CN1268214C - 含有大黄提取物的杀菌剂及其组合物 - Google Patents
含有大黄提取物的杀菌剂及其组合物 Download PDFInfo
- Publication number
- CN1268214C CN1268214C CN 02123720 CN02123720A CN1268214C CN 1268214 C CN1268214 C CN 1268214C CN 02123720 CN02123720 CN 02123720 CN 02123720 A CN02123720 A CN 02123720A CN 1268214 C CN1268214 C CN 1268214C
- Authority
- CN
- China
- Prior art keywords
- consumption
- archen
- chrysophanol
- extract
- emodin
- 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.)
- Expired - Lifetime
Links
- 239000000284 extract Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 241000219061 Rheum Species 0.000 title abstract description 4
- 235000009411 Rheum rhabarbarum Nutrition 0.000 title abstract description 4
- 230000002070 germicidal effect Effects 0.000 title abstract 3
- LQGUBLBATBMXHT-UHFFFAOYSA-N chrysophanol Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O LQGUBLBATBMXHT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 240000001745 Rheum palmatum Species 0.000 claims abstract description 29
- YDQWDHRMZQUTBA-UHFFFAOYSA-N Aloe emodin Chemical compound C1=CC=C2C(=O)C3=CC(CO)=CC(O)=C3C(=O)C2=C1O YDQWDHRMZQUTBA-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 235000008081 Rheum officinale Nutrition 0.000 claims description 42
- NZPQWZZXRKZCDU-UHFFFAOYSA-N chrysophanol Natural products Cc1cc(O)c2C(=O)c3c(O)cccc3Oc2c1 NZPQWZZXRKZCDU-UHFFFAOYSA-N 0.000 claims description 21
- 150000003851 azoles Chemical class 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 239000003899 bactericide agent Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- AXTGDCSMTYGJND-UHFFFAOYSA-N 1-dodecylazepan-2-one Chemical compound CCCCCCCCCCCCN1CCCCCC1=O AXTGDCSMTYGJND-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 2
- 238000009313 farming Methods 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 claims 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims 1
- 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 claims 1
- 241000196324 Embryophyta Species 0.000 abstract description 7
- PKUBGLYEOAJPEG-UHFFFAOYSA-N physcion Natural products C1=C(C)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O PKUBGLYEOAJPEG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 235000008090 Rheum palmatum Nutrition 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- VWDXGKUTGQJJHJ-UHFFFAOYSA-N Catenarin Natural products C1=C(O)C=C2C(=O)C3=C(O)C(C)=CC(O)=C3C(=O)C2=C1O VWDXGKUTGQJJHJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010282 Emodin Substances 0.000 abstract 1
- RBLJKYCRSCQLRP-UHFFFAOYSA-N Emodin-dianthron Natural products O=C1C2=CC(C)=CC(O)=C2C(=O)C2=C1CC(=O)C=C2O RBLJKYCRSCQLRP-UHFFFAOYSA-N 0.000 abstract 1
- YOOXNSPYGCZLAX-UHFFFAOYSA-N Helminthosporin Natural products C1=CC(O)=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O YOOXNSPYGCZLAX-UHFFFAOYSA-N 0.000 abstract 1
- NTGIIKCGBNGQAR-UHFFFAOYSA-N Rheoemodin Natural products C1=C(O)C=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1O NTGIIKCGBNGQAR-UHFFFAOYSA-N 0.000 abstract 1
- RHMXXJGYXNZAPX-UHFFFAOYSA-N emodin Chemical compound C1=C(O)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O RHMXXJGYXNZAPX-UHFFFAOYSA-N 0.000 abstract 1
- VASFLQKDXBAWEL-UHFFFAOYSA-N emodin Natural products OC1=C(OC2=C(C=CC(=C2C1=O)O)O)C1=CC=C(C=C1)O VASFLQKDXBAWEL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003090 pesticide formulation Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 34
- 240000008067 Cucumis sativus Species 0.000 description 18
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 18
- 240000004980 Rheum officinale Species 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 230000003449 preventive effect Effects 0.000 description 15
- 241000221785 Erysiphales Species 0.000 description 14
- 201000010099 disease Diseases 0.000 description 12
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 12
- 238000011081 inoculation Methods 0.000 description 12
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- FFWOKTFYGVYKIR-UHFFFAOYSA-N physcion Chemical compound C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1O FFWOKTFYGVYKIR-UHFFFAOYSA-N 0.000 description 8
- QNBTYORWCCMPQP-JXAWBTAJSA-N (Z)-dimethomorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(Cl)=CC=1)=C/C(=O)N1CCOCC1 QNBTYORWCCMPQP-JXAWBTAJSA-N 0.000 description 7
- 239000005761 Dimethomorph Substances 0.000 description 7
- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000000287 crude extract Substances 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- UGNZSMZSJYOGNX-UHFFFAOYSA-N Isoviocristine Natural products O=C1C=C(C)C(=O)C2=CC3=CC(OC)=CC(O)=C3C(O)=C21 UGNZSMZSJYOGNX-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WLXGUTUUWXVZNM-UHFFFAOYSA-N anthraglycoside A Natural products C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1OC1OC(CO)C(O)C(O)C1O WLXGUTUUWXVZNM-UHFFFAOYSA-N 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 ester class of phthalic acid dimethyl ester Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- KKDONKAYVYTWGY-UHFFFAOYSA-M sodium;2-(methylamino)ethanesulfonate Chemical compound [Na+].CNCCS([O-])(=O)=O KKDONKAYVYTWGY-UHFFFAOYSA-M 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000001225 therapeutic effect Effects 0.000 description 4
