CN108271791A - A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class - Google Patents
A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class Download PDFInfo
- Publication number
- CN108271791A CN108271791A CN201810204391.7A CN201810204391A CN108271791A CN 108271791 A CN108271791 A CN 108271791A CN 201810204391 A CN201810204391 A CN 201810204391A CN 108271791 A CN108271791 A CN 108271791A
- Authority
- CN
- China
- Prior art keywords
- present
- bactericidal composition
- agricultural
- agriculture
- downy mildew
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
Abstract
The present invention provides a kind of agriculture bactericidal composition, and the composition is by the compound with chemical constitution formula (I) with the second active constituent selected from dimethomorph or flumorph according to weight ratio 50:1~1:50 compositions.The present invention also provides the fungicide containing the agriculture bactericidal composition and its in the application of prevention cucumber downy mildew, the downy mildew of garpe late blight of potato.The combination has significant synergistic effect to disease, can effectively reduce times for spraying, reduce drug cost, reduces pollution and the pesticide residue to environment, action site increases, and is conducive to overcome and delay the generation of the drug resistance of germ.The present composition is without obvious harmful effects to trial crops, and leaf color, growing way etc. are all normal, and safety is good, meets the security requirement of pesticidal preparations.
Description
【Technical field】
The invention belongs to technical field of pesticide.More particularly it relates to which a kind of containing ether azoles sulfanilamide (SN) ester type compound
With the agriculture bactericidal composition of the second active constituent of morpholine class, the purposes of the agriculture bactericidal composition is further related to.
【Background technology】
Chinese patent application CN 201610003201.6, denomination of invention " a kind of Fungicidal compounds, microbicide compositions and
Preparation and its application " disclose a kind of ether azoles sulfanilamide (SN) ester type compound with bactericidal activity, take the compound as activity at
The microbicide compositions and preparation and its application, compound (the being referred to as compound Y14079) structure divided are as follows:
The Fungicidal compounds and preparation containing the Fungicidal compounds imitate cucumber downy mildew and rice sheath blight disease controlling
Fruit is notable.
Dimethomorph (dimethomorph) chemical name (E, Z) -4- [3- (4- chlorphenyls) 3- (3,4- dimethoxy benzenes
Base) acryloyl] morpholine, belong to morpholine class disinfectant use in agriculture, is usually used in preventing the downy mildew and late blight of the fruit trees such as grape.
Flumorph (flumorph) chemical name (E, Z) 4- [one 3 one (4 phenyl-monofluorides of 3- (37,4'-=methoxyphenyl)
Base) acryloyl] morpholine, belong to morpholine class disinfectant use in agriculture.It is especially effective to Peronospora, phytophthora element germ.To grape, potato and
Oomycete on tomato, especially Peronosporaceae and Phytophthora bacterium have fungicidal effectiveness.
But a kind of medicament is used alone for a long time, it is easy that pathogen is made to develop immunity to drugs, causes being decreased obviously for drug effect, from
And dosage is caused to rise significantly, cycle time is sprayed, and using effect is poor, increases cost, the increasing of dosage makes
The resistance of pathogen is more serious, while can be impacted to environment.Rational chemical bactericide combination or mixture, which has, to be expanded
Fungicidal spectrum improves the positive features such as control effect, the generation for delaying drug resistance of fungi and development.Therefore, research is opened
Efficient, less toxic, environmental protection the bactericidal composition of hair and fungicide have positive effect to agricultural sustainable development.
【Invention content】
The purpose of the present invention is overcoming single drug defect, a kind of agriculture bactericidal composition is provided and contains the combination
The agricultural bacteriocide of object, and the purposes of the agricultural bactericidal composition or fungicide is provided.
To achieve the goals above, the present invention provides a kind of agriculture bactericidal composition, and the composition is by with following chemistry
The compound of structure formula (I) is with the second active constituent according to weight ratio 50:1~1:50 compositions:
Wherein, the second active constituent is dimethomorph or flumorph.
Preferably, chemical constitution formula (I) compound and the weight ratio of the second active constituent are 20:1~1:20.
The present invention also provides a kind of agricultural bacteriocide, which contains 0.5~95.0% above-mentioned agricultural by weight and kills
Bacteria composition and surplus are agriculturally acceptable carrier and auxiliary agent.
Preferably, it is agriculturally which, which contains 10~60% above-mentioned agriculture bactericidal composition and surplus by weight,
Acceptable carrier and auxiliary agent.
In the present invention, the dosage form of the disinfectant use in agriculture is that water dispersion granule, wettable powder, suspending agent or oil are outstanding
Floating agent.
The present invention also provides above-mentioned agriculture bactericidal compositions or agricultural bacteriocide in prevention cucumber downy mildew, downy mildew of garpe
And/or the purposes in the late blight of potato.
Further, the present invention also provides a kind of methods of prevention crop disease, in crops and/or fruit introduced disease
Before or after, apply above-mentioned bactericidal composition or fungicide to the place of crops and/or fruit and growth or storage.
The present invention is described in more detail below.
The present invention relates to a kind of agriculture bactericidal compositions.The agriculture bactericidal composition is by with following chemical structural formulas
(I) compound is with the second active constituent according to weight ratio 50:1~1:50 compositions:
Second active constituent is dimethomorph or flumorph.
The compound be Chinese invention patent application CN 201610003201.6, denomination of invention " a kind of Fungicidal compounds,
(the also referred to as compound Y14079 of formula (II) compound disclosed in microbicide compositions and preparation and its application ".In the present invention
In to simplify the description, with active constituent Y14079 represent).It is described according to patent application CN 201610003201.6
Prepared by synthetic route (2).
In agriculture bactericidal composition of the invention, when the amount of active ingredient Y14079 is in the range, if second
The amount of active constituent is more than the range of the amount, then can decline because of dosage height, safety, poisoning easily occurs.Similarly, the second activity
, also can be high because of dosage if the amount of active ingredient Y14079 is more than the range of the amount when amount of ingredient is in the range,
Safety declines, and poisoning easily occurs.
Therefore, in agriculture bactericidal composition of the invention, active ingredient Y14079 and the weight ratio of the second active constituent are
50:1~1:50 are reasonable.
Preferably, the weight ratio of active ingredient Y14079 and the second active constituent is 10:1~1:10.
The present invention relates to a kind of agricultural bacteriocides.The agricultural bacteriocide contains by weight described in 0.5~95.0%
Agriculture bactericidal composition and surplus be agriculturally acceptable carrier and auxiliary agent.
In the present invention, the carrier or auxiliary agent are it should be understood that for improving medicine in Pesticide formulation or use
Agent physicochemical property, improve drug effect, be readily transported storage etc. performances auxiliary substances, such as wetting agent, emulsifier, dispersant,
Sticker, stabilizer or synergist etc..It is every that there are these performances and agricultural bacteriocide of the present invention is not appointed according to the present invention
The chemical substance of what negative effect may be used to the present invention, they are all within protection scope of the present invention.
It can be because having if the agriculture bactericidal composition content of the agricultural bacteriocide is less than 0.5% according to the present invention
Effect ingredient is low, is unfavorable for the manufacturing of product from economic angle;If the agriculture bactericidal composition of the agricultural bacteriocide
When content is higher than 95.0%, then because of the too high performance for being unfavorable for drug effect of content and poisoning can be also easy to produce;Therefore, the agricultural sterilization
It is appropriate that the agriculture bactericidal composition content of agent, which is 0.5~95.0%,.
Preferably, the agricultural bacteriocide contains the agriculture bactericidal composition and surplus described in 15~60% by weight
For agriculturally acceptable carrier and auxiliary agent.
In the present invention, the carrier used is solid carrier or liquid-carrier.
The solid carrier is selected from silicate, carbonate, sulfate, oxide, alkali metal salt, vegetalitas carrier or conjunction
At earthfill rockfill concrete riprap RCC carrier etc..
Wherein silicate, carbonate, sulfate and oxide carrier are mineral substance carrier.For example, silicate carrier is high
Ridge soil, sepiolite, nacrite, montmorillonite, mica, vermiculite, pyrophyllite or talcum etc..Carbonate support is calcium carbonate or white clouds
Stone etc..Sulfate carrier is ammonium sulfate, sodium sulphate or calcium sulfate etc..Oxide carrier is quick lime, magnesium lime or diatomite etc..
Alkali metal salt carrier is potassium chloride or sodium chloride etc..
Vegetalitas carrier is citrus pulp, corncob cellulose, rice husk powder, rice husk, big soya bean stem meal, tobacco powder, walnut shell or sawmilling
Powder etc..
Synthetic filling class carrier is winnofil hydrate, winnofil or white carbon etc..
These solid carriers that the present invention uses are sold known to technical staff, currently on the market in the art
The by-product of the product or widely known agricultural byproducts processing sold.
The liquid-carrier (solvent) is selected from water, aromatic hydrocarbons, chlorinated aliphatic hydrocarbon, aliphatic hydrocarbon, alcohols, ethers, ketone, plant
Oil, methylated vegetable oils or other special solvents.For example, aromatic hydrocarbons carrier is benzene, dimethylbenzene, toluene, alkylbenzene, alkylnaphthalene and chlorine
For aromatic hydrocarbons etc..
Chlorinated aliphatic hydrocarbon carrier is vinyl chloride, chloroform, dichloromethane, chloroform, carbon tetrachloride and more chloroethanes etc..
Aliphatic hydrocarbon carrier is petroleum distillate, hexamethylene, light mineral oil or paraffin etc., such as limited by Jiangsu China human relations chemical industry
The S-200 fat hydrocarbon products of company's sale being mainly made of octane and heptane.
Alcoholic vehicle is methanol, ethyl alcohol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, glycerine or fatty alcohol
Deng.
Ethers carrier is Propylene Glycol ether, ethohexadiol ether or petroleum ether etc..
Ketone is acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, isophorone or N- methyl-pyrrolidons etc..
In the present invention, the special solvent is it should be understood that the solvent being used in mixed way with one or more of solvents.It is described
Solvent in special solvent is dimethylformamide, dimethyl sulfoxide (DMSO), polyethylene glycol or nitrile etc..
Vegetable oil is soybean oil, rapeseed oil, peanut oil or sesame oil etc..
Methylated vegetable oils are methylated soya oil, rapeseed oil, peanut oil or sesame oil etc..What the present invention used methylates
Vegetable oil is all in current market sales of product.
The liquid-carrier that the present invention uses all is in the art known to technical staff, current market sales of
Product, for example, sold by Sinopec Group Hangzhou Refinery light mineral oil, by Shanghai Sheng Jun Industry investments Co., Ltd
Propylene Glycol ether, ethohexadiol ether, methyl iso-butyl ketone (MIBK), isophorone, the dimethylformamide of sale.
When using a kind of above-mentioned organic solvent when, this organic solvent can with single use, can also from it is other different
Organic solvent is used in mixed way, or is used in mixed way with water.When used as a mixture, mixed proportion can according to actual use situation into
Row selection, this is that hell and high water is not present for those skilled in the art.
The auxiliary agent that the present invention uses selected from emulsifier, dispersant, stabilizer or wetting agent surfactant, disappear
Infusion, thickener, suspending agent and antifreezing agent.
The surfactant is the surfactant used in emulsifier, dispersant, stabilizer or wetting agent.
The surfactant that the present invention uses can be ionic or nonionic, such as polyacrylic acid sodium salt and calcium
Salt, lignin sulfonic acid sodium salt and calcium salt;With at least 12 carbon atom fatty acids or fatty amine and ethylene oxide and/or epoxy third
The polycondensation product of alkane;Glycerine, dodecanol -1, tetradecanol -1, sorbierite, sucrose or pentaerythritol fatty ester and they
With ethylene oxide and/or the polycondensation product of propylene oxide;The sulfate or sulfonate of the polycondensation product;With at least ten carbon
Atom alkyl sulfuric acid or sulfonate alkali metal or alkali salt, preferably sodium salt, as lauryl sodium sulfate, secondary alkyl sulfuric acid
Sodium, sulfonated castor oil sodium salt, alkylaryl sodium sulfonate or neopelex;Ethylene oxide polymer or ethylene oxide and ring
Ethylene Oxide copolymer.
Emulsifier that the present invention uses is allowed to shape it should be understood that one kind can improve each phase interfacial surface tension in emulsion
At the substance of uniform and stable dispersion or emulsion.It is every that there are these performances and agricultural bacteriocide of the present invention is not appointed
The chemical substance of what negative effect may be used to the present invention, they are all within protection scope of the present invention.
The emulsifier that the present invention uses is nonionic emulsifier.For example, the nonionic emulsifier is selected from polyoxy
Ethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether and Polyoxyethylene fatty ammonia, as ethoxylated castor oil, polyoxyethylene (n20) benzene
Ethyl phenolic group oleic acid ester, alkylaryl polyoxyethylene poly-oxygen propylene aether, alkylaryl formaldehyde resin polyoxyethylene ether, triphen second
Alkenyl phenol polyethenoxy (n20), ether phosphoric acid triethanolamine salt, Diphenethyl phenolic group polyoxyethylene ether (n18) formaldehyde condensation products,
Diphenyl phenol polyethenoxy (n18) polyethenoxy ether (n20) etc., these nonionic emulsifier are all current market sales of
Product, such as the polyoxyethylene (n by the offer of Jiangsu Kai Yuan Science and Technology Ltd.s20) phenethyl phenolic group oleic acid ester, alkylaryl
Formaldehyde resin polyoxyethylene ether, sale diphenyl phenol polyethenoxy (n18) polyethenoxy ether (n20).The emulsification that the present invention uses
Agent can be commercial emulsifier, such as agriculture breast 0201B, agriculture breast 0203B, agriculture breast 100#, agriculture breast 500#, agriculture breast 600#, agriculture breast 600-
2#, agriculture breast 1601, agriculture breast 2201, agriculture breast NP-10, agriculture breast NP-15, agriculture breast 507#, agriculture breast OX-635, agriculture breast OX-622, agriculture breast
OX-653, agriculture breast OX-667, agriculture breast CS-7 or peaceful breasts 36#。
Dispersant that the present invention uses is it should be understood that a kind of in the molecule while having lipophilic fraction and hydrophily portion
Point interfacial agent, it be it is a kind of will can be difficult to be dissolved in the solid in liquid evenly dispersed with liquid particles, simultaneously and also
It can be prevented to settle and agglomerate, form the substance of stable suspension.It is every to there are these performances and to agricultural bacteriocide of the present invention
There is no the chemical substance of any negative effect to may be used to the present invention, they are all within protection scope of the present invention.
The dispersant that the present invention uses is, for example, sodium lignin sulfonate, pull open powder, calcium lignosulfonate, methyl naphthalene sulfonic acid first
Aldehyde condensate, naphthalene sulfonic acid-formaldehyde condensation product, methanonaphthalene sodium sulfonate, oleic acid methylaminoethyl sodium sulfonate, epoxidized polyether, to uncle
Butyl ether, dibutyl naphthalenesulfonic acid formaldehyde condensation produc, phosphate such as calgon, alkylphenol-polyethenoxy based phosphates, alkyl
Phenol polyethenoxy base ether formaldehyde condensation products sulfate, the contracting of N- methyl-fatty acyl group-sodium taurocholate alkyl phenol polyoxyethylene ether formaldehyde
Close object, aralkyl phenol polyethenoxy ether phosphate alkyl phenol polyoxyethylene ether, castor oil ethylene oxide adduct, ethylene oxide-
Propylene oxide block copolymer APES formaldehyde condensation product, alkylphenol-polyethenoxy polyethenoxy ether and methyl are fine
Dimension element.
The dispersant that the present invention uses all is current market sales of product, such as by Nanjing Teva-Chem. Co., Ltd.
N- methyl-fatty acyl groups-sodium taurocholate the APES formaldehyde condensation product of sale, castor oil ethyleneoxide addition
Object, ethylene oxide-propylene oxide block copolymer APES formaldehyde condensation product, alkylphenol-polyethenoxy Ji Mijia
Aldehyde condensate sulfate.
The stabilizer that the present invention uses is, for example, sodium lignin sulfonate.The stabilizer that the present invention uses all is currently on the market
The product of sale, such as the lignin series of products sold by virtue Visco Co..
Wetting agent that the present invention uses it should be understood that one kind can reduce solid material surface tension or interfacial tension,
Water is easily spread out on the surface thereof and the substance that soaks solid material.It is every to there are these performances and to agricultural sterilization of the invention
Agent does not have the chemical substance of any negative effect to may be used to the present invention, they are all within protection scope of the present invention.
The wetting agent that the present invention uses is selected from sldium lauryl sulfate, alkylol polyoxyethylene base ether sodium sulfate, octylphenol polyethylene
Oxyethylene group ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, sodium alkyl sulfonate, dodecyl benzene sulfonic acid
Sodium, Negel, dialkyl succinylsuccinate sulfonate, lauryl alcohol polyethylene glycol oxide base ether sulfonic acid sodium, alkyl amide sodium taurocholate, fat
Fat alcohol polyoxyethylene ether, alkylphenol-polyethenoxy base ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty
Acid esters polyoxyethylene ether etc..
The wetting agent that the present invention uses all is current market sales of product, such as is sold by Xing Fei Chemical Co., Ltd.s
Alkylol polyoxyethylene base ether sodium sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, lauryl alcohol polyethylene glycol oxide
Base ether sulfonic acid sodium, sorbitan fatty acid ester polyoxyethylene ether.
In addition to above-mentioned surfactant, the auxiliary agent that the present invention uses also has antifoaming agent, thickener, suspending agent and antifreezing agent.
The antifoaming agent that the present invention uses is it should be understood that a kind of substance with chemistry and surface chemistry defoaming effect.It is every
There is no the chemical substance of any negative effect to may be used to the present invention with these performances and to agricultural bacteriocide of the present invention, it
All within protection scope of the present invention.
The antifoaming agent is selected from bubble enemy, silicone, C8~10Fatty alcohol, C10~20Saturated fatty acid or amide antifoaming agent;
The antifoaming agent that the present invention uses all is current market sales of product, such as is sold by Nanjing Jie Run Co., Ltds
Bubble enemy, C10~20Saturated fatty acid, amide antifoaming agent.
Thickener that the present invention uses can be improved and be killed it should be understood that one kind can be such that agricultural bacteriocide of the present invention emulsifies
Microbial inoculum viscosity simultaneously reaches stable substance.It is every that there are these performances and do not have any negative shadow to agricultural bacteriocide of the present invention
Loud chemical substance may be used to the present invention, they are all within protection scope of the present invention.
The thickener is selected from carboxymethyl alcohol, polyvinyl alcohol, polyvinyl acetate, xanthans, gelatin, Arabic tree
Glue, polyvinylpyrrolidone, aluminum magnesium silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, carboxymethyl cellulose or seaweed
Sour sodium;
The thickener that the present invention uses all is current market sales of product, such as by Beijing Green Tai Mu Co., Ltds
Carboxymethyl alcohol, the polyvinylpyrrolidone of sale.
The suspending agent that the present invention uses is it should be understood that one kind can increase agricultural bacteriocide viscosity of the present invention to reduce
Wherein particle sinking speed or the increase hydrophilic substance of particle.It is every that there are these performances and do not have to agricultural bacteriocide of the present invention
There is the chemical substance of any negative effect to may be used to the present invention, they are all within protection scope of the present invention.
The suspending agent is selected from glycerine, Arabic gum, tragacanth, peach gum, methylcellulose, sodium carboxymethylcellulose
Or hydroxypropyl cellulose.
The suspending agent that the present invention uses all is current market sales of product, such as by Nanjing Guan Hua trade Co., Ltds
Xanthans, peach gum, the sodium carboxymethylcellulose of sale.
The antifreezing agent that the present invention uses is it should be understood that one kind can prevent agricultural bacteriocide of the present invention in microthermal climate ring
The substance freezed under border.It is every that there are these performances and do not have the chemistry of any negative effect to agricultural bacteriocide of the present invention
Substance may be used to the present invention, they are all within protection scope of the present invention.
The antifreezing agent is selected from glycerine, urea, ethylene glycol or propylene glycol.
The antifreezing agent that the present invention uses all is current market sales of product.
According to the present invention, the agricultural bacteriocide is water dispersion granule, wettable powder, suspending agent or oil-suspending agent
Etc. dosage forms.
Particularly, for water dispersible granules, those skilled in the art are very familiar with completes the present invention using corresponding auxiliary agent.It can
The auxiliary agent used is such as:Dispersant selects polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate;Wetting agent is selected from polyoxyethylene
Alcohol, alkyl sulfate, alkylsulfonate, naphthalene sulfonate;Disintegrant is selected from ammonium sulfate, urea, sucrose, glucose, aluminium chloride, lemon
Lemon acid, succinic acid, sodium bicarbonate;Binder is selected from diatomite, cornstarch, PVA, methylol (ethyl) cellulose family;Filler
Select diatomite, kaolin, white carbon, fine particle calcium carbonate, sepiolite, talcum powder, attapulgite, clay.
For wettable powder, workable auxiliary agent is such as:Dispersant selects polycarboxylate, lignosulfonates, alkylnaphthalene sulphur
Hydrochlorate;Wetting agent is selected from alkyl sulfate, alkylsulfonate, naphthalene sulfonate;Filler is selected from ammonium sulfate, urea, sucrose, grape
Sugar, diatomite, kaolin, white carbon, fine particle calcium carbonate, talcum powder, attapulgite, clay.
For suspending agent, workable auxiliary agent has:Dispersant selects polycarboxylate, lignosulfonates, alkyl naphthalene sulfonic acid
Salt, TERSPERSE 2425 (Huntsman Corporation of the U.S. produces, alkyl naphthalene sulfonic acid salt);It is (general that emulsifier is selected from Nongru-700 #
Name:Alkyl phenol formaldehyde resin polyoxyethylene ether), agriculture breast 2201, this disk -60# (common names:Sorbitan monostearate), breast
Agent T-60 (common names:Sorbitan monostearate polyoxyethylene ether), 1601 (common name of agriculture breast:Phenethyl phenol is poly-
Ethylene oxide polyethenoxy ether), TERSPERSE 4894 (Huntsman Corporation of U.S. product);Wetting agent is selected from alkylphenol-polyethenoxy
Poly- base ether formaldehyde condensation products sulfate, alkylphenol-polyethenoxy base ether phosphate, phenethyl phenol polyoxyethylene groups ether phosphate, alkane
Base sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500 (Huntsman Corporation of U.S. product);Thickener is selected from Huang
Virgin rubber, polyvinyl alcohol, bentonite;Preservative is selected from formaldehyde, benzoic acid, sodium benzoate;Antifoaming agent is organic silicon antifoaming agent;It is anti-
Freeze agent and is selected from ethylene glycol, propylene glycol, glycerine, urea, inorganic salts such as sodium chloride.
For dry suspending agent, workable auxiliary agent has:Lignosulfite, soda pulping waste, animals and plants hydrolyze egg
In vain, soap, thermoplastic water-soluble base.
When agricultural bacteriocide of the present invention is water dispersible granules, preparation method is as follows:Activity is taken based on composition total weight
Ingredient Y140790.1%~80%, dimethomorph or flumorph 10%~90%, surfactant 0%~2%, wetting agent 1%
~15%, dispersant 1%~15%, disintegrant 1%~10%, stabilizer 0%~5%, filler polishing to 100%, mixed powder
It is broken, be added in the comminutor equipped with certain specification sieve and be granulated after adding water to mediate, then through drying, sieve up to graininess
Product.
When agricultural bacteriocide of the present invention is suspending agent, preparation method is as follows:Active constituent is taken based on composition total weight
Y140790.1%~80%, dimethomorph or flumorph 5%~90%, dispersant 1%~8%, increase wetting agent 1%~5%
Thick dose 0.1%~1%, antifreezing agent 2%~5%, water polishing to 100%, using water as medium, by active ingredient, dispersant, wetting
Uniformly mixed add in sand mill such as agent, suspending agent and antifreezing agent is sanded to certain grain size, and thickener shearing is added after filtering
It stirs evenly, prepares the suspending agent of required concentration.
When agricultural bacteriocide of the present invention is wettable powder, preparation method is as follows:Activity is taken based on composition total weight
Ingredient Y140790.1%~80%, dimethomorph or flumorph 10%~90%, wetting agent 2%~10%, dispersant 5%~
10% and filler 8~90% mix, uniform stirring in a stirring kettle reuses airslide disintegrating mill commonly used in the art and crushes
After remix and uniformly obtain the wettable powder.
When agricultural bacteriocide of the present invention is oil-suspending agent, preparation method is as follows:Taken based on composition total weight activity at
Point Y140790.1%~80%, dimethomorph or flumorph 10%~90%, emulsifier 5%~20%, dispersant 1%~
5%, thickener 1%~5%, methyl oleate polishing to 100%.By active constituent Y14079, the second active constituent, emulsifier,
Dispersant, methyl oleate etc. are uniformly mixed, after sand mill is ground to certain grain size.
Conventional method application, such as injection, spraying may be used in bactericidal composition and fungicide of the present invention.Its amount of application can
To be changed according to weather conditions or crop growthing state, can be applied before or after disease occurs.Protective effect is held
The continuous time is usually related with the content of single compound in composition, also related to extraneous factor, such as weather, but by using
Dosage form appropriate can slow down the influence of weather.
Bactericidal composition and fungicide of the present invention can also be mixed with other compounds with weeding, bactericidal property to be made
With can also be used in mixed way with protective agent, growth regulator, nutrient for plants or soil conditioner.
[advantageous effect]
Bactericidal composition of the present invention has following advantageous effects:
(1) compared with single dose, the bactericidal composition is to prevention cucumber downy mildew, downy mildew of garpe and/or potato late blight
There is significant synergistic effect in disease, extend the lasting period, improves effect;Use the complex preparation of the present invention, after administration 7d
83.8-86.5% is reached to downy mildew of garpe preventive effect, 14d reaches 84.9-88.1% to preventive effect after administration, is significantly higher than single dose
Preventive effect.
(2) times for spraying is reduced, lowers drug cost, reduces environmental pollution and pesticide residue;
(3) composition is made of the active ingredient of different role mechanism, and action site increases, and is conducive to overcome and delay cause
The generation of germ drug resistance.The present composition is without obvious harmful effects to trial crops, and leaf color, growing way etc. are all normal, peace
Good perfection meets the security requirement of pesticidal preparations.
【Specific implementation mode】
The present invention is will be better understood that by following embodiments.
One, the preparation of agricultural bacteriocide of the present invention
Embodiment 1:Prepare 60%Y14079 dimethomorph wettable powders
It weighs with 30% chemical constitution formula (I) Y14079 of wettable powder total weight, 30% dimethomorph, dodecyl
Benzene sulfonic acid sodium salt 1.8%, to tertbutyl ether 2%, White Carbon black 10%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to
100%, obtain fungicide according to preparation method above-mentioned.
Embodiment 2:Prepare 60%Y14079 flumorph wettable powders
It weighs with 40% chemical constitution formula (I) Y14079 of wettable powder total weight, 20% flumorph, the wooden dodecyl
Benzene sulfonic acid sodium salt 1%, to tertbutyl ether 1%, White Carbon black 2%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to 100%, presses
Wettable powdered disinfectant is obtained according to preparation method above-mentioned.
Embodiment 3:Prepare 60%Y14079 dimethomorph water dispersion granulas
It weighs with 40% chemical constitution formula (I) Y14079 of total weight, 20% dimethomorph, N- methyl-oleoyl-ox sulphurs
Sour sodium 5%, naphtholsulfonic acid formaldehyde condensation products 8%, sodium sulphate 8%, kaolin complements to 100%, according to preparation method above-mentioned
Obtain fungicide.
Embodiment 4:Prepare 40%Y14079 flumorph water dispersible granules
It weighs with 30% chemical constitution formula (I) Y14079 of total weight, 10% flumorph, sodium lignin sulfonate 10%, first
Base naphthalenesulfonic acid-formaldehyde condensate 5%, epoxidized polyether 5%, bentonite 10%, kaolin complements to 100%, according to system above-mentioned
Preparation Method obtains suspending agent fungicide of the present invention.
Embodiment 5:Prepare 30%Y14079 dimethomorph suspending agents
It weighs with 15% chemical constitution formula (I) Y14079 of total weight, 15% dimethomorph, sodium lignin sulfonate 5%, in vain
The mixture (EFW) 2.0% of carbon black 0.3%, alkylnaphthalene sulfonate and anion wetting agent, potassium dihydrogen phosphate 0.2%, ethylene glycol
4%, tributyl phosphate 0.2%, water complements to 100%, and Wettable powdered disinfectant is obtained according to preparation method above-mentioned.
Embodiment 6:Prepare 30%Y14079 flumorph suspending agents
It weighs with 20% chemical constitution formula (I) Y14079 of total weight, 10% flumorph, the condensation of methyl naphthalene sulfonic acid sodium formaldehyde
The mixture (EFW) 2.0% of object 2.5%, alkylnaphthalene sulfonate and anion wetting agent, agriculture breast OX-6563.0%, glycerine
4%, tributyl phosphate 0.2%, water complements to 100%, and fungicide wettable powder of the present invention is obtained according to preparation method above-mentioned
Agent.
Embodiment 7:Prepare 15%Y14079 dimethomorph oil-suspending agents
It weighs with total weight 12%Y14079,3% dimethomorph, castor oil polyoxyethylene ether 15%, three phenethyl phenols
Polyoxyethylene ether phosphate 3%, organobentonite 1.5%, methyl oleate complements to 100%, is obtained according to preparation method above-mentioned
To fungicide of the present invention.
Embodiment 8:Prepare 0.5%Y14079 flumorph oil-suspending agents
It weighs with total weight 0.25%Y14079,0.25% flumorph, fatty alcohol polyoxyethylene ether 13%, poly alkyl alcohol
Ethylene oxide ether phosphate 2.5%, organobentonite 1%, corn oil complements to 100%, this is obtained according to preparation method above-mentioned
Invention fungicide.
Two, the measurement of bioactivity
In order to further appreciate that the virulence of Y14079 and dimethomorph or flumorph composition, a large amount of recipe determinations have been carried out
Experiment.
Bioassay example 1:Y14079 is with dimethomorph to the Toxicity Determination of cucumber downy mildew
Experiment with reference to bactericide agricultural chemicals indoor bioassay test rule (agricultural industry criteria NY/T1154.7-2006) and
Pesticide bioactivity evaluation SOP (fungicide volume) is formulated, cucumber downy mildew uses spray-on process.
Synergy is calculated using following methods:
Contents (%) of the toxicity index × A of mixed toxicity index (the TTI)=A of theory in mixed
Contents (%) of the toxicity index × B of+B in mixed
Co-toxicity coefficient shows there is synergistic effect if more than 120;If being less than 80, it is shown to be antagonism;It is less than if more than 80
120, it is shown to be summation action.
1 Y14079 of table is acted on dimethomorph mixture synergy
2 Y14079 of table is acted on flumorph mixture synergy
Bioassay example 2:To the Toxicity Determination of the late blight of potato
Subjects:Phytophthora infestans Phytophthora infestans are preserved by this laboratory strain room.
Using mycelial growth rate method.After tested bacterial strain is cultivated 6d on PDA plate, beaten from colony edge take it is a diameter of
Bacteria cake is connected on the tablet of the drug concentrations containing different quality by the bacteria cake of 5mm, when blank control grows to a certain size, is used
Crossing method measures each processing colony diameter.It calculates each processing bacterium colony and increases diameter and inhibiting rate, calculate co-toxicity coefficient.
3 Y14079 of table is acted on dimethomorph mixture synergy
4 Y14079 of table is acted on flumorph mixture synergy
Bioassay example 3, the Toxicity Determination to downy mildew of garpe
Subjects downy mildew of garpe (Plasmopara viticola) is acquired by field.
Test method reference《National Standard of the People's Republic of China GB/T 17980.122-2004》, using spore suspension
Liquid spray inoculation method measures the bioactivity of medicament.The consistent grape seedlings of selection growing way, naturally dry after reagent spray processing, for 24 hours
Distillation washing is dipped with writing brush afterwards and take disease leaf back sporangium, be made into sporangia suspension (2-3 × 105A/ml), it is sprayed with inoculation
Sporangia suspension is uniformly sprayed on grape leave by day with fog (pressure 0.1MPa), then moves to grape seedlings after inoculation manually
(relative humidity 100%, temperature are 21-23 DEG C, light dark period 14h/10h) culture in climatic chamber.It maintains afterwards for 24 hours relatively wet
90% or so moisturizings of degree induce 8-10d backsight blank control incidences and carry out classification investigation, refer to by disease and calculate preventive effect %.Pass through
Control effect finds out the EC of each medicament50, co-toxicity coefficient (CTC) is calculated further according to Sun Yunpei's Method.
