CN1021617C - Pesticidal composition - Google Patents

Abstract

The present invention relates to a pesticidal composition for preventing and treating bacterial diseases of plants, which comprises a nitrofurane derivative in general formula I (2-X-5-Nitrofuran) and optional one or more known fungicides as active ingredients. The active ingredients occupy 1 to 99% of total weight, and X is (a) or (b) in general formula, wherein the proportion of the general formula (I) to the known fungicides is from 1:99 to 99:1, the proportion of two active ingredients is from 1:9 to 9:1 preferably, and the proportion of three active ingredients is from 1:9:0.5 to 1:1:5, preferably from 1:4:1 to 1:1:4. The active ingredients are mixed respectively with inert solid, carrier liquid or diluting agents and frequently-used assistants such as wetting agents, dispersing agents, sticking agents, defoaming agents or antifreeze.

Description

Pesticidal composition

The invention relates to the Pesticidal composition and their production method of control bacterial diseases of plants and on agricultural, use their to prevent and treat a kind of method of bacterial diseases of plants.

According to imagination of the present invention, the Pesticidal composition of control bacterial diseases of plants is provided, its active component is the nitrofuran derivatives shown in general formula (I) and selects one or more known Fungicidal active ingredients arbitrarily that they account for 1～99% of total mixture weight.

/Ⅰ/

X represents group (a) or (b) in the formula:

/a/

/b/

And the ratio of the active component of general formula (I) and known Fungicidal active ingredient is: 1: 99～99: 1.If two kinds of active components, preferably 1: 9～9: 1; If three kinds of active ingredients are 1: 9: 0.5～1: 1: 5, preferably be chosen as 1: 4: 1～1: 1: 4.Active component more respectively with suitable inert solid fillers or liquid-carrier or thinner and auxiliary agent commonly used such as wetting agent, dispersant, sticker, defoamer and (or) anti-agglomerating agent mixes mutually.

Mixture of the present invention is very useful to following bacterial disease or the bacillary and simultaneous disease of fungoid of control plant:

Agrobacterium tumefaciens O(Agrobacterium tumefaciens O)

Agrobacterium tumefaciens C-58(Agrobacterium tumefaciens C-58)

Agrobacterium tumefaciens B-6(Agrobacterium tumefaciens B-6)

Agrobacterium radiobacter K-84(Agrobacterium radiobacter K-84)

Uredo erwinia phage (Erwinia uredowora)

The Hu Luobu soft rot Erwinia is deceived rotten mutation

（Erwinia carotovora var，atroseptica）

Soft rot Erwinia (Erwinia carotovora)

Tomato ulcer rod bacillus (Corynebacterium michiganense)

Corn freckle and wilt disease corynebacteria (Corynebacterium nebraskense)

Xanthomonas (Xanthomona spp.)

Fusarium (Fusarium spp.)

Miliary damping-off Pseudomonas (Rhizoctonia spp.)

Botrytis (Botrytis spp.)

Brown rot Pseudomonas (Sclerotinia spp.)

Alternaric bacteria (Alternaria spp.)

Penicillium (Penicillium spp)

Eurotium (Aspergillus spp.)

Rhizopus (Rhizopus spp.)

Except the compound that comprises general formula (I), Pesticidal composition may also comprise the Fungicidal active compound that one or more are known, any known suitable tag or systemic fungicide all can use.The purpose of using fungicide is the fungicidal spectrum that enlarges mixture.Therefore, preferably use following mycocidal active component:

Benomyl (Benomyl) 0-methyl-N-(1-butylamine formoxyl-2-benzimidazole) carbamate

Carbendazim (MBC) 0-methyl-N-2-benzimidazole carbamate

Thiophanate methyl (Thiophanate-methyl) 1,2-pair-(3 '-methoxycarbonyl-2 '-ghiourea group)-benzene

Thiabendazole (Thiabendazol) 2-(4 '-thiazolyl) benzimidazole

Zineb (Zineb) ethylene-1,2-pair-(aminodithioformic acid) zinc

Maneb (Maneb) ethylene-1,2-pair-(aminodithioformic acid) manganese

The complex compound of mancozeb (Mancozeb) zineb and maneb

Tmtd (TMTD) is two-(dimethylamino thioformyl) two sulphur things

Captan (Captan) N-(trichloro-methylthio) cyclohexene-4-1, the 2-dicarboximide

Active component of the present invention is particularly suitable for protecting the material that was used as breeding before duration of storage or sowing, as seed, stem tuber, bulb, and the cutting etc. of transplanting.Except infecting many fungal diseases, plant yet will usually suffer the caused infringement of various pathogenetic bacterias.