- 241000190150 Bipolaris sorokiniana Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 241000332749 Setosphaeria turcica Species 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000007900 aqueous suspension Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000123650 Botrytis cinerea Species 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 241000411851 herbal medicine Species 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000001018 virulence Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GAPYETXMWCTXDQ-UHFFFAOYSA-N 2-hydroxyethyl hydrogen sulfate Chemical compound OCCOS(O)(=O)=O GAPYETXMWCTXDQ-UHFFFAOYSA-N 0.000 description 1
- 241000352690 Alternaria kikuchiana Species 0.000 description 1
- 241000412366 Alternaria mali Species 0.000 description 1
- 241000212254 Alternaria porri Species 0.000 description 1
- 241000213004 Alternaria solani Species 0.000 description 1
- 241000555706 Botryosphaeria dothidea Species 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 241000410367 Clerodendrum thomsoniae Species 0.000 description 1
- 241000222201 Colletotrichum capsici Species 0.000 description 1
- 241001466031 Colletotrichum gossypii Species 0.000 description 1
- 241001429695 Colletotrichum graminicola Species 0.000 description 1
- 244000247747 Coptis groenlandica Species 0.000 description 1
- 235000002991 Coptis groenlandica Nutrition 0.000 description 1
- 241000223211 Curvularia lunata Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000223195 Fusarium graminearum Species 0.000 description 1
- 241000223221 Fusarium oxysporum Species 0.000 description 1
- 241000233732 Fusarium verticillioides Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 235000013717 Houttuynia Nutrition 0.000 description 1
- 240000000691 Houttuynia cordata Species 0.000 description 1
- 244000309489 Leptosphaeria maydis Species 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 241001499733 Plantago asiatica Species 0.000 description 1
- 241000317981 Podosphaera fuliginea Species 0.000 description 1
