Compound bactericide for preventing and treating pepper anthracnose | |
| CN114938808B (en) | Magnolol and nuciferine pharmaceutical composition and preparation method thereof | |
| CN114766492B (en) | Pesticide composition containing bixafen and application thereof | |
| CN115251080B (en) | Weeding composition for preventing and treating wild spotted maigre and application thereof | |
| CN111838161A (en) | Pyridachlorometyl and fluorobenzene ether amide-containing bactericidal composition and application thereof | |
| CN107114393B (en) | Preparation and application of suspended seed coating agent for preventing and treating cyst nematodes of wheat crops |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |