CN1190533A - Biocide composition for plant pathogenic microganism, preparation method and application thereof - Google Patents
Biocide composition for plant pathogenic microganism, preparation method and application thereof Download PDFInfo
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- CN1190533A CN1190533A CN98101038A CN98101038A CN1190533A CN 1190533 A CN1190533 A CN 1190533A CN 98101038 A CN98101038 A CN 98101038A CN 98101038 A CN98101038 A CN 98101038A CN 1190533 A CN1190533 A CN 1190533A
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- composition
- acid
- isocyanuric acid
- plant
- phosphate
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000001717 pathogenic effect Effects 0.000 title claims description 16
- 230000003115 biocidal effect Effects 0.000 title 1
- 239000003139 biocide Substances 0.000 title 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 23
- 241000233866 Fungi Species 0.000 claims abstract description 8
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 33
- 239000004094 surface-active agent Substances 0.000 claims description 25
- -1 chlorine fluorine isocyanuric acid Chemical compound 0.000 claims description 23
- 230000000694 effects Effects 0.000 claims description 23
- DZZOJKGQQSORQI-UHFFFAOYSA-N N1C(=O)NC(=O)NC1=O.ClBr Chemical compound N1C(=O)NC(=O)NC1=O.ClBr DZZOJKGQQSORQI-UHFFFAOYSA-N 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 230000002147 killing effect Effects 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 241000894006 Bacteria Species 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
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- 235000021317 phosphate Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 11
- 208000035240 Disease Resistance Diseases 0.000 claims description 10
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- 239000010452 phosphate Substances 0.000 claims description 10
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- 150000002148 esters Chemical class 0.000 claims description 7
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 7
- 229930182490 saponin Natural products 0.000 claims description 7
- 150000007949 saponins Chemical class 0.000 claims description 7
- 229950009390 symclosene Drugs 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052736 halogen Inorganic materials 0.000 claims description 5
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- 125000000217 alkyl group Chemical group 0.000 claims description 4
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
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- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000036783 anaphylactic response Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000003196 chaotropic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 235000003373 curcuma longa Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 208000010801 foot rot Diseases 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 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
- 239000002207 metabolite Substances 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 239000002855 microbicide agent Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000001338 necrotic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229940007046 shigella dysenteriae Drugs 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940079862 sodium lauryl sarcosinate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- ADWNFGORSPBALY-UHFFFAOYSA-M sodium;2-[dodecyl(methyl)amino]acetate Chemical compound [Na+].CCCCCCCCCCCCN(C)CC([O-])=O ADWNFGORSPBALY-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 235000013976 turmeric Nutrition 0.000 description 1
- 201000008297 typhoid fever Diseases 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 230000003253 viricidal effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invented composition is composed of at least one kind of halogenated isocyanuric acid, at least one kind of earth alkali metal phoophate, at least one kind of anionic surfactant and the other auxiliary components. Said invention also relates to the preparation method thereof and the application in various plant diseases caused by pathogenic bacteria, fungi, virus and microorganism.
Description
The present invention generally relates to a kind of new Synergistic microbicidal compositions, particularly relating to the isocyanuric acid derivative that replaces with halogen is the Synergistic microbicidal compositions of primary activity composition, the application in the various plant diseases that the plant of control plant, particularly crops, vegetables, forest, fruit tree and ornamental plants and its seed or fruit cause because of pathogenic microorganisms such as bacterium, fungi or viruses of its preparation method and said composition.