- 241000813090 Rhizoctonia solani Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241001123668 Verticillium dahliae Species 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 241001609931 bacterium 20 Species 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical class OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 239000002855 microbicide agent Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000009329 organic farming Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种大黄提取物及其组合物，属于农药领域。本发明是从一种植物大黄(拉丁文名称为：Rheum palmatum)中提取大黄素、大黄酚、芦荟大黄素及其二种、三种混合物以及将它们制成各种农药剂型用于作物杀菌。实验证明，本发明的生物农药防治效果与化学农药相当。
Description
技术领域
本发明涉及一种大黄提取物及其组合物，本发明属于农药领域。
技术背景
随着人类社会的发展，人们对环境保护及食品安全的要求越来越高，“绿色农业”、“有机农业”已成为农业发展的方向。而伴随着人类活动的加剧，环境恶化日趋严重，病虫害危害更为频繁。能够有效地控制植物病原菌生长并能把农药残留降低至最低，并为人们提供无公害农产品一直是农药领域的研究人员所追求的，利用中草药为原料制造植物杀菌杀虫剂成为实现上述目的有效途径之一。中国专利申请00129782公开了一种以黄连、鱼腥草、薄荷、大黄、车前草为原料制成植物农药的方法。中国专利申请01127595公开了一种从大黄提取液分离出大黄总游离蒽醌类化合物的方法，它有如下步骤：1.将大黄提取液加酸后加热水解，优选的酸是盐酸，2.将水解液加碱调节pH至8-10，3.将碱化后的水解液过阴离子交换树脂分离柱，弃去流出液，用水洗至中性，4.用氢氧化钾一醇溶液洗脱，收集洗脱液，5.在洗脱液中加水或不加水后蒸去醇，然后加酸沉淀出大黄总游离蒽醌，主要为大黄酸、大黄素、芦荟大黄素、大黄酚、大黄素甲醚。但这些技术均因研究不深入或者可操作性不强而无法实施。本发明通过大量试验，从中药大黄中提取一系列的化合物，经过大量的药效试验表明，它对植物的很多的病原具有很好的防治作用，并且与环境相容，具有残留低、防效高、杀菌谱广等特点。
发明内容
本发明是从一种植物大黄(拉丁文名称为：Rheum palmatum)中提取大黄素、大黄酚、芦荟大黄素及其二种、三种混合物(以下简称大黄提取物)以及将它们制成各种农药剂型用于作物杀菌。
一种含有大黄提取物的杀菌剂，其特征在于该杀菌剂含有大黄酚和/或大黄素和/或芦荟大黄素。
本发明的大黄提取物大黄素、大黄酚、芦荟大黄素及其二种、三种混合物可以和其他化学杀菌剂混配成组合物，本发明所述的化学杀菌剂可以是烯唑醇、霜脲氰、烯酰吗啉等之中的任一种；进一步说，本发明的组合物含有0.01％---90％的大黄素和/或大黄酚和/或芦荟大黄素等大黄提取物和0.01％---90％的烯唑醇或霜脲氰或烯酰吗啉。
利用上述本发明所说的组合物，配以本领域内技术人员公知助剂(包括溶剂、填充物、增效剂等)可以制成本发明的多种剂型，其有效成分含量为：
大黄提取物大黄素和/或大黄酚和/或芦荟大黄素0.01％---90％
烯唑醇或霜脲氰或烯酰吗啉 0.01％---90％
本发明可能加工的剂型是：
A、乳油
B、可湿性粉剂
C、油悬浮剂
D、水悬浮剂
A、乳油是通过将有效成分溶在一种或多种有机溶剂中，用于本发明的溶剂可以是甲醇、乙醇、氯仿、二甲苯、甲苯等之中的一种或多种组合物；用于本发明的乳化剂可以是脂肪醇聚乙二醇硫酸盐、脂肪酰胺N-甲基牛黄酸钠盐、脂肪醇聚氧乙烯醚硫酸钠之中的一种或多种物质，通常用量为1---30％；本发明还包含渗透剂T、氮酮、YZ-901，通常用量为0.1---20％。
B、可湿性粉剂是在水中可均匀分散的制剂，本发明的可湿性粉剂除加有白碳黑、轻质碳酸钙、陶土、硅藻土等稀释剂或惰性物质以外，它含有离子型或非离子型表面活性剂(润湿剂、分散剂)，例如：脂肪醇聚乙二醇醚硫酸盐，脂肪酰胺N-甲基牛黄酸钠盐，脂肪醇聚氧乙烯醚硫酸钠，十二烷基苯磺酸钠-钙，木质素磺酸钠-钙，SOPA等之中的一种或多种物质，含量为1-30％；本发明还包含渗透剂T、氮酮、YZ-901通常用量为0.1---20％。
C、油悬浮剂是由原药、表面活性剂加入矿物油或植物油而制成，本发明的表面活性剂包括邻苯二甲酸二甲脂、丁脂、二异丁脂、二月桂醇酯、二环酯、二环乙酯、二环辛酯及脂肪酸、脂肪醇的液体酯类，通常用量1-80％；可做乳化剂的脂肪醇聚乙二醇醚硫酸盐、脂肪酰胺N-甲基牛磺酸钠盐、脂肪醇聚氧乙烯醚硫酸钠、十二烷基苯磺酸钠-钙、木质素磺酸钠-钙、SOPA，通常用量1-30％。
D、水悬浮剂是将大黄的提取物与烯唑醇或霜脲氰或烯酰吗啉进行混用，在加入增效剂、助剂后，经过球磨、砂磨制成的制剂，本发明的助剂可以是脂肪醇聚乙二醇醚硫酸盐、脂肪酰胺N-甲基牛磺酸钠盐、脂肪醇聚氧乙烯醚硫酸钠、十二烷基苯磺酸钠-钙，木质素磺酸钠-钙、烷基酚聚氧乙烯醚、三苯乙基苯酚聚氧乙烯之中的一种或多种物质，通常用量1---30％，本发明还含有渗透剂T，通常用量0.1---30％，乙二醇、CMC、黄原胶通常用量0.1---10％。
本发明杀菌剂组合物的优选配比是(重量百分比)：
大黄素和/或大黄酚和/或芦荟大黄素 0.1---60％
烯唑醇或霜脲氰或烯酰吗啉 0.1---90％
