CN107258804B - Bactericide composition and application thereof - Google Patents

Bactericide composition and application thereof Download PDF

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Publication number
CN107258804B
CN107258804B CN201710608365.6A CN201710608365A CN107258804B CN 107258804 B CN107258804 B CN 107258804B CN 201710608365 A CN201710608365 A CN 201710608365A CN 107258804 B CN107258804 B CN 107258804B
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zhongshengmycin
chitosan oligosaccharide
sodium
acid
chelating agent
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CN107258804A (en
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丁文明
罗湘仁
孙良宏
陈坤
张孝武
母金良
潘静
高敬雨
刘润峰
东琴
陶代雨
张磊
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Yunfa Biotechnology (Shanghai) Co.,Ltd.
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Shanghai Mingdelida Biotechnology Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/22Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, 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
    • A01N43/04Biocides, 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
    • A01N43/14Biocides, 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
    • A01N43/16Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a bactericide composition and application thereof, the bactericide composition contains active ingredients and a chelating agent, the active ingredients contain zhongshengmycin and chitosan oligosaccharide, and the weight ratio of the zhongshengmycin to the chitosan oligosaccharide to the chelating agent is 1: (0.1-15): (5-30). The chelating agent comprises at least one of ethylenediamine tetraacetic acid, sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, potassium sodium tartrate and nitrilotriacetic acid. The wettable powder, the water dispersible granule and the soluble liquid prepared by the bactericide composition disclosed by the invention are not flocculated, precipitated and the like when being used with other bactericides with different compositions and dosage forms in a tank mixing manner, and the pesticide effect of the tank mixing manner is obviously improved.

Description

Bactericide composition and application thereof
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a bactericide composition and application thereof.
Background
In agricultural production practice, the mixed occurrence of different types of diseases often exists, for example, in tomato, cucumber, hot pepper, Chinese cabbage, apple and other crops, bacterial wilt, late blight, virus diseases, soft rot, scab, apple ring rot, downy mildew, anthracnose, gibberellic disease, powdery mildew and the like are diseases which often exist simultaneously or sequentially.
The common diseases such as bacterial wilt, late blight, virus disease, apple ring spot and the like are prevented and controlled by the conventional zhongshengmycin-chitosan oligosaccharide bactericide composition, but the composition has no obvious control effect on downy mildew, anthracnose and gibberellic disease, so that the zhongshengmycin-chitosan oligosaccharide composition is often required to be mixed with bactericides with different dosage forms and different effective components for use in a barrel. However, we have found that the conventional zhongshengmycin-chitosan oligosaccharide composition is subjected to flocculation, precipitation and other phenomena when being tank-mixed with suspending agents, missible oil, microcapsule suspending agents, wettable powder and the like, so that the drug effect is seriously reduced, and the reason is due to the existence of chitosan oligosaccharide.
Therefore, the technical problem of how to avoid flocculation and precipitation when the composition containing the biotins and the chitosan oligosaccharide bactericide is mixed with bactericides with other compositions and dosage forms needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a bactericide composition and application thereof, the bactericide composition does not generate flocculation, precipitation and the like when being used with other bactericides with other compositions and dosage forms in a tank mixing way, and the pesticide effect of the tank mixing way is obviously improved.
In one aspect, the invention provides a bactericide composition, which comprises an active ingredient and a chelating agent, wherein the active ingredient comprises zhongshengmycin and chitosan oligosaccharide, and the weight ratio of the zhongshengmycin to the chitosan oligosaccharide to the chelating agent is 1: (0.1-15): (5-30).
Optionally, the chelating agent comprises at least one of ethylenediaminetetraacetic acid, sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, potassium sodium tartrate, and nitrilotriacetic acid; preferably, the chelating agent is ammonium citrate.
Optionally, the weight ratio of zhongshengmycin, chitosan oligosaccharide and the chelating agent is 1: (0.5-10): (10-25).
Optionally, the weight ratio of zhongshengmycin, chitosan oligosaccharide and the chelating agent is 1: (1-5): (15-20).
Optionally, the germicide composition further contains adjuvants including at least one of solvents, dispersants, wetting agents, emulsifiers, stabilizers, preservatives, thickeners, binders, defoamers, acid adjusting media, base adjusting media, colorants, and solid inert carriers.