Klement has summed up the caused disease most important characteristic of plant pathogenetic bacteria (" plant protection " 1982 № 3)

The symptom type pathogen causes the bacterial substances of symptom

Withered spot venereal disease evil pseudomonad (Pseudomonas) bacterial polysaccharides

Produce the material of withered spot

The green parent toxin of cancer shape growth Xanthomonas campestris (Xanthomonas)

Wilting (Wilting) woods spot toxin

The cellulose of withered (Withering) excellent bacillus (Corynebacterium) catabolic enzyme

Cause withered toxin

The pectin of soft rot Erwinia (Erwinia) catabolic enzyme

Tumour bacillus (Agrobacterium) is by plasmid-encoded

Information substance

With regard to pathogenetic bacteria colony, those can infect breeding material-seed, stem tuber, bulb, various nursery stocks-bacterial classification be particular importance.For example corynebacterium ulcerrans on the tomato and the freckle on the corn and wilt disease corynebacterium; Agrobacterium tumefaciens have caused massive tumor on the breeding material of multiple fruit tree and grape, and the material that is infected can not be eaten.Is harmful especially by multiple Ou Wenshi pathogenetic bacteria in caused soft rot on the high storage harvested product of liquid and juice content and on the breeding material at stem tuber, bulb, onion root, because it has caused very big economic loss:

Potato be caused by the black rotten mutation of pathogen carrot soft rot Erwinia, and under the situation that does not also have effectively protection so far, caused loss may be very huge in the rot of duration of storage.

According to the estimation (" plant protection " " Noev é nyvedelem " 1982. № 3) of Pint é r, the potato 5% is taken place under the situation of soft rot, and caused loss amounts to will surpass 100,000,000 forint.

Formerly have in the technical literature, at length discussed by the black rotten mutation of Hu Luobu soft rot Erwinia that cause with importance simultaneous fungal disease.(referring to Stachewich, 1974., Nachr.Blatt Pflschutz., 28,2; Wellving, Sweed.Seed.Assoc 31; Anonym/Merkbl.des Pflschutz, 1974.10).

Therefore, potato is at duration of storage with all may be subjected to infecting of fungi and bacterium simultaneously prior to seeding.

Table 1 has been summarized the pesticide activity component that is used to prevent and treat simultaneous bacterium and fungal disease, has also listed the source of prior art document in the table.

Table 1

Pathogen active component document source

Hu Luobu soft rot Erwinia phenyl-alanine Gupta, Tripathi

Indian J.E.1976.

4./3./

Black rotten mutation aminonialyase (ammonialiase), polyphenol 4./3./

Streptomycin kanamycin A lbergiana,

Phytopath.Zeit.

81./2./

Neomycin

Erythromycin (erithromycin)

Chloramphenicol

Sickle spore bacterium benomyl Leach, 1975 USDA 17.

Jellis，Taylor Ann.

Appl.Biol.

Thiabendazole Munzel, Bayer

Land.1976.52./2./

Hu Luobu soft rot Erwinia carbendazim+chloramphenicol., Ratba, Spez.

Pflsch.1977.1.

Black rotten mutation+sickle spore bacterium benomyl+chloramphenicol, Burth, Jahn

Akad.Landw.Wiss.

/140/

Zineb+chloramphenicol,

Zineb+chloramphenicol, Anonymus, Gops.

Soil.1975.30./1./

Erwinia+pseudomonad antibiotic+fungicide Sahurai, 1975.

J.Antibiotics，29.

/11./

But neither one can play complete preventive and therapeutic effect in the above-mentioned medicament, so antibiotic is used to control infecting of bacterium fully, but most countries forbids on agricultural using antibiotic.

Purpose of the present invention is exactly these weak points that overcome known control bacterial diseases of plants method.More particularly, the objective of the invention is to illustrate:

A kind of to the effective guard method of bacterial diseases of plants and

A kind of plant protection product that is suitable for preventing and treating simultaneous bacillary and fungal disease.

Recognize that from animal doctor's practice nitrofuran derivatives is effectively to some Gram-negative bacteria, but use nitrofuran derivatives in plant protection, the document in past was not also put down in writing fully.

According to preliminary test of being carried out and in vitro test, the present invention has tested following Nitrofuran compound:

CH-819, Furazolidone=5-nitro-furyl methene-3-amido-2-oxazolidinone

CH-1237, Nitrofurantoine=N-(5-nitro-furyl methene-2-)-the 1-amido-glycolyurea

CH-1552=3-(5-nitro-furyl methene-amino)-imidazoles-2-mercaptan

CH-2007=2-(5-nitro-furyl methene-amino)-4-chloromethyl-5-(2-chloroethyl)-thiazole

CH-2011=2-(5-nitro-furyl methene-amino)-4-methyl-5-(2-chloroethyl)-thiazole

CH-2103=2-(5-nitro-furyl methene-amino)-4-methyl-5-(2-hydroxyethyl)-thiazole

It the results are shown in the table 2

Table 2

Nitro on single kind bacteria culture media

The bacterial action extremely of furan derivatives

Minimum inhibitory concentration (MIC) mg/ml

Bacterium strain CH-819 1,237 1,552 2,011 2013

Agrobacterium tumefaciens O 4-8 1000 8-16 A A

Agrobacterium tumefaciens C-58 4-8 1000 8-16 A A

Agrobacterium tumefaciens B-6 4-8 1000 8-16 A A

Agrobacterium radiobacter K-84 2-4 1000 4-8 A A

The living Erwinia D5 1000 A 1000 A A of grass

（Erwinia herbicola D5）

Uredo erwinia phage 0.2-05 A 2-4 A A

（Erwinia Uredovora）

Black rot Erwinia 4-8 A 8-10 A A

（Erwinia atroseptica）

Soft rot Erwinia 4-8 A 8-10 A A

Angular leaf spot of cucumber pseudomonad 8-16 A 30-60 A A

（Pseudomonas lachrymans）

Choose canker pseudomonad 1000 A 1000 A A

（Pseudomonas mors-prunorum）

Bean bacterial northern wilt pseudomonad 30-60 A 60-120 A A

（Pseudomonas phaseolicola）

Pseudomonad 250-500 A 1000 A A

（Pseudomonas pisi）

Pseudomonas fluorescens 1000 A 1000 A A

（Pseudomonas fluorescens）

Soybean root disease bacterium 8-16 A 30-60 A A

（Rhizobium japonicum）

Lucerne place leaf spot Xanthomonas campestris 30-60 A 60-120 A A

（Xanthomonas alfalfae）

Broccoli black rot Xanthomonas campestris 1000 A 1000 A A

（Xanthomonas campestries）

Xanthomonas campestris 30-60 A 60-120 A A

（Xanthomonas fus.pv.phaseoli）

Nandina certain herbaceous plants with big flowers leaf spot Xanthomonas campestris 30-60 A 60-120 A A

（Xanthomonas pelargonii）

Capsicum spot disease Xanthomonas campestris 1000 A 1000 A A

（Xanthomonas vesicatoria）

Paddy rice is to leaf spoting bacteria

（Xanthomonas orisae）

Twine excellent bacillus 15-30 A 60-120 A A

（Corynebacterium fascians）

Bean bacterial northern wilt rod bacillus 30-60 A 60-120 A A

（Corynebacterium flaccumfac.）

Tomato canker rod bacillus 4-8 A 8-16 A A

（Corynebacterium michiganense）

Corn ephelides and wilt disease rod bacillus 4-8 A 8-16 A A

（Corynebacterium nebraskense）

Ovshinsky rod bacillus 60-120 A 250-500 A A

（Corynebacterium oortii）

A＝＞1000mg/ml

It should be noted that soft rot Erwinia and Agrobacterium tumefaciens are extremely sensitive to Compound C H-819, then is moderate sensitivity to Compound C H-1552.

For the biologically active of the mixture of measuring some nitrofuran derivatives and nitrofuran derivatives and Fungicidal active ingredient, on the basis of preliminary test, further carried out in vitro test again.

The present invention will give to describe in detail further in the following embodiments, and protection domain of the present invention is not limited in these embodiment certainly.

Embodiment 1

Test compound is to the activity data of the black rotten mutation of Hu Luobu soft rot Erwinia in the culture dish test

Test is done five times to each dosage and is repeated.The medium that uses is the medium of the black rotten mutation separation and Culture of suitable Hu Luobu soft rot Erwinia.Bacterium breeds growth on the slant agar medium, separate the bacterium suspension that obtains from the pure culture base and be inoculated on the medium that is chilled to 40～50 ℃ with following method.

20 milliliters of medium are poured in the culture dish of 10 cm diameters, and after medium solidified, each culture dish was made a call to four holes, inject the 0.1 milliliter of suspension that will test in each hole, and the temperature of inoculation is 25 ℃, and its result is as shown in table 4.

Table 4

Review time after handling (hour)

Substances concentration mg/ml dosage ml 24 48 72 96

Inhibition zone diameter (mm)

CH-819 1.5 0.1 0 1～2 5 10

1.5 0.1 0 2 10 15

CH-1237 1.0 0.1 0 0 0 0

1.5 0.1 0 0 0 0

CH-1552 1.0 0.1 0 0 1 3～5

1.5 0.1 0 1 1～2 5～7

CH-2007 1.0 0.1 0 0 0 0

1.5 0.1 0 0 0 0

CH-2011 1.0 0.1 0 0 0 0

1.5 0.1 0 0 0 0

CH-2013 1.0 0.1 0 0 0 0

1.5 0.1 0 0 0 0

CH-819+ benomyl 1.5+1.5 0.2 0 1～2 5～6 8～10

CH-819+ carbendazim 1.5+1.5 0.2 015 8～10

CH-1552+ carbendazim 1.5+1.5 0.2 00 1～2 3～5

Benomyl 1.5 0.1 0000

Carbendazim 1.5 0.1 0000

According to inhibition zone size description in the table 4 CH-810 in the nitrofuran derivatives and CH-1552 black rotten mutation is 1.0～1.5mg/ml in concentration to the Hu Luobu soft rot Erwinia, dosage is to be effectively under the condition in 0.1ml/ cave, and benomyl and carbendazim do not improve the bacterial activity of killing of nitrofuran derivatives.

Embodiment 2

Potato (kind in accordance with regulations) stem tuber is cut in half, and making a call to five diameters is 10 millimeters, and concentration is 15 millimeters aperture, and the distance in these five holes is roughly relative mutually, repeats to make a call to five holes again.

The bacterium hanging drop that will contain the black rotten mutation bacterium of Hu Luobu soft rot Erwinia is added in the duck eye, and (0.1 milliliter in every hole) after half an hour, joins test compound in the cave that usefulness bacterium liquid was handled in advance with micropipette.Stem tuber that handled and that contaminated is placed on and cultivates 3 days (72 hours), evaluation results then in the dampening chamber.Hole is vertically cut in half along original tangent plane, dig out rot part and weighing.Compare with untreated control sample by the grade of stipulating below and to estimate the effect of processing.

Infect classification

0＝0～5% 1＝6～10% 2＝11～25%

3=25～more than 50% 4=50%

The representative of above-mentioned percent value since the germ gelling of Ou Wenshi weight of digging out material and the control group weight ratio of digging out material." 0 " expression is the most orderly, and " 4 " then represent the most invalid processing.The result as shown in Table 5.

Table 5

Treatment dosage (mg/ml)

The weight ratio 50 25 12 63 1.5 of test compound component

CH-819 100 0 0 0 0 0 1

CH-1237 100 4 4 4 4 4 4

CH-1552 100 0 0 0 1 2 2

CH-2007 100 3 4 4 4 4 4

CH-2011 100 3 3 4 4 4 4

CH-2012 100 3 4 4 4 4 4

CH-2013 100 2 3 4 4 4 4

Benomyl 100 334444

Carbendazim 100 344444

CH-819+ benomyl 50,+50 000000

CH-819+ carbendazim 50,+50 000012

CH-819+ carbendazim 50,+25,+25 000012

+ mancozeb

CH-1552+ carbendazim 50,+50 000023

Similar with the result of culture dish test, above-mentioned result of the test is to CH-819, and the mixture of CH-1552 and they and fungicide also is effective.

With regard to the mixture of fungicide and bactericide, with the tool activity of the mixture of CH-819+ carbendazim+mancozeb (active ingredient Mancozeb) when ratio is 50%+25%+25%.

The present invention is based on and has recognized Compound C H-819, and CH-1552 has very high activity to the pathogen of soft rotten Erwinia.So Pesticidal composition of the present invention is well suited for control bacterial disease or bacterium and the simultaneous disease of fungi.

Plant protection product can be processed into various preparations, its composition can consider the machinery of application conditions, plant culture technics and use select the decision.For stem tuber, bulb, piece root and the rhizome of protecting duration of storage, must be at these breeding materials of storage pre-treatment, it is identical or similar with so-called " seed dressing " that the technology of being addressed is actually.Seed dressing is breeding part and the seedling that is generally used for sowing the above-mentioned plant of pre-treatment.Seed dressing can be carried out at different time.

Pesticidal composition of the present invention can be processed into commonly used and formulation easily, as pulvis, and wetting powder, suspension concentrates, granule or the like.

The formulation preparation of mixture of the present invention comprises two basic steps, and this two step often interosculates.

The first step is the active ingredient that preparation has suitable granularity.For the control efficiency that obtains expecting, 70% particle grain size must be below 10 μ m.This step can realize with two kinds of methods: the one, and dry way process, the active ingredient with agricultural chemicals for example is being crushed to needed particle size in the airslide disintegrating mill exactly; The 2nd, wet process is to carry out waterproof pulverization to needed particle size in for example ball mill or sand mill.According to an embodiment preferred of this method, the chemical reaction for preparing active effective ingredient is should have under the desired particle diameter condition at the product that generates to carry out; So just do not needed high-octane very expensive reducing mechanism.

Second step for preparing required formulation is that above-mentioned active ingredient particle is mixed mutually with adjuvant, carrier, thinner, sticker, synergist and colouring agent etc.

Wetting powder

The particle that a very important requirement is an active ingredient should be to disperse in water at an easy rate, and after being applied to the position that crop will protect, suspension should produce one and cover uniformly.For this reason, mixture should comprise so-called wetting agent.The chemical constitution of these materials will comprise a nonpolar and polarity part.From the angle of chemistry, these compounds belong to following a few compounds:

The anion active compound

Carboxylate (ester) class

Soap

Has the amino carboxylic acid of HMW and their salt

Acyl groupization and amino carboxylic acid condensation

Sulphate (ester) class

The sulphate of fatty acid

The sulphate of derivative of fatty acid

Alkyl sulfate

Sulfonate (ester) class

The sulfonate of fatty acid, fatty acid ester, fatty acid amide etc.

The sulfonate of fatty alcohol, ether, nitrile compounds

Alkylsulfonate

The sulfonate of ester, ether or acid amides

The sulfonate of fragrance or hydrogenated aromatic compound

The aromatic alkyl sulfonate of HMW

Aromatic sulphonic acid or aromatic sulphonic acid ether or aromatic sulphonic acid amide compound

Phosphorus compound

Phosphate (ester), phosphoro-amidate (ester)

Phosphite (ester)

Phosphonate (ester)

Phosphite (ester)

The borate of HMW

Fluorine compounds

Non-ionic compound

Polyol

The alkylene oxide of HMW

The polyglycol ether that replaces

The alkylamide of ethoxylation

The macrogol ester that replaces

The sulfuric ester of polyethylene glycol

Cationic active compounds

Amine derivative

Salt derivative

The oxide of amine

Amphoteric compound

Protein derivatives

That replace and Sulfobetain

The amino carboxylic acid, amidosulphuric acid and the phosphoramidic acid that replace

Alicyclic compound

Polymer

The anion active compound

The nonionic reactive compound

Cationic active compounds

Amphoteric compound

When selecting the adjuvant of being addressed, can consult for example following books:

Kurt Lindner，Tenside，Textilhitfsmittel，Waschrohstoffe，

Wissenschaftliche Verlaggesellschaft MbH，Stuttgart。

Prior requirement is in use to preparation, and the suspension that is generated by the wettable and dispersed particles of active ingredient should be stable, for example deposition should not take place at duration of storage, changes because deposition can cause undesirable concentration.This point can use suitable dispersant to achieve the goal.This dispersant has been the macromolecular compound of protective colloid action, the calcium salt of lignosulfonate for example, and sodium salt or ammonium salt, water miscible polymer, mucus etc. can be used as dispersant.

Carrier or filler can be selected to use chippy mineral matter, as china clay, and kaolin, bentonite, calcium carbonate, gypsum etc.

Also can contain sticker in the composition of wetting powder.More particularly, sticker can be selected water miscible big molecule organic polymer, and preferred representative compounds has: carboxy methylation starch, carboxy methylation cellulose, PVP(polyvinyl pyrrolidone).

In order to improve control efficiency, can also comprise some mineral salt (as sodium sulphate), organic acid (as tartaric acid), vegetable oil and mineral wet goods in the mixture.

In order to improve storage property, also can comprise the big silicic acid of surface area that some are synthetic in the mixture, aluminium oxide etc.

Concerning the user, the foaming effect during use is a serious problem, uses defoamer can overcome this shortcoming.For this purpose can be used oil emu.Defoamer can prepare by mixing suitable emulsifier system: can consider to come oil emulsion with oil, under suitable stirring, the mixture that obtains like this be poured in the water again.If when not allowing water in preparation, the oil that comprises emulsifier so can directly be mixed in mixture.In this case, when active ingredient is made into suspension, oil will be brought into play its effect.It is important that employed defoamer should have the character of self-emulsification.Vegetable oil or mineral oil emulsion, particularly silicone oil emulsion can be used as defoamer.

Defoaming emulsion also can partly saponification vegetable oil or mineral oil obtain with sodium hydroxide or potassium hydroxide.The advantage of the stable emulsion that obtains like this is that employed material all is natural product, and their very easy decomposition and fully being decomposed in the vital movement of crop.

In plant protection technology, the effect of suspension concentrates promptly increases.The composition of said this formulation comprises active ingredient and adjuvant, and active ingredient exists with the form that suspends, and adjuvant exists with the form of the aqueous solution or oil solution.The effect of water and oil is a solvent, also is filler and thinner simultaneously.Suspension concentrates has following advantage:

Because each involved component all is a suspending agent, just got rid of the danger of inevitable formation dust;

Moistening slowly normally serious problem of the caused suspension pulvis of faint wettable character of active ingredient particle, but this situation is impossible in suspension concentrates;

In solution, also added the adjuvant that improves adhesivity and other character, thus caking avoided, so during sprinkling, nozzle can not get clogged, and can obtain well-proportioned sprinkling;

Mixture has good suspendability.

Suspension concentrates generally comprises wetting agent and the dispersant of enumerating in wetting powder.Comprise that also some increase the auxiliary agent of suspension stability, that is those water miscible larger molecular organicses, the material that can be used for this purpose has the derivative of carbohydrate, synthetic polymer and formulation texture modifier (as the very big bentonite of synthetic silicic acid, aluminium oxide and surface area, organophilic bentonite etc.)

The anti-agglomerating agent that reduces set point also may be the components by weight percent that contains aqueous suspension agent, can select particularly polyethylene glycol of polyalcohol for use in order to reach this purpose.

The stability of suspension also may utilize proper proportion vegetable oil, animal oil or mineral oil emulsification and improve with preferable methods.These additives have also improved the biologically active of mixture.

The microorganism that lives in the soil can be controlled by a method that is called soil disinfection.It is very desirable that this purpose is used particle formulation agricultural chemicals.After this preparation was executed in the soil, under the effect of the moisture in soil, active ingredient was released, thereby and in soil, move and eliminated this unwanted pathogen, and give cultivated plant to be suitable for growth interference-free environment.

Granular pesticide can will grind to form active ingredient, carrier, filler and auxiliary agent (for example wetting agent, dispersant, the sticker of certain particle diameter, regulate the release regulator that active ingredient discharges, anti-agglomerating agents etc.) water mixes, pinch should mixture, and make it pass through the sieve of certain size sieve aperture, or with other known method granulation, drying grinds or atomized drying.According to the another one method, the particle of active ingredient is administered on the surface of a suitable carrier particle diameter that the particle diameter of carrier is worked into expectation in advance distribute (for example organic or inorganic particle).If a kind of or all active ingredients all are liquid, used carrier granular needs the hole of certain absorption capacity, and liquid can be absorbed in the porous particle of being mentioned.At active ingredient partly is solid, and part is under the situation of liquid, and can carry out like this: the solid active composition is dispersed in the liquid active ingredient, uses the resulting liquid of carrier absorption of porous then, by means of this, solid particle has also just adhered on the carrier.If what use is the active ingredient of solubility, can adopt following processing method, be about to active ingredient and be mixed with solution, then with this solution of carrier absorption, solvent evaporated again.

Sticker preferably is chosen in the material that natural world exists, such as cellulose derivatives, and carbohydrate, gelatin, natural gum, vegetable oil, animal oil or mineral oil, fat etc. all can use.Certainly, also can use synthetic sticker, for example: polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyacrylamide and polyvinylpyrrolidone etc.

On Shi Yan the basis, carried out in vivo testing the effect of killing bacterium and fungi in vitro to measure.Employed in these trials mixture prepares by following embodiment.

Embodiment 3

Prepared and had the active component that following particle diameter distributes

10 μ m above 20.3%

5～10μm 31.0%

5 μ m following 48.7%

Particle diameter is to measure with the ultrasonic Microtraps that Retsch factory produces.

Claim 100kg active component CH-819; 3kg Diotilan; 5kg Totanin B; the Tylose C of 41kg Neuburg Chalk and 1kg places in one 600 1 Loedige type flash mixer by comminutor (grinding granulator) and to stir 10 minutes.Can (per hour can pulverize 200kg) in Alpine UP315 attrition mill for the close contact that guarantees various compositions pulverizes, in one 300 L Nautamix blender, evenly mix again, just obtain the product of required particle diameter component, product is packed.

The suspensibility of the CH-819 80 WP wetting powders that obtain like this can reach the standard of 80%(by WHO, measures with 0.5% suspension).

Embodiment 4

CH-819 active ingredient with having the particle diameter distribution that proposes among the embodiment 3 prepares following mixture:

CH-819 160kg

Evidet27 2kg

Alkene 6kg

BoresperseNA 10kg

Tylose C 1000p 1kg

Aerosil300 1kg

Calcium carbonate pp 20kg

Because the wetting powder that obtains like this has high active ingredient content, so be particularly suitable for the bacterial treatment of killing of potato and root crops.

Embodiment 5

Absorption fungicide in also adding except adding bactericide in mixture just can obtain the medicament that effectively preventing fungi and bacterium are infected simultaneously, and present embodiment has prepared following mixture:

Benomyl 60kg

CH-819 40kg(particle diameter distributes with embodiment 3)

Genapol PGM 10kg

Useless sulphite powder 10kg

Starch calcium carbonate pp 80kg

Except Genapol PGM; other composition all places in the flash mixer of one 600 1 Loedige model by comminutor; stirred 3 minutes; Genapol PGM(Genapol PGM is moisture 50% thickness wetting agent) directly add; promptly, evenly mixed then ten minutes not by comminutor.Mixing the back material places KFSZ-20-SH type pneumatic conveyer dryer (fluidization drier) lining that agitator is housed dry again, in Alpine AS-200 airslide disintegrating mill, pulverize then, in 300 1 Nautamix blenders, carry out last evenly mixing again, at last with the packing of product.

Embodiment 6

Prepare following mixture

CH-819 26.4kg(particle diameter distributes with embodiment 3)

Benomyl 68.0kg

Mancozeb 20.0kg

Diotilan 2.0kg

Evidet27 2.0kg

Tylose H 20 2.0kg

Aerosil 300 1.0kg

Rodamin B 0.6kg

Calcium carbonate pp 68.0kg

Mixture thoroughly evenly mixes last packaging product then being crushed to average grain diameter 5 μ m in the Alpine AS-200 airslide disintegrating mill with the 10kg methyl-sulfoxide in 300 1 Nantamix blenders.

Embodiment 7

With 183.35g water and 55g ethylene glycol mixing, under 40 ℃, 16.5g Tensiofix B4725 and 16.5g Tensiofix CG11 are dissolved in the aqueous solution of above-mentioned ethylene glycol, under the help with agitator of high shear force (model is Ultra-Turrax) very, the 143g particle diameter CH-819 identical with embodiment 3 that distribute is distributed in the above-mentioned solution.

Continue to disperse under the stirring condition, the mixture of 99g paraffin oil and 11g Tritox X-45 joined in the above-mentioned suspension, Gu stir be performed until obtain one uniformly oil--water system.Stir and in this system, to add 2%(weight down) 25.7g Tensiofix 821 aqueous solution, continue again to stir this mixture, up to obtaining uniform mixture.If bubble, need when this EOS, to add 1.1g Tensiofix L051 defoamer during stirring.The preparation that obtains like this can adhere on the crop well, and suspension has good stability, and suspensibility is greater than 95%.

Embodiment 8

By means of dissolvers 228.3kg water and 7kg ethylene glycol are mixed, under further stirring, infiltrate following ingredients:

1.5kg Atlox4875

0.5kg Atlox1225

1.5kg Atlox4852/b

Above-mentioned surfactant solution is placed in the dissolvers, add 21kg CH-819 and 34kg mancozeb active component, make to be suspension.