助剂为OP---10、0201、0203、农乳500、1600、1601、1602、2201、0208、十二烷基苯黄酸钠-钙，木质素黄酸钠-钙、SOPA中的任意一种或多种组合物，通常用量1---30％。
增效剂为渗透剂T、氮酮、YZ---901中的任意一种或多种组合物，通常用量1---30％。
填充物为CMC、黄原胶、白碳黑、陶土、硅藻土中的的任意一种或多种组合物，通常用量0.1---80％。
按照上述配比称取各组分，经配制加工可制成本发明的可湿性粉剂。
本发明大黄素杀菌剂的最佳配方为：
大黄素 0.2％
SOPA 15％
乙醇 20％
二甲苯 补足至100％
本发明杀菌剂较已有的技术相比有如下优点：
1、无残留。本发明的产品是无公害农药。
2、杀菌谱广对多种菌具有很好的防治作用。
3、增效作用明显。
附图简要说明：
图1为本发明大黄主要成分提取流程图
图2为本发明大黄提取物对黄瓜白粉病的防效变化曲线
实施方式：
本发明大黄提取物防治黄瓜白粉病的研究报告
1材料和方法
1.1材料
1.1.1植物材料 大黄(拉丁文名称为：Rheum palmatum)
11.2菌种 黄瓜白粉病菌(Sphaerotheca fuliginea)(采自河北省植保所)；番茄灰霉病菌(Botrytis cinerea)、小麦根腐病菌(Cochliobolus sativus)等20种致病菌(河北农大毒素室提供)
1.1.3黄瓜品种 长春密刺(承德长城种业公司)
1.1.4化学药剂 15％粉锈宁WP(张家港市第二农药厂)；20％腈菌唑WP(浙江一帆农药厂)
1.1.5药品及仪器
无水乙醇、乙醚、碳酸钠、碳酸氢钠、盐酸、氯仿、吡啶、异戊醇(均为分析纯)Fs-100小型粉碎机、旋转蒸发器、离心机
1.2方法
1.2.1大黄粗提物的初筛
1.2.1.1大黄粗提物的制备
大黄粉碎→提取(中草药∶80％乙醇＝1∶5(w/v))→振荡(2d，150r·min-1，25℃)→离心(3500r·min-1，20min)取上清液→40℃旋转蒸发→用80％乙醇定容(药液毫升数与大黄克数相等)→4℃冰箱保存备用。
1.2.1.2黄瓜苗的培育
采用无土栽培方法，参照文献介绍的塑料日光温室春茬早黄瓜栽培技术。
1.2.1.3白粉菌菌种的保存
将用于保存菌种的黄瓜苗与测试所用的黄瓜苗隔离，接种，在20℃～24℃的温室中培育备用。
1.2.1.4接种
采接种后9天的发病叶片，用毛笔将分生孢子刷于盛有清水的烧杯中，将其配成在10×10倍显微镜下每视野约20个分生孢子的悬浮液。然后将孢子悬浮液均匀的喷在破心期植株的叶片上。
1.2.1.5保护和治疗效果测定
在黄瓜破心期喷提取物，设清水、80％乙醇和化学药剂(保护效果测试用粉锈宁1000倍液，治疗效果测试用腈菌唑3000倍液)对照，每个处理10株，置于24℃～26℃下，塑料布覆盖保湿，待清水对照充分发病时调查各处理病情，记录严重度，计算病情指数和防效。保护和治疗效果分别指接种前24h和接种后24h喷药的效果(保护作用测试用50倍液，治疗作用测试用100倍液)。
病情指数(％)＝平均严重度×普遍率×100
防效(％)＝(对照病指-处理病指)/对照病情指数×100
1.2.2毒力测定
将粗提物分别稀释600、800、1000、1200、1400、1600、1800倍，然后测试其对黄瓜白粉病的保护作用，计算出Ec50和Ec90。
1.2.3持效期测试
在接种前1、2、3、4、5、6d用粗提物100倍液处理10株幼苗，且在接种前1d设清水、80％乙醇、粉锈宁1000倍液等对照处理而后统一接种，待清水对照严重发病时调查各处理严重度并记录结果，计算病情指数和防效。
1.2.4抑菌谱的测试
将1mL提取液加入到100mL融化的PDA培养基中，倒皿(d＝9cm)，用d＝0.6cm的打孔器打菌盘接种(设清水、80％乙醇作对照，每处理4次重复)。放入25℃恒温培养箱中培养，待对照菌落长到7cm左右测量菌落直径，并计算抑制率。
抑制率(％)＝(CK净生长量-处理净生长量)/CK净生长量×100
注：净生长量＝菌落直径-菌盘直径
1.2.5大黄中主要成分活性测试
将标准品大黄酸、大黄酚分别用吡啶、无水乙醇溶解稀释500x、1000x，然后加水继续稀释1万、5万、10万、20万倍4个浓度，大黄素用10％乙醇稀释500x和1000x，然后设清水、10％、2％、1％、0.5％吡啶和10％、2％、1％、0.5％乙醇对照测其活性。同时用所提取到的大黄素、大黄酸、大黄酚与大黄素甲醚等粗提品1000倍液测试对黄瓜白粉病菌的保护活性。
1.2.7与化学药剂配比试验
将粗提物制成0.2％水剂，与烯唑醇按有效成分比3∶1，1∶1，1∶3等3个比例进行混配，然后分别测其和各单剂的Ec50，计算其共毒系数。
2结果与分析
2.1大黄粗提物对黄瓜白粉病的保护和治疗作用的测试结果与分析
2.1.1保护作用测试结果
大黄植物粗提物活性较高，其50倍液防效与化学药剂粉锈宁1000倍液处于同一显著水平。
表1 大黄提取物对黄瓜白粉病的保护效果测试结果
| 处理 | 平均严重度/％ | 普遍率/％ | 病情指数/％ | 防效/％ | 差异显著性 |
| 粉锈宁大黄80％乙醇清水 | 2.0023.2586.0086.25 | 40.00100.00100.00100.00 | 0.8023.2586.0086.25 | 98.9073.040.290.00 | nsns**** |
| 粉锈宁大黄清水80％乙醇 | 4.0030.0083.0088.00 | 40.00100.00100.00100.00 | 1.6024.0083.0088.00 | 98.0771.080.00-6.02 | nsns**** |
注：ns表示处理与粉锈宁之间差异不显著；*表示处理与粉锈宁之间差异显著(置信度为0.05)；**表示处理与粉锈宁之间差异极显著(置信度为0.01).
为不同批次分隔线.