As far back as the sixties in this century, people have just known cyanuric acid and the salt thereof that single or multiple chlorine atom replaces, can be under proper condition (as contacting the back with water) discharge active chlorine, with performance sterilization and bacteriostatic activity, be used for the sterilization of water body, environment and vessel, promptly so-called active chlorine release type disinfectant.After this some patent documentations disclose in succession that many to relate to dichloro-or tri chloroisocyanuric acid be active component, and add the composition of various other auxiliary elements, with the solvability of improving main compound, improve dissolution velocity and improve the method for storage stability.For example, these auxiliary elements comprise increases the deliquescent alkali metal hydrogencarbonate of chlorated fulminuric acid (United States Patent (USP) 4,389,318); The alkaline earth metal dissolving promotes additive (United States Patent (USP) 4,498,921); Na as chelating agent
2HPO
4With NaHCO as effervescent agent
3(United States Patent (USP) 3,276,726); Be used to increase aluminum sulfate (United States Patent (USP) 5,021,186) and the low melting point paraffin wax (BP GB2143251A) and the suitable stabilizing agent (talcum powder) and the chaotropic agent (NaHCO of storage stability
3+ boric acid) (Chinese patent application CN86104098A).Japan Patent JP85021967 discloses a kind of bactericide that instant long-acting is arranged that dichloro-and tri chloroisocyanuric acid salt and sodium sulphate or NaCl are mixed; Japan Patent JP93087042 discloses a kind of sterilizing cleaning agent tablet that tri chloroisocyanuric acid and hydrophilic adipic acid or benzoic acid and hydrophilic potassium sulphate or succinic acid are mixed and made into.Moreover, United States Patent (USP) 5,128,342 disclose a kind of dry powdered form, the antimicrobial compositions of storage-stable for a long time, said composition comprises chlorated fulminuric acid or its salt, fluorinated anionic surfactant (perfluoroalkyl percarboxylic acids ammonium), saleratus and potassium hydrogen phosphate.
Generally speaking, chlorated fulminuric acid be a class contain active chlorine 1,3,5-trichlorine (or 1, the 3-dichloro)-and S-triazine, 2,4, the 6-3 ketone, these compounds decompose under the wet condition of chance and discharge active chlorine, thereby can be used as the sterilization that disinfectant is used for water body (particularly sewage), cleaners and polishes etc.But the active chlorine that also there are poor stability in these compounds, disengaged is easy to produce the problem of harmful substances such as chloroform in water.
The mid-80, people find during this class Microbicidal compound in further investigation, this is similar for the chemical property of bromine disinfectant in water and chloro, and in water basically with the form existence of hypobromous acid (HOBr).The kill bacteria of bromine, virus, brood cell's effect are than chlorine stronger (referring to the Jiang Guangbo chief editor, sterilization is sterilized, and is anticorrosion, preservation, People's Health Publisher's version in 1986,310-316 page or leaf).Discover, as obtaining chlorine bromine or dibromo isocyanurate, particularly chlorobromide isocyanuric acid (RHBrCl) for one or two chlorine atom on 1,3 of the dichloro-isocyanuric acid with bromo.Chlorobromide isocyanuric acid is being met wet back decomposition generation hypobromous acid, thereby performance is than the microbicidel effect of independent bromine and chlorine stronger (strong approximately 3-4 doubly).Someone proved once that concentration was that the chlorobromide isocyanuric acid of 50mg/L can kill the colibacteriophage f of solids surface contamination fully
2, and can kill hepatitis type B virus (HBV) in the serum.Concentration is about 1, and 000mg/L can kill wax shape bacillus gemma (Ge Chiyi, sterilization and sterilization, 4,216,1986) fully.Research shows that further chlorobromide isocyanuric acid is not seen mutagenesis under high concentration, its LD
50Be worth obviously greater than sodium dichloro cyanurate, and do not see chronic toxicity (referring to Ge Chiyi, environment and health magazine, 4,7,1985).
Based on above-mentioned result of study, someone utilizes chlorobromide isocyanuric acid as main active, preparation has the disinfectant of wide spectrum function of killing microorganism, for example by what is called " CB " disinfectant (inside information) of HBV effect extremely that has of the common exploitation of Military Medical Science Institute and gold bead applied chemistry research institute.In addition, Chinese patent 93102874 (notification number 1079609) discloses and has been specifically designed to ginger, kill the bactericidal composition of turmeric sporangium (Xanthomonas zingiberi), said composition is by sym-closene, triacontanol (as plant hormone), and p-nitrophenol sodium (as carrier) and water are formed.Yet, there is no the relevant halo isocyanuric acid, particularly chlorobromide isocyanuric acid of using in all prior aries as the report that is used for the microbicide of plant.
The inventor just has been engaged in the chemosynthesis and the microbicidel Research on effect thereof of cyanuric acid derivative from the eighties always since the phase.The inventor is surprised to find, and carries out condensation reaction with pre-synthetic bromine chloride (BrCl) with cyanuric acid under cryogenic conditions, and makes Br
+And Cl
-Replace chlorobromide isocyanuric acid that the H atom on 1,3 of the cyanuric acids makes respectively not only when being used for water body, environment and daily necessities surface sterilization, than dichlord isocyanurice acid stronger bactericidal effect is arranged, and when becoming suspension to be sprayed on the plant surface its water, the pathogenic microorganism on kill plants stem, the leaf surface effectively.Based on this discovery, the inventor further studies and has prepared with the halo isocyanuric acid, particularly chlorobromide isocyanuric acid is the killing plant pathogenic microorganism formulation of primary activity composition, and its antimicrobial spectrum, storage stability, safety, working concentration and the possible mechanism of action to human body and plant carried out research widely, thereby finished the present invention.
Therefore, an object of the present invention is to provide a kind of killing plant pathogenic microbial composite, the isocyanuric acid that said composition is replaced by at least a halogen basically, at least a alkali earth metal phosphate, at least a non-ionic surface active agent, and appropriate carriers or excipient and/or other auxiliary elements composition.
According to this purpose of the present invention, isocyanuric acid halide derivative content is 15 to 55% (W/W) in the wherein said composition, alkali earth metal phosphate content is 5% to 20%, anionic surfactant concentration is 5% to 15%, and all the other are conventional carrier or excipient or alkali metal hydrogen chlorine compound.
The preferred embodiment of this purpose according to the present invention, the isocyanuric acid derivative that wherein said halogen replaces is selected from dichlord isocyanurice acid, sym-closene, chlorobromide isocyanuric acid and chlorine fluorine isocyanuric acid, but wherein particularly preferably be chlorobromide isocyanuric acid.
The preferred embodiment of this purpose according to the present invention, wherein said alkali earth metal phosphate is selected from potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate and sodium dihydrogen phosphate, but particularly preferably is potassium dihydrogen phosphate and tripotassium phosphate.
This purpose preferred embodiment according to the present invention, wherein said non-ionic surface active agent is selected from sulphonic acid ester, fatty acid list or two sulfuric ester of glycerols, polyether thiourea acid alkyl ester, glycerin ether sulfonic acid higher alkyl esters, alkyl sulfonic ester, alkyl aryl sulphonic acid acid, the alkyl sulfate of Tea Saponin, monokaryon aromatic sulfonic acid higher alkyl esters, alkene sulfonic acid ester, higher alcohol, but wherein particularly preferably is Tea Saponin and dodecyl sodium sulfate.
Embodiment of this purpose according to the present invention, said composition also can contain one or more has similar or synergistic its homicide phytomicroorganism compound or their mixture to halo isocyanuric acid derivative.
Another object of the present invention provides the method for the above-mentioned killing plant pathogenic microbial composite of preparation, this method comprises that one or more alkali earth metal phosphates introducings that will grind to form fine powder have in the container of agitating device, and fully mix, introduce halogenation isocyanuric acid and non-ionic surface active agent then, and other necessary auxiliary elements.
A further object of the present invention provides the application of above-mentioned killing plant pathogenic microbial composite in the disease of preventing and treating plant to cause because of bacterium, fungi and virus.According to this purpose of the present invention, wherein said plant comprises ripe plant, seedling, seed and the fruit thereof of unifacial leaf and dicotyledonous crops, vegetables, forest, fruit tree and ornamental plants.
The present invention relates to a kind of killing plant pathogenic microbial composite, said composition contains isocyanuric acid, at least a alkali earth metal phosphate as plant disease resistance inductor and buffer, at least a non-ionic surface active agent that at least a halogen as the primary activity composition replaces, and acceptable carrier or excipient on the suitable agricultural chemicals.According to embodiment of the present invention, the basic pathogenic microorganism active component that kills that is used for the present composition is the isocyanuric acid derivative with halogen atom replacement of following general structure (1):
R wherein
1And R
2Each is Cl, Br naturally, works as R
1And R
2In one be halogen atom the time, another can be H, Cl, Br or alkoxyl, halogenated alkoxy.
According to the preferred embodiments of the invention, R in above-listed structural formula
1And R
2In one when being chlorine, another is bromine or fluorine.
Under high humidity, show on having that the halo isocyanuric acid of structural formula (1) is subjected to hydrolysis, discharge active chlorine and/or bromine gradually, and exist with the form of hypochlorous acid (HOCl) and hypobromous acid (HOBr) respectively.Under aqueous environment, hypochlorous acid and hypobromous acid have very strong oxidation and bleaching character.Their chemical property is very unstable, but under the situation of cyanuric acid condensation, can react and generate the very stable dichloro of chemical property, three chlorine or bromine symclosenes with it.These acid all have very strong oxidability, and so as to bringing into play its anti-microbial effect.Experimental result shows that under aqueous environment, HOBr is approximately higher 4 times than the microbicidel ability of HOCl.
With regard to the primary activity composition in the killing plant pathogenic microbial composite of the present invention, representational and preferred halo isocyanuric acid is a chlorobromide isocyanuric acid.Our experimental study shows, in the time will containing this composition of active components aqueous solution and spray on plant leaf, stem surface, it can discharge active chlorine and the bromine that exists with HOBr and HOCl form, and can act synergistically, thereby bring into play the effect of directly killing plant pathogenic microorganisms in the part with the alkali metal salt in the composition.In addition, said compound also may enter in the plant tissue by systemic action, influences some constituent and the enzymic activity of plant, to reach the effect that suppresses symptom or delay the disease development.After compound discharged Br and Cl, s-triazine that stays (ADHL) or triazinediones (DHT) parent ring structure had very strong microbicidel, particularly viricidal activity equally.G.Schuster once reported DHT and ADHL has tangible fragmentation effect to potato virus X (PUX), marmor upsilon (DVY) and tobacco mosaic virus (TMV).Therefore, primary activity composition as killing plant pathogenic microbial composite of the present invention, the biological action of chlorobromide isocyanuric acid is dual, promptly it can the form with hypochlorous acid and hypobromous acid discharge active bromine chloride in the wet back of the local chance of plant on the one hand, directly kills the pathogenic microorganism in plant surface and the superficial tissues; On the other hand, the parent ring structure s-triazine of molecule and triazinediones can pass through systemic action, the effect that stops pathogenic microorganisms such as bacterium, virus to divide and breed away from the performance of dispenser position on plant.In addition, s-triazine is well known by persons skilled in the art as the weed killer herbicide of another kind of type.
The microbicidal active ingredients chlorobromide isocyanuric acid that can be used for the present composition according to method preparation known in the chemosynthesis technical field.Briefly, this method comprises: be raw material with bromine and concentrated hydrochloric acid at first, in low temperature (0-3 ℃) reaction down, and feed chlorine in reactant mixture, after treating that bromine is finished dissolving, obtain the reactant mixture that bromine chloride content wherein is at least 40-45% (W/V).Then this reactant mixture is added drop-wise in highly basic (NaOH) solution of cyanuric acid, under the temperature that reduces fully after the reaction (at least 90 minutes), the resulting sediment of centrifugal collection, and obtain the white micro-crystals body of chlorine bromine isouric acid after the drying.
In killing plant pathogenic microbial composite of the present invention, can be with chloro or chlorine bromo isocyanuric acid as the single-activity composition, but for the consumption that reduces the isocyanuric acid derivative and improve the microbicidel effect, be preferably in and add one or more alkaline earth metal or alkali metal phosphates, particularly alkali earth metal phosphate in the said composition as plant disease resistance inductor.
As far back as the beginning of this century, people have just found many biotic factors (as bacterium, virus, fungi and metabolite thereof), physical agent (penetrating processing as mechanical damage, electromagnetism and the width of cloth), but and disease resistance response of inducing plant all such as chemokines, be these factors can make plant produce so-called system's resistance of inducing (Induced Systemie Resistance, ISR).In general, plant disease resistance inductor does not have selection pressure and direct killing effect to pathogen, does not therefore have the pesticide resistance problem.Plant disease resistance inductor is to realize by the disease resistance that strengthens plant to the preventive and therapeutic effect of plant disease, thereby can be used for preventing and treating the disease that is caused by multiple pathogenic microorganisms such as bacterium, fungi and viruses; In addition because disease-resistant derivant is to resist disease by the resistance against diseases that improves plant, so these factor pair non-pathogenic microorganisms, for example saprophytic bacteria, not influence basically such as antagonism bacterium, thereby more help reducing environmental pollution and keeping the ecological balance; At last, the plant disease-resistant response class that disease-resistant derivant activates is similar to and makes plant become new disease-resistant varieties, so can make plant avoid suffering infecting of multiple less important disease.
The available use of plant disease resistance inductor of number of different types is arranged.The inventor has taken into full account the toxicity of compound, synergy and possibility good effect with key component, and application target and method of application and with factor such as cost, result of use to compounds such as dichloro-isonicotinic acid, ethyl phosphine aluminium, salicylic acid, jasmonic, alkali earth metal phosphates has been carried out experiment screening repeatedly, and final decision adopts alkali earth metal phosphate as the disease-resistant derivant that is used for the present composition.These compounds comprise but are not only limited to K
3RO4, KH
2PO4, Na
3PO4, NaH
2PO4, Na
2HPO4, but wherein preferably potassium phosphate, particularly KH
2PO4.Experiment in the past shows, the aqueous solution of these compounds is sprayed on crops or vegetables blade, it raises but inducing plant body endoperoxide enzyme and chitinase are active, thereby gives plant with general resisting pathogenic microbes resistance when necrotic plaque is caused in the part.The inventor's experiment then further proves, unites and uses chlorobromide isocyanuric acid and K
2PO4, in the body of gained mixture and external microbicidel effect higher approximately by 20% than using chlorobromide isocyanuric acid (50% (W/W) wettable powder) separately, and the storage stability of gained mixture and solvability also obtain improvement to a certain degree.
According to a preferred embodiment of the invention, better using mol ratio is 1: 1 potassium phosphate (K
3PO4) and potassium dihydrogen phosphate (K
2PO4) mixture is as plant disease resistance inductor.This mixture also can be used as the carrier of water solube powder composition, and brings into play certain PH cushioning effect under dissolved state in gained solution.
Know, in active chlorine release compound, sneak into organic surface active agent, water soluble anionic surfactant particularly, not only can improve the dispersity and the wetability of primary activity composition, and play emulsification, but also can strengthen the disinfecting power (referring to United States Patent (USP) 5.128,342, specification first hurdle) that the gained active chlorine discharges compound effectively.Killing plant pathogenic microbial composite of the present invention equally also is added with suitable surfactant.The surfactant that is used for the present composition can be non-ionic surface active agent or anion surfactant.Ionic surfactant pack commonly used has been drawn together partial fatty-acid ester of polyol, polyoxyethylene aliphatic alcohol ether, polyxyethylatedization phenolic ether etc.Anion surfactant commonly used comprises sulphonic acid ester, fatty acid list or two sulfuric ester of glycerols, polyether thiourea acid alkyl ester, glycerin ether sulfonic acid higher alkyl esters and the oleate etc. of the benzene sulfonamide acid esters that contains 10-16 carbon atom in saponin such as Tea Saponin, sodium alkyl sulfonate, sodium alklyarylsulfonate, senior alkyl monokaryon aromatic sulfonic acid ester such as the alkyl group, hydroxy alkyl sulfonic acid ester, sodium lauryl sarcosinate, alkene sulfonic acid ester, higher alcohol.According at alkali condition lower surface activating agent to the suspensibility of main active chlorobromide isocyanuric acid and the influence degree of wetability, particularly preferred ionic surface active agent is a non-ionic surface active agent in the composition of the present invention, particularly saponin Tea Saponin for example, and/or the sulfuric ester of higher alcohol is lauryl sodium sulfate for example.Their part by weight in the present composition are respectively 0.5-2% and 5-10%.