Optionally, the solvent comprises at least one of toluene, xylene, DMF, NMP, # 150 mineral spirits, # 120 mineral spirits, methanol, mixed benzene, mineral oil, cyclohexanone, DMSO, dichloromethane, chloroform, ethyl acetate, sec-butyl acetate, isopropanol, and tetrahydrofuran; the dispersing agent comprises at least one of alkyl naphthalene sulfonate, a bis (alkyl) naphthalene sulfonate formaldehyde condensate, aryl phenol polyoxyethylene succinate sulfonate, octyl phenol polyoxyethylene ether sulfate, polycarboxylate, lignin sodium sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl benzene sulfonic acid calcium salt, naphthalene sulfonate formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty amine polyoxyethylene ether and fatty acid polyoxyethylene ester; the wetting agent comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, washing powder, pesticide emulsion 2000# series, sodium lauryl sulfate, wetting penetrant F, wetting agent T, Chinese honeylocust fruit powder, tea seed cake, silkworm excrement and soapberry powder; the emulsifier comprises cationic surfactant and anionic surfactantAt least one of an agent, a nonionic surfactant, and a zwitterionic surfactant; the thickening agent comprises at least one of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin; the binder comprises at least one of starch, gypsum, glucose, polyvinyl alcohol, gum arabic, and dextrin; the defoaming agent comprises silicone and C8-10Fatty alcohols, C10-20Saturated fatty acid, C10-20At least one of saturated fatty acid amide, silicone oil and polysiloxane compound; the acid regulating medium comprises at least one of ammonium chloride, hydrochloric acid, citric acid, ammonium sulfate, ammonium nitrate and acetic acid; the alkali adjusting medium comprises at least one of sodium hydroxide, triethanolamine, triethylamine, ammonia water and sodium ethoxide; the solid inert carrier comprises at least one of clay, silicon dioxide, diatomite, kaolin, attapulgite, montmorillonite, bentonite, talcum powder and light calcium carbonate.
Optionally, the dosage form of the bactericide composition comprises at least one of wettable powder, water dispersible granules and soluble liquid.
Optionally, the bactericide composition is in the form of wettable powder.
Optionally, the active ingredient is present in the fungicide composition in an amount of 1 to 95% by weight.
On the other hand, the invention also provides the application of the bactericide composition in preventing and treating crop diseases, wherein the diseases comprise at least one of bacterial wilt, late blight, fusarium wilt, virus disease, soft rot, scab, apple ring spot, downy mildew, anthracnose, gibberellic disease, powdery mildew, banded sclerotial blight, early blight, rice blast and leaf spot.
The bactericide composition of the invention does not generate flocculation, precipitation and the like when being used with other bactericides with other compositions and dosage forms in a tank mixing way, the pesticide effect of the tank mixing way is obviously improved, and the control effect on various diseases of crops is obviously improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a photograph showing the case where a conventional zhongshengmycin-chitosan oligosaccharide composition and a disinfectant composition of the present invention are mixed with a suspending agent in equal amounts, respectively.
FIG. 2 is a photograph showing the case where a conventional zhongshengmycin-chitosan oligosaccharide composition and the bactericide composition of the present invention are mixed with an equal amount of a microcapsule suspension preparation.
FIG. 3 is a photograph showing the case where a conventional zhongshengmycin-chitosan oligosaccharide composition and the bactericidal composition of the present invention are mixed with an emulsifiable concentrate chemical in equal amounts.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a bactericide composition, which can contain an active ingredient and a chelating agent, wherein the active ingredient can contain zhongshengmycin and chitosan oligosaccharide, and the weight ratio of the zhongshengmycin to the chitosan oligosaccharide to the chelating agent can be 1: (0.1-15): (5-30).
The Zhongshengmycin has the English name of Zhongshengmycin, the chemical name of 1-N-glucoside intrachain diriginyl-2-amino-L-lysine-2 deoxygulosamine and the molecular formula of C19H34O8N8Relative molecular weight 502, the structural formula is as follows:
the zhongshengmycin can inhibit the germination of spores and kill the spores by inhibiting the synthesis of mycoprotein of bacteria and deforming hypha of fungi, so that harmful bacteria and germs are ineffective, such as gram-positive and negative bacteria, mycobacteria, yeast and fungi, and can be used for preventing and treating bacterial diseases such as bacterial blight bakanae disease of rice, vegetable bacterial angular leaf spot disease, bacterial blight, soft rot disease, fruit canker disease, anthracnose, alternaria leaf spot and the like. However, the antibiotic pesticide can increase the resistance of pathogenic bacteria when being used singly for a long time, and the control effect is worse and worse along with the time.
Chitosan oligosaccharide is also called amino-oligosaccharide, has the chemical name of beta-1, 4-oligosaccharide-glucosamine, has the molecular weight of about polymerization degree multiplied by 161, is an oligosaccharide product obtained by degrading Chitosan into the polymerization degree of 2-20, is the only cationic basic amino-oligosaccharide with positive charge in nature, and is animal cellulose. The structural formula is as follows:
n=2~20,
the amino-oligosaccharin can induce plant body to produce disease-resistant factor, dissolve the cell wall of pathogenic fungi, bacteria and the like, interfere the synthesis of virus RNA and achieve the purpose of preventing and treating diseases through the action on plant cells. The chitosan oligosaccharide can also be used as a plant growth regulator to activate plant cells, regulate and promote plant growth, improve stress resistance, enhance cold resistance, drought resistance and waterlogging resistance of crops, and remove phytotoxicity, thereby increasing crop yield and improving crop quality. The flocculation mechanism of the chitosan oligosaccharide mainly has three functions of chelation, electric neutralization and adsorption bridging, and the three functions are mutually influenced.
1. Chelation
Chelation of chitosan oligosaccharides depends on its specific structure. The molecular formula of the chitosan oligosaccharide is (C)6H11NO4) And n, n is 2-20, and each monomer contains two hydroxyl groups and one amino group. Amino and hydroxyl are good coordination groups and can react with heavy metal ions such as Hg2+、Cd2+、Pb2+、Cu2+、Ag+Etc. to form stable chelates. The chitosan oligosaccharide can adsorb metal ions through electrostatic interaction. For example, in an aqueous system, metal ions form an anionic chelate through coordination, and the chelate can be combined with the protonated positively charged amino group of the chitosan oligosaccharide under the electrostatic action.
2. Electrical neutralization
Research shows that under the action of dilute acid, such as hydrochloric acid, formic acid, acetic acid, etc., the amino group on the chitosan oligosaccharide molecule is protonated to form-NH3+So as to lead the chitosan oligosaccharide to be positively charged and form a cationic polymeric flocculant. As a plurality of auxiliary agents such as phosphate, sulfonate, polycarboxylate, calcium dodecylbenzenesulfonate and the like in the pesticide preparation have negative charges, chemically synthesized bulk drugs mostly have negative charge groups, and chitosan oligosaccharide can effectively reduce the negative charges on the surfaces of the substances and reduce the zeta potential of the substances under the action of electric neutralization, so that the substances are destabilized and settled.
3. Adsorption bridging action
For chitosan oligosaccharide, adsorption-bridging action usually occurs after electrostatic action, auxiliaries and active ingredients in the preparation are destabilized through the electrostatic action, and destabilized particles are mutually polymerized to form flocculent precipitates. Under the action of static electricity, the cationic chitosan oligosaccharide polymer is easily adsorbed on the surface of a negatively charged substance to form a ring, so that the distance between the coated substance and a solution is increased. The dispersed part of the solution is connected with the ring of another particle to form bridging action, and the bridging action and efficiency are related to the relative molecular mass of the chitosan oligosaccharide.
As the polymerization degree of the chitosan oligosaccharide is only 6-20, the adsorption and bridging effects are relatively small, and the chelation effect and the electric neutralization effect are mainly shown.
According to the present invention, the chelating agent may include at least one of ethylenediaminetetraacetic acid, sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, sodium potassium tartrate, and nitrilotriacetic acid. The chelating agent may include one or more of ethylenediaminetetraacetic acid, sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, potassium sodium tartrate, and nitrilotriacetic acid; preferably, the chelating agent may be ammonium citrate.
The inventor of the application discovers through thousands of experiments that the bactericide composition is formed by compounding one or more chelating agents with the zhongshengmycin and the chitosan oligosaccharide, the chelating agents can shield amino cations of the chitosan oligosaccharide through chelation, and then flocculation and precipitation can be avoided when the zhongshengmycin-chitosan oligosaccharide medicament is mixed with medicaments of other compositions and dosage forms, meanwhile, the chelating agents can not cause any negative effect on the bactericide composition, and the pesticide effect is remarkably improved when the bactericide composition is mixed with medicaments of other compositions and dosage forms.
The inventor of the application researches the principle that flocculation and precipitation occur when the composition of the common zhongshengmycin-chitosan oligosaccharide is tank-mixed with preparations of different formulations, and finds that the electric neutralization and the adsorption bridging effect play the main roles. By adding a chelating agent into the zhongshengmycin-chitosan oligosaccharide composition, one or more of Ethylene Diamine Tetraacetic Acid (EDTA), sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, potassium sodium tartrate and nitrilotriacetic acid (NTA) are utilized to shield amino cations of the chitosan oligosaccharide, so that the amino cations cannot generate electric neutralization and adsorption bridging action with auxiliary agents and active ingredients in preparations, the problems of flocculation and precipitation when the zhongshengmycin-chitosan oligosaccharide composition is mixed with different preparations in a barrel are solved, and the pesticide effect of the composition containing zhongshengmycin and chitosan oligosaccharide and pesticide mixing barrels with other compositions and dosage forms is obviously improved.
FIGS. 1 to 3 in the drawings of the specification show the case where a conventional zhongshengmycin-chitosan oligosaccharide composition and a bactericide composition of the present invention are mixed with a suspending agent, a microcapsule suspending agent and a cream agent in equal amounts, respectively, wherein the mixed liquid in the graduated cylinder on the left side of each picture reflects the case where the conventional zhongshengmycin-chitosan oligosaccharide composition is mixed with other dosage forms of the bactericide composition containing the specific chelating agent of the present invention, and the mixed liquid in the graduated cylinder on the right side of each picture reflects the case where the bactericide composition of the present invention containing the specific chelating agent is mixed with other dosage forms of the bactericide composition, and it can be seen from FIGS. 1 to 3 that the problems of serious flocculation, precipitation and the like occur when the conventional zhongshengmycin-chitosan oligosaccharide composition is mixed with other dosage forms of the bactericide composition consisting of zhongshengmycin, chitosan oligosaccharide and the complex chelating agent, and substantially no flocculation, precipitation and the, the flocculation and precipitation degree of the zhongshengmycin-chitosan oligosaccharide composition when being mixed with other medicament forms is obviously reduced.
According to the present invention, the weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the chelating agent may be 1: (0.5-10): (10-25).
According to the present invention, the weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the chelating agent may be 1: (1-5): (15-20).
The weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the chelating agent is 1: (0.1-15): (5-30), the purpose of the invention can be realized, and the bactericide composition containing the zhongshengmycin and the chitosan oligosaccharide does not generate flocculation and sedimentation when being tank-mixed with medicaments with other compositions and dosage forms; preferably, the weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the chelating agent is 1: (0.5-10): (10-25), more preferably, the weight ratio of the Zhongshengmycin, the chitosan oligosaccharide and the chelating agent is 1: (1-5): (15-20), the above-mentioned fungicide composition is more excellent in tank-mixing property, can be tank-mixed with various dosage forms of preparations, and does not produce flocculation, precipitation, etc. during tank-mixing, and its medicinal effect is further raised, and its control effect is further raised.
According to the present invention, the fungicide composition may further contain an auxiliary agent, which may be formulated as required with ingredients commonly used in the art, for example, the auxiliary agent may include at least one of a solvent, a dispersing agent, a wetting agent, an emulsifier, a stabilizer, a preservative, a thickener, a binder, an antifoaming agent, an acid adjusting medium, a base adjusting medium, a colorant, and a solid inert carrier. When the bactericide composition is prepared into different dosage forms, the dosage of the auxiliary agent can be selected from conventional dosage, which is well known by the person skilled in the art and is not described herein again.
According to the invention, the auxiliary agent can be selected from substances commonly used in the field, and the solvent can comprise at least one of toluene, xylene, DMF, NMP, No. 150 solvent naphtha, No. 120 solvent naphtha, methanol, mixed benzene, mineral oil, cyclohexanone, DMSO, dichloromethane, trichloromethane, ethyl acetate, sec-butyl acetate, isopropanol and tetrahydrofuran; the dispersant may include alkyl naphthalene sulfonate, bis (alkyl) naphthalene sulfonate formaldehyde condensate, aryl phenol polyoxyethylene succinate sulfonate, octyl phenol polyoxyethylene ether sulfate, polycarboxylate, lignin sulfonic acid sodium salt, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl benzene sulfonic acid calcium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenolAt least one of polyoxyethylene ether, fatty amine polyoxyethylene ether and fatty acid polyoxyethylene ester; the wetting agent can comprise at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, washing powder, pesticide emulsion 2000# series, sodium lauryl sulfate, wetting penetrant F, wetting agent T, Chinese honeylocust fruit powder, tea seed cake, silkworm excrement and soapberry powder; the emulsifier may include at least one of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and a zwitterionic surfactant, and the emulsifier may include calcium dodecylbenzenesulfonate, sodium sulfosuccinate, styrylphenol polyoxyethylene ether phosphate, benzylphenol polyoxyethylene ether phosphate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan alcohol hexastearate, polyethylene glycol fatty acid esters, polyoxyethylene sorbitol ether beeswax derivatives, polyethylene glycol monostearate, sorbitan sesquioleate, glycerol monostearate, sorbitan monooleate, sorbitan monostearate, dibenzylphenol polyoxyethylene ether, diethylene glycol fatty acid esters, diethylene glycol monolaurate, sorbitan monolaurate, polyoxyethylene lauryl ether, and zwitterionic surfactants, One or more of polyoxyethylene monopalmitate, alkylphenol ethoxylates, sorbitan polyoxyethylene ether, polyoxyethylene sorbitan monooleate, styryl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether and castor oil polyoxyethylene ether; the thickener may include at least one of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, and phenolic resin; the binder may include at least one of starch, gypsum, glucose, polyvinyl alcohol, gum arabic, and dextrin; the defoaming agent may include silicones, C8-10Fatty alcohols, C10-20Saturated fatty acids (e.g. capric acid), C10-20At least one of saturated fatty acid amide, silicone oil and polysiloxane compound; the acid adjusting medium may include at least one of ammonium chloride, hydrochloric acid, citric acid, ammonium sulfate, ammonium nitrate, and acetic acid; the alkali adjusting medium can comprise sodium hydroxide, triethanolamine, triethylamine, ammonia water and sodium ethoxideAt least one of; the solid inert carrier may include at least one of clay, silica, diatomaceous earth, kaolin, attapulgite, montmorillonite, bentonite, talc and precipitated calcium carbonate. The stabilizers, preservatives and colorants can be those commonly used in the art, and are well known to those skilled in the art and will not be described in detail herein.
According to the present invention, the formulation of the fungicide composition may include at least one of wettable powder, water dispersible granule and soluble liquid.
According to the present invention, the formulation of the fungicide composition is preferably a wettable powder from the viewpoint of the method of using the fungicide.
The above dosage forms have no special requirements for other auxiliary ingredients except for the active ingredient and the chelating agent, and the content and active ingredient content thereof, and can adopt conventional proportions in the field, such as:
wettable powders may generally contain from 3 to 95% by weight of active ingredient, from 0.5 to 10% by weight of dispersant, from 0.5 to 5% by weight of wetting agent, from 0 to 10% by weight of other auxiliaries, such as stabilizers and the like, and the balance solid inert carriers, such as kaolin and the like.
Water dispersible granules may generally contain 3 to 95% by weight of active ingredient, 0.5 to 10% by weight of dispersant, 0.5 to 5% by weight of wetting agent, 0 to 10% by weight of other auxiliaries such as stabilizers, binders, and the balance solid inert carriers such as kaolin and the like. The water dispersible granule can be prepared into particles with 10-100 meshes of international standard mesh (1676-.
The soluble liquor can generally contain 0.1 to 40 wt.% of active ingredient, 5 to 15 wt.% of emulsifier, 0.1 to 10 wt.% of antifreeze, further auxiliaries such as stabilizers, preservatives, thickeners, antifoams, and the balance solvents, cosolvents. Soluble solutions are generally prepared by mixing and stirring various materials.
In the present invention, there is no special requirement for the preparation method of various dosage forms, and various methods known in the art can be adopted, and are not described herein again. The various formulations of the bactericide composition of the present invention can be diluted for use as required.
According to the present invention, there is no particular requirement for the content of the active ingredient in the fungicide composition, and a conventional amount may be selected according to various formulation forms of composition formulation, which are well known to those skilled in the art, for example, the content of the active ingredient in the fungicide composition may be 1 to 95% by weight.
In another aspect, the invention also provides the use of the fungicide composition in the control of crop diseases, wherein the diseases can include at least one of bacterial wilt, late blight, fusarium wilt, virus disease, soft rot, scab, apple ring rot, downy mildew, anthracnose, gibberellic disease, powdery mildew, banded sclerotial blight, early blight, rice blast and leaf spot.
The bactericide composition can be used in tank mixing with preparations of different compositions and dosage forms for preventing and treating different diseases of various crops, and the pesticide effect is obviously higher than that of the conventional zhongshengmycin-chitosan oligosaccharide composition in tank mixing with the preparations of different dosage forms.
When in application, the bactericide composition can be mixed with other active components and agents of dosage forms (such as suspending agents, water dispersible granules, wettable powder, missible oil, microcapsule suspending agents and the like) in a barrel for preventing and treating one or more crop diseases. By adding the chelating agent, the bactericide composition of the invention can not generate flocculation, precipitation and the like when being used with other medicaments with one or more compositions and dosage forms in a tank mixing way, thereby ensuring the full play of the drug effects of different active ingredients when various preparations are used in the tank mixing way, and playing the synergistic interaction effect by mutually matching, and greatly improving the drug application convenience and the drug effect.
In the present invention, the fungicide composition can be used by a method commonly used in the art, for example, it can be directly spread in the field or diluted and sprayed in the field. Preferably, the bactericide composition can be used in a tank-mix manner with preparations of different active ingredients and different dosage forms. From the aspects of pesticide utilization rate, pathogenic bacteria resistance reduction and comprehensive control, the preferred application method of the bactericidal composition is that the bactericidal composition is sprayed in the field after being mixed and diluted with preparations with different active ingredients and different formulations.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Table 1: weight ratio of Zhongshengmycin, Chitosan oligosaccharide and the chelating agent in examples 1-9
Zhongshengmycin: chitosan oligosaccharide: the chelating agent
Example 1 1:0.1:30
Example 2 1:15:5
Example 3 1:12:7
Example 4 1:0.5:25
Example 5 1:10:10
Example 6 1:0.7:12
Example 7 1:1:20
Example 8 1:5:15
Example 9 1:3:17
Example 12.2% Zhongshengmycin Chitosan oligosaccharide soluble liquid formulation
(the weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the sodium tripolyphosphate is 1: 0.1: 30) and 40 percent of fluazinam-iprodione suspending agent are mixed in a bucket.
The zhongshengmycin-chitosan oligosaccharide soluble liquid consists of: 2 percent of zhongshengmycin, 0.2 percent of chitosan oligosaccharide, 60 percent of sodium tripolyphosphate, 7 percent of bis (alkyl) naphthalenesulfonate formaldehyde condensate, 3 percent of sodium dodecyl benzene sulfonate, 0.2 percent of polysiloxane antifoaming agent and corn starch, wherein the weight percentage of the corn starch is 100 percent.
The weight ratio of 2.2% of the zhongshengmycin-chitosan oligosaccharide soluble liquid to 40% of the fluazinam-iprodione suspending agent is 1: 1.
Example 240% Zhongshengmycin Chitosan oligosaccharide soluble liquor (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and EDTA 1: 15: 5) was tank mixed with 40% fluazinam iprodione suspension.
The zhongshengmycin-chitosan oligosaccharide soluble liquid consists of: 2.5 percent of zhongshengmycin, 37.5 percent of chitosan oligosaccharide, 12.5 percent of ethylene diamine tetraacetic acid, 7 percent of polycarboxylate, 3 percent of sodium lauryl sulfate, 0.2 percent of polysiloxane antifoaming agent and corn starch, wherein the weight percentage is 100 percent.
The weight ratio of the 40% Zhongshengmycin-chitosan oligosaccharide soluble liquid to the 40% fluazinam-iprodione suspending agent is 1: 1.
Example 332.5% Zhongshengmycin Chitosan oligosaccharide soluble liquor (1: 12: 7 weight ratio of Zhongshengmycin, Chitosan oligosaccharide and sodium pentametaphosphate) was tank mixed with 40% fluazinam suspending agent.
The zhongshengmycin-chitosan oligosaccharide soluble liquid consists of: 2.5 percent of zhongshengmycin, 30 percent of chitosan oligosaccharide, 17.5 percent of sodium pentametaphosphate, 7 percent of sodium lignosulfonate, 3 percent of nekal BX, 0.2 percent of polysiloxane antifoaming agent and corn starch, wherein the weight percentage of the corn starch is 100 percent.
The weight ratio of 32.5 percent of the zhongshengmycin-chitosan oligosaccharide soluble liquid to 40 percent of the fluazinam-iprodione suspending agent is 1: 1.
Example 43.75% Zhongshengmycin Chitosan oligosaccharide water dispersible granule (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and ammonium citrate is 1: 0.5: 25) is tank mixed with 40% fluazinam iprodione suspending agent.
The zhongshengmycin-chitosan oligosaccharide water dispersible granule comprises the following components: 2.5 percent of zhongshengmycin, 1.25 percent of chitosan oligosaccharide, 62.5 percent of ammonium citrate, 7 percent of aryl phenol polyoxyethylene succinate sulfonate, 7 percent of alkyl benzene sulfonate calcium salt, 0.2 percent of polysiloxane antifoaming agent and ammonium sulfate added to 100 percent by weight.
The weight ratio of 3.75% Zhongshengmycin-chitosan oligosaccharide water dispersible granule to 40% fluazinam-iprodione suspending agent is 1: 1.
Example 527.5% Zhongshengmycin Chitosan oligosaccharide water dispersible granule (weight ratio of Zhongshengmycin, Chitosan oligosaccharide, potassium sodium tartrate is 1: 10: 10) is tank mixed with 40% fluazinam iprodione suspending agent.
The zhongshengmycin-chitosan oligosaccharide water dispersible granule comprises the following components: 2.5 wt% of zhongshengmycin, 25 wt% of chitosan oligosaccharide, 25 wt% of potassium sodium tartrate, 7 wt% of bis (alkyl) naphthalene sulfonate formaldehyde condensate, 7 wt% of sodium dodecyl benzene sulfonate, 0.2 wt% of polysiloxane antifoaming agent and ammonium sulfate added to 100 wt%.
The weight ratio of 27.5% Zhongshengmycin-chitosan oligosaccharide water dispersible granule to 40% fluazinam-iprodione suspending agent is 1: 1.
Example 68.5% Zhongshengmycin-Chitosan oligosaccharide water dispersible granule (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and nitrilotriacetic acid is 1: 0.7: 12) and 40% fluazinam-iprodione suspending agent are mixed in a tank.
The zhongshengmycin-chitosan oligosaccharide water dispersible granule comprises the following components: 5 wt% of zhongshengmycin, 3.5 wt% of chitosan oligosaccharide, 60 wt% of nitrilotriacetic acid, 7 wt% of alkylphenol polyoxyethylene, 3 wt% of sodium dodecyl benzene sulfonate, 0.2 wt% of polysiloxane antifoaming agent and 100 wt% of ammonium sulfate.
The weight ratio of 8.5 percent of zhongshengmycin-chitosan oligosaccharide water dispersible granule to 40 percent of fluazinam-iprodione suspending agent is 1: 1.
Example 76% Zhongshengmycin Chitosan oligosaccharide wettable powder (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and ammonium citrate is 1: 1: 20) and 40% fluazinam iprodione suspension are mixed in a bucket.
The zhongshengmycin-chitosan oligosaccharide wettable powder consists of: 3 weight percent of zhongshengmycin, 3 weight percent of chitosan oligosaccharide, 60 weight percent of ammonium citrate, 7 weight percent of fatty amine polyoxyethylene ether, 3 weight percent of sodium dodecyl benzene sulfonate, 0.2 weight percent of polysiloxane antifoaming agent and 100 weight percent of kaolin.
The weight ratio of 6% Zhongshengmycin-chitosan oligosaccharide wettable powder to 40% fluazinam-iprodione suspending agent is 1: 1.
In example 812% Zhongshengmycin Chitosan oligosaccharide wettable powder (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and ammonium citrate is 1: 5: 15) and 40% fluazinam Isomycrea suspension are mixed in a bucket.
The zhongshengmycin-chitosan oligosaccharide wettable powder consists of: 2% of zhongshengmycin, 10% of chitosan oligosaccharide, 30% of ammonium citrate, 7% of bis (alkyl) naphthalene sulfonate formaldehyde condensate, 3% of wetting penetrant T, 0.2% of polysiloxane antifoaming agent and kaolin added to 100% by weight.
The weight ratio of 12% Zhongshengmycin-chitosan oligosaccharide wettable powder to 40% fluazinam-iprodione suspending agent is 1: 1.
Example 98% Zhongshengmycin Chitosan oligosaccharide wettable powder (weight ratio of Zhongshengmycin, Chitosan oligosaccharide and ammonium citrate is 1: 3: 17) and 40% fluazinam iprodione suspension are mixed in a bucket.
The zhongshengmycin-chitosan oligosaccharide wettable powder consists of: 2% of zhongshengmycin, 6% of chitosan oligosaccharide, 34% of ammonium citrate, 7% of bis (alkyl) naphthalene sulfonate formaldehyde condensate, 3% of sodium dodecyl sulfate, 0.2% of polysiloxane antifoaming agent and 100% of kaolin.
The weight ratio of 8% Zhongshengmycin-chitosan oligosaccharide wettable powder to 40% fluazinam-iprodione suspending agent is 1: 1.
Comparative example 1
10% Zhongshengmycin-chitosan oligosaccharide can be mixed with 40% fluazinam-iprodione suspending agent in a bucket (the ratio of Zhongshengmycin to chitosan oligosaccharide is 1: 3).
Zhongshengmycin-chitosan oligosaccharide wettable powder consists of: 2.5 percent of zhongshengmycin, 7.5 percent of chitosan oligosaccharide, 7 percent of bis (alkyl) naphthalene sulfonate formaldehyde condensate, 3 percent of sodium dodecyl benzene sulfonate, 0.2 percent of polysiloxane antifoaming agent and kaolin added to 100 percent by weight.
The dosage ratio of 10% Zhongshengmycin-chitosan oligosaccharide wettable powder to 40% fluazinam-iprodione suspending agent is 1: 1.
Comparative example 2
Spraying with water only.
Test example 1
Test site: the test soil is yellow clay, the texture is sticky and heavy, the pH value is 6.0-6.5, the test soil is slightly acidic, the management level is medium, the soil fertility is medium, and tomatoes in each treatment area after being planted are managed according to the conventional production. The tomato variety is Hanmu No. seven.
The tomatoes are sprayed by the tank-mixed agents of examples 1-9 and comparative example 1, the test water of comparative example 2 is sprayed, and the dilution times of the soluble liquid agent, the water dispersible granule or the wettable powder agent and the suspending agent after tank mixing are 750 times. The diluted medicament is respectively sprayed on the front and back surfaces of the tomato leaf surface, and the liquid medicament is uniformly sprayed on the two surfaces of the tomato leaf surface to the extent that the liquid medicament does not drip. The area of the test cell is 20m2And spraying is repeated for 4 times in each test area, and the conditions of soil, cultivation, water and fertilizer management and the like in each test area are consistent. The investigation statistical method of tomato diseases is as follows:
investigating the control effect of the tomato bacterial wilt and virus diseases after the application of the drugs for 3d, 7d and 15d respectively, wherein the specific method comprises the following steps:
sampling is carried out at random 5 points in each treatment area, 30 plants are investigated in each treatment area, the plant disease rate and the disease index of the diseases in the seedling stage of each treatment area are investigated, and the control effect is calculated according to the formula (I) and the formula (II).
The statistics of the disease states of the tomato bacterial wilt and the virus diseases refer to the pesticide field efficacy test criteria.
The tomato disease control effect is shown in table 2.