5 Y14079 of table is acted on dimethomorph mixture synergy
6 Y14079 of table is acted on flumorph mixture synergy
The effect of Y14079 and dimethomorph synergy is shown in Table 1,3,5, Y14079 acts on flumorph synergy and being shown in Table
2、4、6.As can be known from the table data, the composition of Y14079 and dimethomorph or flumorph for examination target to having very high work
Property, show notable synergistic effect after Y14079 and dimethomorph or flumorph mixture, it is single that the activity of mixture is significantly higher than control
Agent, the two can be compounded.
Three, Field information is tested
Field trial 1:Prevent downy mildew of garpe field control effectiveness test
Example of formulations 1, embodiment 4, embodiment 5 are measured under field condition to the control effect of downy mildew of garpe.Root
It is carried out according to the regulation of " pesticide field efficacy medicine test criterion (one) microbiocidal agent prevents GB/T 17980.122-2004 ".
Test result:Example of formulations 1, embodiment 4, embodiment 5, embodiment 6,7d is to downy mildew of garpe after first time medicine
Preventive effect is 83.8%~86.5%, and comparison medicament dimethomorph and flumorph are respectively 70.5% He to the preventive effect of downy mildew of garpe
The preventive effect of 72.1%, 30%Y14079 suspending agent is 71.3%, and the preventive effect of mixture is above comparison medicament;7d pairs after second of medicine
Downy mildew of garpe preventive effect is 84.9%~88.1%, and comparison medicament dimethomorph and flumorph distinguish the preventive effect of downy mildew of garpe
Preventive effect for 73.8% and 74.7%, 30%Y14079 suspending agents is 75.6%, and the preventive effect of mixture is above comparison medicament.
Y14079 and dimethomorph or flumorph mixture prevention downy mildew of garpe are efficient.
Field control effectiveness test result of 7 mixture of table to downy mildew of garpe
Field trial 2:Prevent late blight of potato field control effectiveness test
Example of formulations 2, embodiment 3, embodiment 5, embodiment 6 is measured under field condition to prevent the late blight of potato
Control effect.According to " pesticide field efficacy medicine test criterion (one) microbiocidal agent prevents late blight of potato GB/T 17980.34-
2000 " regulation carries out.
Test result:Example of formulations 2, embodiment 3, embodiment 5, embodiment 6,10d is to potato evening after first time medicine
Epidemic disease preventive effect is 84.2%~87.7%, and comparison medicament dimethomorph and flumorph are respectively to the preventive effect of the late blight of potato
The preventive effect of 73.4% and 72.6%, 30%Y14079 suspending agent is 70.5%, and the preventive effect of mixture is above comparison medicament;Second
10d is 85.2%~87.6% to late blight of potato preventive effect after medicine, and comparison medicament dimethomorph and flumorph are to potato evening
The preventive effect of epidemic disease is respectively 74.6% and 73.7%, and the preventive effect of 30%Y14079 suspending agents is 71.4%, and the preventive effect of mixture is high
In comparison medicament.Y14079 and dimethomorph or the flumorph mixture prevention late blight of potato are efficient.
Field control effectiveness test result of 8 mixture of table to the late blight of potato
Field trial 3, prevention cucumber downy mildew field control effectiveness test
According to medicine inspecting institute of the Ministry of Agriculture " GB/T 17980.26-2000 pesticide field efficacy medicine test criterions (two) --- fungicide
The regulation of prevention cucumber downy mildew ", test medicine, comparison medicament and the processing of the cell of blank control are arranged using random district's groups,
10 plants of plot area open country, 4 repetitions, disease first time at initial stage dispenser, secondary dispenser after 7d, 7d investigation morbidities after secondary medicine
Rate, disease index.Per 4 points of experimental plot random searching, every is investigated two plants, is investigated whole blades, is remembered by following stage division
Record the sick numbers of sheets and total number of sheets at different levels.
Test result:Example of formulations 3, embodiment 6, embodiment 7,7d is to cucumber downy mildew after first time medicine
83.2%~86.2%, 7d is 82.5%~86.7% to cucumber downy mildew after second of medicine, and the preventive effect of mixture is above
Comparison medicament.Y14079 and dimethomorph or flumorph mixture prevention cucumber downy mildew are efficient.
Field control effectiveness test result of 9 mixture of table to cucumber downy mildew
Y14079 and the selected from dimethomorph or flumorph are can be seen that from above-mentioned field trial (table 7,8 and 9) result
Cucumber downy mildew, downy mildew of garpe or the late blight of potato can be effectively prevented after two active constituents compounding, compared with single dose, this is killed
Bacteria composition has significant synergistic effect to disease, improves bactericidal effect;
Times for spraying is reduced, drug cost is reduced, reduces the pollution to environment and pesticide residue;
Composition is conducive to overcome and delay the drug resistance of germ since different mechanism of action, action site increase
It generates.The present composition is without obvious harmful effects to trial crops, and leaf color, growing way etc. are all normal, and safety is good, meets agriculture
The security requirement of medicine preparation.
Plurality of plant diseases especially downy mildew, early blight of the bactericidal composition of the present invention to flowers, fruit tree, vegetables
There is good preventive effect with late blight.
Claims (7)
1. a kind of agricultural bactericidal composition, it is characterised in that it is lived by the compound with following chemical constitution formula (I)s with second
Property ingredient is according to weight ratio 50:1~1:50 compositions:
Second active constituent is dimethomorph or flumorph.