2.2大黄毒力测试结果与分析
根据图2 大黄提取物对黄瓜白粉病的防效变化趋势曲线得到其相关拟合方程：y＝-1.7706x2-2.6837x+107.51(R2＝0.9882)，根据此方程计算出大黄提取物对黄瓜白粉病的Ec50为1398.30倍，其Ec90为1051.21倍。
2.3大黄的保护作用的持效期测试结果
从表2中可以看出，提前1d～6d喷大黄提取物100倍液，其防效均在90％以上，显著优于粉锈宁1000倍液，由此可以得出，大黄提取物的保护作用的持效期至少可达6d。
表2 大黄提取物对黄瓜白粉病菌保护作用的持效期
| 处理 | 病情指数/％ | 防效/％ | 5％显著水平 | 1％极显著水平 |
| 80％乙醇清水粉锈宁接种前1d接种前6d接种前5d接种前2d接种前4d接种前3d | 89.1387.1222.168.596.424.172.111.520.30 | -2.310.0073.4192.6092.6095.6397.5798.2799.65 | aabccccec | AABCCCCCC |
2.4大黄提取物抑菌谱的测试结果
从表3中可以看出，大黄提取物100倍液对供试的20种真菌都有一定的抑制作用，其中抑制率达50％以上的有10种，占供试菌的50％，且对小麦根腐病菌(Cochliobolus sativus)和玉米大斑病菌(Exserohilum turcicum)抑制率达到了80％左右。
表3 大黄提取物对20种致病真菌菌落直径的抑制作用
| 供试真菌 | 80％乙醇抑菌率/％ | TS-109抑菌率/％ | 供试真菌 | 80％乙醇抑菌率/％ | TS-109抑菌率/％ |
| Cochliobolus sativusExserohilum turcicumGibberella ceaeRhizoctonia solaniPythnm gramuneacolaFusarium moniliformeBotryosphaeria berengerianaCurvularia lunataColletotrichum capsiciFusarium oxysporum | 2.58-33.409.3625.793.428.06-6.465.823.0916.46 | 82.2179.6966.0063.0660.5760.2858.1456.6651.9751.92 | Alternaria solaniColletotrichum graminicolaAlternaria porriFusarium graminearumRizoctonia certalisLeptosphaeria maydisColletotrichum gossypiiAlternaria kikuchianaAlternaria maliVerticillium dahliae | 9.095.845.21-20.29-4.87-4.844.701.34-1.15-3.37 | 49.7949.0447.1343.9742.1141.0933.3730.5421.4720.45 |
2.5大黄提取物有效成分鉴定结果
从表4可以看出，标准品大黄酸对黄瓜白粉菌无活性，大黄素表现出一定活性，而大黄酚表现出高活性，其10000倍液与烯唑醇3000倍液的防效处于同一显著水平。从表5可以看出，粗提品大黄酸对黄瓜白粉病菌无活性，而大黄素、大黄酚与大黄素甲醚表现出较高活性。因此可以得出：大黄酸为防治白粉病的非有效成分，大黄素与大黄酚是其有效成分。
表4 大黄中主要成分的活性测试结果(标准品)
| 处理 | 病情指数/％ | 防效/％ | 5％显著水平 | 1％极显著水平 |
| 10％乙醇2.0％乙醇大黄酸(5万倍)大黄酸(10万倍)2.0％吡啶大黄酸(20万倍)0.5％吡啶1.0％吡啶清水大黄酸(1万倍)1.0％乙醇0.5％乙醇大黄酚(20万倍)大黄酚(10万倍)大黄酚(5万倍)大黄素(1000倍)大黄素(500倍)大黄酚(1万倍)烯唑醇1000 | 97.810594.749794.151494.143992.770091.771591.756590.783590.756588.565884.641783.168752.412051.445834.04040.50000.30000.00000.0000 | -7.78-4.44-3.70-3.70-2.22-1.23-1.110.000.002.476.678.3342.2243.3362.5694.4996.69100.00100.00 | aaaaaaaaaaaabbcdddd | AAAAAAAAAAAABBBCCCC |
表5 大黄提取液中主要成分活性测定结果(粗提品)
| 处理 | 病情指数/％ | 防效/％ | 5％显著水平 | 1％极显著水平 |
| 80％乙醇清水大黄酸大黄素大黄酚和大黄素甲醚 | 100.0092.0090.0010.800.800 | -8.700.002.1788.2699.13 | aaabb | AAABB |
2.5大黄提取物与烯唑醇的配比试验结果：
由毒力方程得出：烯唑醇 Ec50＝0.523ppm
大黄提取物 Ec50＝0.970ppm
大黄提取物∶烯唑醇 Ec50ppm 共毒系数
3∶1 0.986 121.06
1∶1 0.282 240.98
1∶3 0.603 138.02
由共毒系数可知，大黄提取物与烯唑醇的有效成分按3∶1-1∶3的比例配比具有明显的增效作用，二者可按此比例混配。
用本领域内人员共知的技术，按上述方法可分别得出大黄酚和/或大黄素和/或芦荟大黄素分别与烯唑醇或霜脲氰或烯酰吗啉复配的共毒系数，即在大黄酚和/或大黄素和/或芦荟大黄素0.01％---90％，烯唑醇或霜脲氰或烯酰吗啉0.1％---90％的范围内复配具有明显的增效作用。
二、配方实施例：
按照本发明所述的各物质的数值范围，称取有效成分、助剂、乳化剂、溶剂的量可配制本发明的乳油，同样的方法可制得本发明的可湿性粉剂、油悬浮剂、水悬浮剂等。
Claims (2)
1、一种含有大黄提取物的杀菌剂，其特征在于该杀菌剂含有下述重量百分比组分：
大黄酚、大黄素和芦荟大黄素中的一种或多种 0.01％-90％
烯唑醇 0.1％-90％。
2、根据权利要求1所述的杀菌剂，其特征在于所述杀菌剂含有下述重量百分比的组分：
大黄酚、大黄素和芦荟大黄素中的一种或多种，用量为0.1-60％；
烯唑醇，用量为0.1％-90％；
助剂为OP-10、0201、0203、农乳500、1600、1601、1602、2201、0208、十二烷基苯磺酸钠、十二烷基苯磺酸钙、木质素磺酸钠、木质素磺酸钙、SOPA中的任意一种或多种组成，用量为1-30％；