TABLE 2
As can be seen from the test data of examples 1-6 in Table 2, the effect of different chelating agents alone is very different; as can be seen from comparison of examples 4 and 7-9, the same chelating agent has a distinct effect between different dosage forms; comparing the data tested in comparative examples 1-9 and comparative examples 1-2, it can be seen that the zhongshengmycin-chitosan oligosaccharide composition containing the special chelating agent has better tank-mixing control effect for the common zhongshengmycin-chitosan oligosaccharide composition because the compositions do not have the phenomena of flocculation and sedimentation when tank-mixing with other preparations, and the difference is obvious. Different chelating agents, different chelating agent dosages, different zhongshengmycin-chitosan oligosaccharide dosages and proportions have different drug effects. The technical problem of the present application is not solved by any conventional chelating agent species and dosage, and the inventor of the present application has learned through thousands of experiments that a bactericidal composition with strong barrel-mix property can be obtained only by using the chelating agent species described in the present application and mixing the chelating agent species according to the weight ratio, wherein the preferable weight ratio of the zhongshengmycin, the chitosan oligosaccharide and the chelating agent is 1: (1-5): (15-20), the chelating agent is preferably ammonium citrate, the preferred formulation of the bactericide composition is wettable powder, the bactericide composition under the preferred conditions has good effect when being used alone, can most effectively prevent flocculation and precipitation when being mixed with other formulations and other medicaments, can well play a synergistic effect, and has better control effect on crop diseases.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the invention.

Claims (9)

1. A bactericide composition, wherein the bactericide composition comprises an active ingredient and a chelating agent, and the active ingredient comprises zhongshengmycin and chitosan oligosaccharide; the chelating agent comprises at least one of ethylenediamine tetraacetic acid, sodium pentametaphosphate, sodium tripolyphosphate, ammonium citrate, potassium sodium tartrate and nitrilotriacetic acid; the weight ratio of the zhongshengmycin to the chitosan oligosaccharide to the chelating agent is 1: (0.1-15): (5-30); the dosage form of the bactericide composition comprises at least one of wettable powder, water dispersible granules and soluble liquid.
2. A bactericide composition according to claim 1, wherein said chelating agent is ammonium citrate.
3. The bactericide composition as claimed in claim 1, wherein the weight ratio of zhongshengmycin, chitosan oligosaccharide and said chelating agent is 1: (0.5-10): (10-25).
4. A bactericide composition according to claim 3, wherein the weight ratio of zhongshengmycin, chitosan oligosaccharide and the chelating agent is 1: (1-5): (15-20).
5. The germicidal composition of any of claims 1-4, further comprising an adjuvant comprising at least one of a solvent, a dispersant, a wetting agent, an emulsifier, a stabilizer, a preservative, a thickener, a binder, an anti-foaming agent, an acid adjusting medium, a base adjusting medium, a colorant, and a solid inert carrier.
6. The germicidal composition of claim 5, wherein the solvent comprises at least one of toluene, xylene, DMF, NMP, No. 150 mineral spirits, No. 120 mineral spirits, methanol, mixed benzene, mineral oil, cyclohexanone, DMSO, methylene chloride, chloroform, ethyl acetate, sec-butyl acetate, isopropanol, and tetrahydrofuran; the dispersing agent comprises at least one of alkyl naphthalene sulfonate, a bis (alkyl) naphthalene sulfonate formaldehyde condensate, aryl phenol polyoxyethylene succinate sulfonate, octyl phenol polyoxyethylene ether sulfate, polycarboxylate, lignin sodium sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl benzene sulfonic acid calcium salt, naphthalene sulfonate formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty amine polyoxyethylene ether and fatty acid polyoxyethylene ester; the wetting agent comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, washing powder, pesticide emulsion 2000# series, sodium lauryl sulfate, wetting penetrant F, wetting agent T, Chinese honeylocust fruit powder, tea seed cake, silkworm excrement and soapberry powder; the emulsifier comprises at least one of a cationic surfactant, an anionic surfactant, a nonionic surfactant and a zwitterionic surfactant; the thickening agent comprises at least one of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin; the binder comprises at least one of starch, gypsum, glucose, polyvinyl alcohol, gum arabic, and dextrin; the defoaming agent comprises at least one of silicone, C8-10 fatty alcohols, C10-20 saturated fatty acids, C10-20 saturated fatty acid amides, silicone oil and polysiloxane compounds; the acid regulating medium comprises at least one of ammonium chloride, hydrochloric acid, citric acid, ammonium sulfate, ammonium nitrate and acetic acid; the alkali adjusting medium comprises at least one of sodium hydroxide, triethanolamine, triethylamine, ammonia water and sodium ethoxide; the solid inert carrier comprises at least one of clay, silicon dioxide, diatomite, kaolin, attapulgite, montmorillonite, bentonite, talcum powder and light calcium carbonate.
7. The bactericide composition as claimed in claim 1, wherein said bactericide composition is in the form of wettable powder.
8. The fungicidal composition according to claim 1, wherein the active ingredient is contained in an amount of 1 to 95% by weight in the fungicidal composition.
9. Use of the fungicide composition according to any one of claims 1 to 8 for controlling crop diseases, wherein said diseases include at least one of bacterial wilt, late blight, wilt, virus disease, soft rot, scab, apple ring spot, downy mildew, anthracnose, gibberellic disease, powdery mildew, banded sclerotial blight, early blight, rice blast and leaf spot.
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