2. agricultural bactericidal composition according to claim 1, it is characterised in that chemical constitution formula (I) compound is lived with second
The weight ratio of property ingredient is 20:1~1:20.
3. a kind of agricultural bacteriocide, it is characterised in that it contains 0.5~95.0% according to claim 1 or claim 2 by weight
Agriculture bactericidal composition and surplus be agriculturally acceptable carrier and auxiliary agent.
4. agricultural bacteriocide according to claim 4, it is characterised in that it contains by weight 10~60% according to right
It is required that the agriculture bactericidal composition and surplus described in 1 or 2 are agriculturally acceptable carrier and auxiliary agent.
5. agricultural bacteriocide according to claim 4 or 5, it is characterised in that its dosage form is water dispersion granule, wettable
Property pulvis, suspending agent or oil-suspending agent.
6. agricultural bactericidal composition or according to described in any one of claim 3-5 claims according to claim 1 or claim 2
Purposes of the agricultural bacteriocide in prevention cucumber downy mildew, downy mildew of garpe and/or the late blight of potato.
7. it is a kind of prevention crop disease method, before or after crops and/or fruit introduced disease, to crops and/
Or fruit and the place of growth or storage are applied and are appointed in agriculture bactericidal composition or claim 3-5 described in claims 1 or 2
Agricultural bacteriocide described in one claim.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810204391.7A CN108271791A (en) | 2018-03-13 | 2018-03-13 | A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810204391.7A CN108271791A (en) | 2018-03-13 | 2018-03-13 | A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108271791A true CN108271791A (en) | 2018-07-13 |
Family
ID=62809551
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810204391.7A Pending CN108271791A (en) | 2018-03-13 | 2018-03-13 | A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108271791A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110734433A (en) * | 2018-07-19 | 2020-01-31 | 东莞市东阳光农药研发有限公司 | Triazole compound and application thereof in agriculture |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105693638A (en) * | 2016-01-05 | 2016-06-22 | 华中师范大学 | Bactericidal compound and bactericide composition and preparation and application thereof |
CN107960416A (en) * | 2017-12-31 | 2018-04-27 | 成都格瑞赛斯科技有限公司 | A kind of bactericidal composition and its application containing dimethomorph |
-
2018
- 2018-03-13 CN CN201810204391.7A patent/CN108271791A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105693638A (en) * | 2016-01-05 | 2016-06-22 | 华中师范大学 | Bactericidal compound and bactericide composition and preparation and application thereof |
CN107960416A (en) * | 2017-12-31 | 2018-04-27 | 成都格瑞赛斯科技有限公司 | A kind of bactericidal composition and its application containing dimethomorph |
Non-Patent Citations (1)
Title |
---|
马安民等: "《园林植物杀菌剂应用技术》", 31 October 2016, 河南科学技术出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110734433A (en) * | 2018-07-19 | 2020-01-31 | 东莞市东阳光农药研发有限公司 | Triazole compound and application thereof in agriculture |
CN110734433B (en) * | 2018-07-19 | 2020-09-11 | 东莞市东阳光农药研发有限公司 | Triazole compound and application thereof in agriculture |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104839168B (en) | Bactericidal composition and its application | |
CN107821404A (en) | A kind of bactericidal composition and its application containing benziothiazolinone and fluorine thiazole pyrrole ethyl ketone | |
CN108633916A (en) | A kind of Pesticidal combination containing beauveria bassiana and ethyl pleocidin | |
CN104365611B (en) | A kind of bactericidal composition and application containing amisulbrom and mandipropamid | |
CN108271791A (en) | A kind of agriculture bactericidal composition containing the second active constituent of ether azoles sulfanilamide (SN) ester type compound and morpholine class | |
CN104054712B (en) | Sterilization composition containing boscalid | |
CN108605961A (en) | A kind of bactericidal composition containing fluorine azoles bacterium acyl azanol and its application | |
CN108849918A (en) | Bactericidal composition | |
CN105052997B (en) | A kind of composition pesticide and bactericide containing toxic fluoride phosphate and antimicrobial fungicides | |
WO2022089447A1 (en) | Quinolone compound-containing synergistic bactericidal composition, and application thereof | |
CN106982837A (en) | A kind of Pesticidal combination containing fluorine cyanogen insect amide and its application | |
CN108353910A (en) | A kind of agriculture bactericidal composition containing ether azoles sulfanilamide (SN) ester type compound and prothioconazoles | |
CN106342843A (en) | Insecticide composition containing haloxyfop furanone | |
CN108477199A (en) | A kind of bactericidal composition and application thereof | |
CN111567535A (en) | Bactericidal mixture containing succinate dehydrogenase inhibitor and application thereof | |
CN109953027A (en) | A kind of bactericidal composition of fluorine-containing phenylate amide and antibiotic in pyrimidine nucleoside class | |
CN108353908A (en) | A kind of agriculture bactericidal composition containing ether azoles sulfanilamide (SN) ester type compound and cyazofamid | |
CN104068033B (en) | Fungicidal composition containing boscalid | |
CN108651514A (en) | A kind of composition pesticide containing fosthiazate and fluxapyroxad | |
CN104336028B (en) | A kind of bactericidal composition containing amisulbrom and dimethomorph | |
CN108576008A (en) | Bactericidal composition and its application | |
CN108157382A (en) | A kind of pyrrole bacterium benzene prestige bactericidal composition and its application | |
CN108207966A (en) | Bactericidal composition | |
CN113229293A (en) | Bactericidal composition and application thereof | |
CN106172453A (en) | A kind of bactericidal composition and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180713 |