增效剂为渗透剂T、氮酮、YZ-901中的任意一种或多种组成，用量为1-30％；
填充物为CMC、黄原胶、白碳黑、陶土、硅藻土中的任意一种或多种组成，用量为0.1-80％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123720 CN1268214C (zh) | 2002-06-20 | 2002-06-20 | 含有大黄提取物的杀菌剂及其组合物 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123720 CN1268214C (zh) | 2002-06-20 | 2002-06-20 | 含有大黄提取物的杀菌剂及其组合物 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1387765A CN1387765A (zh) | 2003-01-01 |
| CN1268214C true CN1268214C (zh) | 2006-08-09 |
Family
ID=4745193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02123720 Expired - Lifetime CN1268214C (zh) | 2002-06-20 | 2002-06-20 | 含有大黄提取物的杀菌剂及其组合物 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1268214C (zh) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425139C (zh) * | 2007-06-08 | 2008-10-15 | 河南师范大学 | 小麦抗干热风保护剂及其喷施方法 |
| CN100425142C (zh) * | 2007-06-08 | 2008-10-15 | 河南师范大学 | 西瓜增甜促进剂及其喷施方法 |
| AR077432A1 (es) * | 2009-07-30 | 2011-08-24 | Marrone Bio Innovations | Combinaciones de inhibidor de patogenos de planta y metodos de uso |
| AR080551A1 (es) * | 2009-10-05 | 2012-04-18 | Marrone Bio Innovations | Derivados que contienen antraquinona como productos agricolas bioquimicos |
| CN103392699A (zh) * | 2010-06-30 | 2013-11-20 | 杨红宇 | 一种杀菌剂及其组合物 |
| SI2635119T1 (en) * | 2010-11-04 | 2018-08-31 | Marrone Bio Innovations, Inc. | Use of a composition comprising parieten as growth promoters |
| CN103338635A (zh) * | 2011-02-02 | 2013-10-02 | 马罗内生物创新公司 | 一种含蒽醌的配制剂/木素的制剂 |
| CN102349511B (zh) * | 2011-08-12 | 2014-12-10 | 温文 | 一种杀藻剂 |
| CN106962354A (zh) * | 2017-04-27 | 2017-07-21 | 江苏辉丰农化股份有限公司 | 一种包含蒽醌类化合物和苯氧喹啉的杀菌剂组合物 |
| CN115191450B (zh) * | 2022-08-12 | 2023-05-16 | 山东农业大学 | 一种促进番茄植株生长的中草药大黄制剂及其使用方法 |
| CN116982621B (zh) * | 2023-08-04 | 2024-07-26 | 贵州道元生物技术有限公司 | 一种农作物联合增效杀菌剂及其应用 |
-
2002
- 2002-06-20 CN CN 02123720 patent/CN1268214C/zh not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1387765A (zh) | 2003-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Halleen et al. | An integrated strategy for the proactive management of grapevine trunk disease pathogen infections in grapevine nurseries | |
| CN1268214C (zh) | 含有大黄提取物的杀菌剂及其组合物 | |
| WO2014026396A1 (zh) | 具有增效作用的杀菌组合物 | |
| CN106508970B (zh) | 一种复配杀菌组合物及其应用 | |
| CN103039468A (zh) | 一种壳寡糖与丙森锌的植保用组合物 | |
| CN105961399A (zh) | 杀菌组合物及其应用 | |
| CN104770368A (zh) | 含丁香菌酯和辛菌胺的杀菌组合物及其应用 | |
| CN101810181A (zh) | 杀菌农药组合物及其制备方法和用途 | |
| Massoud et al. | Impact of chitosan, Trichoderma harzianum, thyme oil and jojoba extract against Fusarium wilt disease of strawberry | |
| CN102308806B (zh) | 一种含有喹啉铜和氟环唑的农药组合物 | |
| CN101836634B (zh) | 含嘧菌酯的杀菌农药组合物及其应用 | |
| CN107318891A (zh) | 一种防治大豆根腐病的可湿性粉剂 | |
| CN103081920B (zh) | 一种含有戊菌唑的杀菌组合物 | |
| Ye et al. | Screening of fungicide to control Ciboria carunculoides under laboratory conditions | |