With suspension be placed on per hour can grind 2001 501 grinding in ball grinder to average solid particle size less than 5 μ m, the suspension that this is ground places in the device that agitator is housed, under agitation add 9kg paraffin oil and 1kg Triton X45, fully behind the mixing, at 2% aqueous solution that continues to add under the stirring 5kg Tensiofix821.Continue to mix, and go aggregation apparatus to make resulting suspended emulsion system stabilityization by one.Add 0.3kg Tensiofix L051 defoamer at the last of this step and before the last formation of preparation.The mixed insecticide preparation of making like this has good pulverability, and more employed agricultural chemicals all can more easily adhere on the plant better than so far for it.

Embodiment 9

Prepare following mixture

20 parts of carbendazim (weight ratio)

20 parts of CH-819 (weight ratio)

3 parts of Tensiofix B4725 (weight ratio)

3 parts of Tensiofix CG21 (weight ratio)

10 parts of ethylene glycol (weight ratio)

2% 5 parts of 821 aqueous solution of Tensiofix (weight ratio)

40 parts in water (weight ratio)

Embodiment 10

CH-819 infects the effect of bacterium and the fungi of potato to duration of storage

The each processing of storage pre-treatment potato tubers (kind Somogy Gyoengye) used the 50kg stem tuber, repeats five times, and stem tuber storage until evaluation finishes, calculates the stem tuber number of disease potato number and different infection processes in the storage of potato chamber.

The results are shown in Table 6

Table 6

Mixture

Feature symptom embodiment 3 embodiment 5 embodiment 6

2kg/T 3kg/T 3kg/T

Sick potato several 27.4 22.8 19.7

Sickle spore bacterium dry rot 18.0 12.5 12.5

（Fusarium dry rot）

Chain lattice spore dry rot 6.0 5.8 2.4

（Alternaria dry rot）

Hu Luobu soft rot Erwinia 3.4 4.5 5.8

Black rotten mutation

Table 6 is continuous

Mixture

Feature symptom embodiment 7 embodiment 8 contrasts

21/to 21/to

Sick potato several 31.0 25.4 53.0

Sickle spore bacterium dry rot 21.0 15.0 29.0

（Fusarium dry rot）

Chain lattice spore dry rot 5.6 5.2 8.0

（Alternaria dry rot）

Hu Luobu soft rot Erwinia 4.4 5.2 16.0

Black rotten mutation

It is only effective to Erwinia only to contain the nitrofuran derivatives formulations of active ingredients, but can use the preparation that adds fungicidal composition in this nitrofuran derivatives to prevent and treat by the rot that sickle spore bacterium and alternaric bacteria cause.Mixture among the embodiment 5,6 and 9 demonstrates the effect that better control is infected, and particularly embodiment 6, CH-819+ benomyl+mancozeb=13+34+10%(percentage by weight) effect that obtains is best.

Embodiment 11

After the potato tubers (UT-1) that is used to do kind digs out, handled October 23, with the test compound of doses with wet-treating (wet dressing) (potato seed per ton with 15 liters of pharmacy solutions), potato with the machine results carries out treatment and purification before processing, choose soil block, stem tuber that is left and sick potato are all disallowable.Each is handled with 200 potato seeds, and each dosage is established three repetitions, and the potato piece after the processing is put into cloth bag, is placed in the big accumulation formula storage facilities of a ventilation, and the duration of storage temperature is transferred to and is lower than 15 ℃, and relative moisture is 80～90%.Change the environmental parameter of prismatic storage facilities, as temperature, moisture, the appropraite condition that provides pathogen to grow.

Estimated the result the April in 1 year 30.Calculate the weight of potato piece healthy and that infected and their ratio, determine inhibiting rate and infection process degree.The result is as shown in table 7.

The result of above-mentioned industrial-scale pilot has proved the validity of mixture controlling plant diseases of the present invention, does not have the potato seed handled because the loss maximum that the dry rot of sickle spore bacterium causes, and because the loss that soft rot Erwinia causes also is very high.Mixture according to embodiment 5 and 9 preparations is effective especially to sickle spore bacterium and soft rot Erwinia, and the mixture of preparing by embodiment 6 is the most effective to sickle spore bacterium+soft rot Erwinia+alternaric bacteria.

Embodiment 12

Be the seed dressing machine of GUMOTOX prior to seeding with model, handle potato (kind in accordance with regulations) with test compound, dosage is 6.51 treatment fluids/ton potato seed.Sowing is carried out with 4-Sa BP-75 sower, and the area of test fritter is 0.5 hectare, repeats 3 times, and sowing quantity is 2.8 tons/hectare.

Sow 15 days and add up later on because rhizopus (Rhizoctonia germ) infects the not germinative number that causes, measure the radical that 200 offspring are infected by rhizopus in 4 * 50 square metres of areas, 200 potato pieces of every group of investigation calculate situation about being infected by germ (Thizoctonia) and determine to have the ratio of the potato piece of 4～6 centimetres of diameters.The results are shown in Table 8.