What also should particularly point out here is as the surface active agent composition in the present composition, also can select the organic surface active agent of fluoridizing for use.The organic surface active agent of fluoridizing is the known chemical individual of a class, and available fluorine replaces whole or the most of effective hydrogen in the surfactant molecule and makes.Research in the past is verified, and when using the organic surface active agent fluoridize, the effective halogen atom that contains in the compound of active halogen atom (as the chlorine atom) can not act on the organic surface active agent of fluoridizing, to form stable compositions.In addition, found to replace hydrogen in the surfactant molecule with fluorine, can improve significantly the gained surfactant wetting, penetrate and emulsifiability, thereby can significantly reduce the consumption of surfactant.If use the surfactant of fluoridizing, its concentration in composition should not surpass 2%, otherwise will reduce the storage stability of resulting composition under higher temperature.
Be applicable to the present composition, particularly carrier in the composition of soluble powder form or excipient comprise but are not only limited to clay, kaolin, diatomite, floats and talcum powder and make soluble powder.Certainly, in some cases, also available aforesaid plant disease resistance inductor potassium phosphate is as the carrier or the excipient of pulvis or other forms of solid composite, to help improving the stability of composition.
In addition, can when preparation composition of the present invention, add the potassium chloride of q.s, so that after adding water or other water-bearing media diluted compositions, be used as filler and synergist.
Can be according to method known in the pesticide producing field, and use conventional auxiliary material, composition of the present invention is made wetting powder, tablet, granule, capsule or microcapsules, and suspending agent or the agent of liposome bag.But, preferably make soluble powder for easy to use.
In order to prepare the present composition of soluble powder form, can be according to methods known in the art, alkali earth metal phosphate, potassium cyanide and non-ionic surface active agent are added in rotary drum or the impeller-type stirrer successively by suitable part by weight, mix with the slow-speed of revolution.Add new synthetic halo isocyanuric acid then, and can add or not add other suitable auxiliary elements and carrier or excipient simultaneously, and continue to mix and stir reasonable time, till abundant mixing.Whole mixed preparing process is preferably under normal temperature and the low-humidity environment carries out.The instantiation of killing plant pathogenic microbial composite prescription of the present invention is as follows: recipe ingredient weight ratio (%)
1 chlorobromide isocyanuric acid 50
(effectively bromine chloride 28%)
Tea Saponin 2
Dipotassium hydrogen phosphate (K
2HPO4) 48
2 chlorobromide isocyanuric acids 30
(effectively bromine chloride 18%)
Lauryl sodium sulfate 10
Biphosphate (KH
2PO4) 20
Potassium chloride (KOH) 15
Kaolin 25
Be killing plant pathogenic microorganism purpose, generally composition of the present invention can be mixed with halo isocyanuric acid content is the pulvis of 15-50%.Under the situation of using 50% chlorobromide isocyanuric acid, available active bromine chloride weight ratio is about 28% in the composition.Face when using, can be according to application target and actual needs, the soluble powder that branch is installed suspends or is dissolved in the water of proper volume, to dilute it.
Under this activity compound concentration and active BrCl content condition, the field application concentration is about 0.5 ‰.The above-mentioned pulvis of 30-60g is used in every mu of farmland approximately.