| CN1613847A (zh) | 芳香二脒类具杀菌活性的化合物及其用途 | |
| CN104430401A (zh) | 一种防治水稻虫害的农药悬浮制剂及其制备方法 | |
| CN104381293B (zh) | 一种含硅噻菌胺和井冈霉素的杀菌组合物 | |
| CN103548855B (zh) | 一种含中生菌素的杀菌组合物及其应用 | |
| CN115462386A (zh) | 一种杀菌组合物及其应用 | |
| CN117322427B (zh) | 一种含苯并烯氟菌唑的杀菌组合物用于防治柑橘炭疽病的用途 | |
| CN114747582B (zh) | 一种含Isoflucypram和喹啉铜的农药组合物及其应用 | |
| CN105994421A (zh) | 一种植物源杀菌制剂及在防治蔬菜枯萎病中的应用 | |
| CN105104396B (zh) | 一种含有丙硫唑和氨基寡糖素的农药组合物 | |
| CN104430390A (zh) | 氨基寡糖素与噻唑菌胺复配农用杀菌剂 | |
| CN105076169A (zh) | 含有丙硫咪唑和咯菌腈的杀菌组合物及应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20050524 Pledge (preservation): Preservation |
|
| PD01 | Discharge of preservation of patent |
Date of registration: 20060525 Pledge (preservation): Preservation |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHEN ZENGSHU Free format text: FORMER OWNER: PLANT PROTECTION COLLEGE, HEBEI AGRICULTURAL UNIV. Effective date: 20131105 Free format text: FORMER OWNER: HEBEI XUANHUA PESTICIDE CO., LTD. Effective date: 20131105 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 071000 BAODING, HEBEI PROVINCE TO: 050700 SHIJIAZHUANG, HEBEI PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20131105 Address after: 050700 Xinle Seed Co., Ltd., 71 auditorium street, Hebei, Xinle Applicant after: Chen Zengshu Address before: 071000 Baoding City, Hebei Province Applicant before: PLANT PROT College HEBEI AGRIC Applicant before: HEBEI XUANHUA PESTICIDE Co.,Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: FUJI BIOTECH (SHANGHAI) CO., LTD. Free format text: FORMER OWNER: CHEN ZENGSHU Effective date: 20150812 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150812 Address after: 200443 Shanghai City, Baoshan District No. 588 South Building 10C Ji Yun Patentee after: FUJI BIOLOGICAL TECHNOLOGY DEVELOPMENT (SHANGHAI) CO.,LTD. Address before: 050700 Xinle Seed Co., Ltd., 71 auditorium street, Hebei, Xinle Patentee before: Chen Zengshu |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20171228 Address after: 518123 Gold South Road, South Bay Street, 21, Longgang District, Shenzhen, Guangdong, 3 Patentee after: SHENZHEN QIANHAI FJ BIOLOGICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 200443 Shanghai City, Baoshan District No. 588 South Building 10C Ji Yun Patentee before: FUJI BIOLOGICAL TECHNOLOGY DEVELOPMENT (SHANGHAI) CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190404 Address after: 712100 North Side of Qingxin Road, Small and Medium-sized Enterprise Park, Wuquan Town, Yangling Demonstration Area, Xianyang City, Shaanxi Province Patentee after: YANGLING FJ BIOTECHNOLOGY CO.,LTD. Address before: 518123 3rd floor, 21 Jinnan Road, Nanwan Street, Longgang District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN QIANHAI FJ BIOLOGICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060809 |
|
| CX01 | Expiry of patent term |