Because the seed dressing of carrying out before the sowing is handled, output of crop and the weight of potato crop (%) have risen to degree highly significant.

Embodiment 13

Pathogenic and bacterium are to the susceptibility of the carbendazim and the CH-819 mixture of different proportion

Carried out bacteria test extremely in vitro.Minimum inhibitory concentration to described two kinds of various different proportion mixtures of bactericide is measured as follows:

Prepare the preparation of two kinds of bactericide different proportions, then they are mixed in medium, make to have following different concentration: the final concentration of CH-819 is respectively 1000,100,10,1 and 0.1mg/l, the concentration of carbendazim in medium is then according to the ratio of mixing and difference.

Calculate in 25 experimental series under each different mixing proportion the relative control efficiency of the CH-819 of each test.The result calculates the equation Svab 1981:Biometrical methods in research that has utilized Mc Kiney, Mezoegazdas á gi Kiad ó Budapest)

The result is shown among Fig. 1

Making us alert has very found: if carbendazim is preponderated in mixture, the bactericidal activity of CH-819 has very big growth, that is in some cases, can reach 100 times (seeing Table 3) of growth, this synergistic effect can at length be observed in the test of control Xanthomonas campestris (Xanthomonas genus).

Medium

Agar medium (Humon OEV) 26g

Bacto agar 2.5g

Glucose 3g

Yeast extract 1g

Bacto peptone 2g

Potassium dihydrogen phosphate 0.55g

Potassium chloride 0.1g

Sodium chloride 0.1g

Magnesium sulfate 0.125g

Calcium chloride 0.125g

Ironic citrate 0.02g

Press the trace element solution of Hoagland and Arnon method preparation

The 1ml/l culture fluid

Medium pH value 2N NH ₄OH solution transfers to PH=6.5

Inoculation

Test compound was added to before medium solidifies in 50 ℃ the medium, by common bacteriological method, treated to inoculate after medium solidifies.

Embodiment 14

Handle to eliminate the infecting of leaf spot bacteria (Xanthomonas oryze) of paddy rice with seed dressing

Pathogen is to separate from the seed from the Far East, and they show uncertain infectivity.

These seeds are to handle like this: each processing is 250 seeds, handles with Kofugo 25 FW of suitable dosage and the mixture (embodiment 7) of CH-819 30 FW before seed sprouting.Because Kolfugo 25 FW are complete non-activities to the pure culture base, so do not handle seed with it.These seeds are placed on the wet filter paper vernalization and cultivated 48 hours, (this is a kind of " dopog " method that typically is called), each is handled and all uses 200 seeds that basic bud is arranged, with the stem acanthopore of a pin at these seed base-roots, the planting seed of handling like this in aseptic soil, and in artificial climate chamber incubation growth 15 days.(artificial climate chamber illumination is 12 hours, 28 ℃ of daytimes, 25 ℃ of evenings), evaluation result after 15 days.

The pathogenic seed institute of the seed that causes a disease that the CH-819 carbendazim of sowing germinates

The ratio that seed number g/t g/t seed number number accounts for, %

200 0 0 178 61 34.2

200 300 0 184 5 2.7

200 300 700 178 0 0

200 150 1350 170 0 0

Claims (4)

1, the Pesticidal composition of control bacterial diseases of plants, its effective ingredient comprise the nitrofuran derivatives shown in the following general formula (I) and any one or both known Fungicidally active compositions of selecting, and they account for 1～99% to 1～80% of total mixture weight,

X represents group (a) or (b) in the formula:

And the ratio of the active ingredient of general formula (I) and known Fungicidally active composition is: if two kinds of active ingredients, then this ratio is 1: 1.5～9; If three kinds of active ingredients, then this ratio is (1～2): (1～4): 1, active ingredient more respectively with suitable inert solid or liquid-carrier or thinner, and adjuvant commonly used such as wetting agent, dispersant, sticker, defoamer with (or) anti-agglomerating agent mixes mutually.

2,, wherein comprise the Fungicidally active composition of one or both following compounds according to the described mixture of claim 1:

Benomyl 0-methyl-N-(1-butylamine formoxyl-2-benzimidazole) carbamate

Carbendazim 0-methyl-N-2-benzimidazole carbamate

Thiophanate methyl 1,2-pair-(3 '-methoxy polyamides-2 '-ghiourea group)-benzene

Zineb ethylene-1,2-pair-(aminodithioformic acid) zinc

Maneb ethylene-1,2-pair-(aminodithioformic acid) manganese

The complex compound of mancozeb zineb and maneb

3, preparation is according to the method for the Pesticidal composition of the described control bacterial diseases of plants of claim 1, comprising with the reactive compound of a kind of general formula (1) (in claim 1 illustrated) with one or both known antifungal compositions of selection and suitable inert solid or liquid-carrier or thinner and optional suitable formulation excipient mix mutually arbitrarily.

4, the method for control bacterial diseases of plants, comprising effective dose of the mixture of using claim 1 defined in plant, in soil or its environment.