Killing plant pathogenic microbial composite of the present invention can be widely used in to be killed or plant is infected in deactivation, particularly the various pathogenic microorganisms that comprise bacterium, fungi, mould and virus of grain and oil crop, vegetables, fruit tree, forest and ornamental plants.These pathogenic microorganisms for example comprise but are not only limited to the white tikka bacterium of paddy rice, paddy rice slice spot bacterium, rice blast fungus, the withered bacterium of rice line, ralstonia solanacearum, ginger plague bacterium, Chinese cabbage soft-rot fungi, gibberella saubinetii spore, wheat striped germ, peanut Ralstonia solanacearum, potato X or Y virus, tobacco mosaic virus, citrus ulcer bacteria, sigatoka bacterium etc.Therefore, explanation as an example, the plant disease of available composition for preventing and controlling of the present invention comprises but is not only limited to paddy bacterial striped pinta, bacterial leaf-blight, rice blast, bakanae disease, wheat scab, banded sclerotial blight; Soft rot of cabbage, downy mildew, virus disease; Downy mildew, fusarium wilt, angular leaf spot, the root rot of cucumber, watermelon, muskmelon etc.; Tomato, peanut and eggplant eqpidemic disease, stem foot rot, bacterial wilt; Capsicum and fabaceous fusarium wilt, root rot, virus disease; Bacterial wilt of ginger, the root rot of root crops such as dirt ginger and Ma Lingzhu; Citrus, apple, pears canker, anthracnose, rot, shot hole, scab; Cotton verticillium wilt, damping off, and tobacco and tealeaves virus disease.
For the purpose of easy to use and saving, usually can be when the plant symptom occurs, being the plant disease initial phase adds 1 with 50% dust composition of the present composition, 000 to 2, after the water dilution of 000 times of volume, spray on leaf in plant, the stem surface with conventional sprayer unit, or crops, or on the surfaces of fruit-picking fruit or vegetables.Generally use once, use 1-2 time but also can append with the proper spacing phase according to degree of disease.As being used to flood crop seed, the concentration of the composition therefor aqueous solution is generally 0.5-1 ‰ (W/W).
In vitro test shows that the minimal effective concentration of the present composition is 6.25-100ppm, and be 2-10 minute action time.Because of containing phosphorus, potassium compound in the composition of the present invention, and the parent ring structure (cyanuric acid) of halo isocyanuric acid can decompose the generation nitrogen substance under certain condition, and therefore composition of the present invention also has certain fertilizer efficiency function.
As a kind of broad-spectrum disinfectant, composition of the present invention also can be killed shigella dysenteriae, golden yellow grape bacillus, typhoid bacillus, Escherichia coli, cured sample brood cell etc. effectively, and viruses such as hepatitis type B virus, rotavirus, AIDS virus, livestock foot-and-mouth disease virus, newcastle disease virus and Marek's disease poison.Therefore, composition of the present invention also can be used as universal decontaminant, is used for sterilization industry and sanitary sewage and swimming pool water body, all contaminations, facility and apparatus etc. in work and the living environment.Comparative experiments shows that when being used for these purposes, the pathogenic microorganism composition that kills of the present invention obviously is better than bleaching powder, clorox, ammonia amine T and contains dichloro or other routine disinfection agent of sym-closene on the microbicidel effect.
We use in the body that the SD big white mouse carries out (per os and through skin), and the toxicology testing result shows that the present composition is to the LD of rat
50Value>2, the 000mg/kg body weight.Routine is not seen the positive findings that can detect to local anaphylaxis that large ear rabbit is done and stimulation test.
Claims (10)
1. killing plant pathogenic microbial composite, the isocyanuric acid derivative that said composition is replaced by at least a halogen shown in structural formula (I) basically, at least a alkali earth metal phosphate, at least a non-ionic surface active agent, and appropriate carriers or excipient and/or other auxiliary elements composition.
2. according to the composition of claim 1, isocyanuric acid halo derivatives weight content ratio is 15% to 55% in the wherein said composition, alkali earth metal phosphate is 5% to 20%, and non-ionic surface active agent is 5% to 15%, and all the other are other conventional auxiliary element or excipient.
3. according to the composition of claim 1, the isocyanuric acid halo derivatives as the primary activity composition in the wherein said composition is selected from dichlord isocyanurice acid, sym-closene, chlorobromide isocyanuric acid, chlorine fluorine isocyanuric acid.
4. according to the composition of claim 3, wherein said isocyanuric acid halo derivatives is a chlorobromide isocyanuric acid.
5. according to the composition of claim 1, the alkali earth metal phosphate as plant disease resistance inductor in the wherein said composition is selected from potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate and tertiary sodium phosphate.
6. according to the composition of claim 1, the non-ionic surface active agent in the wherein said composition is selected from sulphonic acid ester, fatty acid list or two sulfuric ester of glycerols, polyether thiourea acid alkyl ester, glycerin ether sulfonic acid higher alkyl esters, alkyl sulfonic ester, alkyl aryl sulfonate and the alkyl sulfate of Tea Saponin, monokaryon aromatic sulfonic acid higher alkyl esters, alkene sulfonic acid ester, higher alcohol.
7. according to the composition of claim 1, wherein said composition also can contain one or more has similar or synergistic its homicide phytomicroorganism compound or their mixture to halo isocyanuric acid derivative.
8. preparation is according to the method for each killing plant pathogenic microbial composite in the claim 1 to 7, this method comprise will grind to form one or both alkali earth metal phosphates of fine powder introduce in the container that has agitating device and fully mix, introduce halo isocyanuric acid and non-ionic surface active agent and other necessary auxiliary elements then, and further fully mixing it.
9. preventing and treating plant according to the composition of any one in the claim 1 to 7 because of the application in bacterium, fungi or the viral plant disease that causes.
10. according to the application of claim 9, wherein said plant comprises ripe plant, seedling, seed and the fruit thereof of unifacial leaf and dicotyledonous grain or oil crop, vegetables, forest, fruit tree and ornamental plants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101038A CN1190533A (en) | 1998-03-20 | 1998-03-20 | Biocide composition for plant pathogenic microganism, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101038A CN1190533A (en) | 1998-03-20 | 1998-03-20 | Biocide composition for plant pathogenic microganism, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1190533A true CN1190533A (en) | 1998-08-19 |
Family
ID=5216422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98101038A Pending CN1190533A (en) | 1998-03-20 | 1998-03-20 | Biocide composition for plant pathogenic microganism, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1190533A (en) |
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| CN1295961C (en) * | 2004-12-20 | 2007-01-24 | 周安兴 | Sodium dibromoisocyanurate as disinfectant and its production process |
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| CN1295961C (en) * | 2004-12-20 | 2007-01-24 | 周安兴 | Sodium dibromoisocyanurate as disinfectant and its production process |
| CN101156627B (en) * | 2007-09-21 | 2011-04-27 | 华南农业大学 | Citrus corrosion protection antistaling agent with tea saponin |
| CN102001881A (en) * | 2010-10-09 | 2011-04-06 | 徐坤 | Preparation for preventing and curing ginger bacterial wilt |
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| CN102898252B (en) * | 2012-09-24 | 2014-10-15 | 华南农业大学 | Organic fertilizer, preparation method thereof and method for controlling soil-borne diseases and insect pests |
| CN102863283B (en) * | 2012-09-24 | 2014-12-17 | 华南农业大学 | Organic fertilizer, preparation method thereof and method for preventing soil-borne pest diseases |
| CN102863297A (en) * | 2012-09-24 | 2013-01-09 | 华南农业大学 | Organic fertilizer and preparation method thereof and method for controlling soil borne disease |
| CN102863296B (en) * | 2012-09-24 | 2014-12-17 | 华南农业大学 | Organic fertilizer and preparation method thereof and method for controlling soil borne disease |
| CN104255801A (en) * | 2014-08-29 | 2015-01-07 | 浙江大洋生物科技集团股份有限公司 | Crop potassium supplement composition with sterilization function as well as preparation method and application of crop potassium supplement composition |
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