CN102113485A - Bactericidal composition containing ethirimol and kresoxim-methyl - Google Patents

The invention discloses a bactericidal composition containing ethirimol and kresoxim-methyl and a preparation method and application thereof. The bactericidal composition is characterized by containing the ethirimol, the kresoxim-methyl and other aids, wherein the weight ratio of the ethirimol to the kresoxim-methyl is (0.1-50):(0.1-60). The bactericidal composition can be applied to various diseases of cereals, melons, fruits, vegetables and the like. The composition has a wide application range, low cost and good effects. Indoor tests prove that: the composition has obvious synergy. Moreover, the compounding of the ethirimol and the kresoxim-methyl is not reported in China and foreign countries, so the bactericidal composition is provided.

A kind of bactericidal composition that contains phonetic phenol of second and kresoxim-methyl

Technical field

The invention belongs to the agriculture chemical compounding field, relate to a kind of bactericidal composition and application thereof, especially a kind of is the bactericidal composition and the application thereof of main active with phonetic phenol of second and kresoxim-methyl.

Background technology

Using chemical agent is the most effectively means of control fungal diseases of plants.But long-term use single chemical bactericide continuously high dose, cause problems such as residual, the environmental pollution of medicament and anti-pesticide resistance fungi development easily.Reasonably chemical bactericide is composite or be mixed and have the expansion fungicidal spectrum, improve control efficiency, prolong the optimum period for applying fertilizer, reduce dosage, reduce poisoning, reduce residual, delay fungi drug resistance and positive characteristics such as drug-fast generation and development, bactericide compounded or to be mixed be one of the effective method the most that addresses the above problem.Exploitation new product bactericide price is constantly soaring, and by contrast, exploitation is efficient with research, the composite of low toxicity, low-residual has small investment with being mixed, and the lead time is short and be subjected to domestic and international attention, strengthens the development dynamics one after another.

The phonetic phenol of second (ethirimol) is a kind of adenosine deaminase inhibitors, systemic fungicide.CAS number: 23947-60-6, chemical name: 5-butyl-2-ethylamino-4-hydroxyl-6-methylpyrimidine, the phonetic phenol of second is efficient mitochondrial respiratory inhibitor, and its activity is present 3 times with series bactericidal agent, can control most of diseases such as Ascomycetes, Basidiomycetes, deuteromycetes, Oomycete.The phonetic phenol of second has very strong inhibitory action to the growth of spore germination and leaf intramatrical mycelium, has protection and therapeutic activity.The characteristics that long, resistance of rainwater washing against of permeability and local systemic activity, lasting period is arranged because of this medical instrument, the lasting period can reach 10～14d after the dispenser, is widely used in preventing and treating the disease on wheat, paddy rice, peanut, grape, vegetables, potato, banana, lemon, coffee, fruit tree, walnut, tea tree, tobacco and ornamental plants, lawn and other field crops.Yet the intrinsic resistance risk of the phonetic phenol of second is very high, if long-term single use unavoidably can produce resistance, and this medicine cost height, popularize and promote relatively difficulty in each field of agricultural production.By carrying out composite with other effective bactericide is to reduce production costs, and delays the effective way that pesticide resistance produces, prolongs its service life.

Kresoxim-methyl (kresoxim-methyl) belongs to novel half systemic fungicide, with the gaseous form diffusion, both can stop germ spore germination, germ tube elongation and the intrusion of blade, fruit surface, plays the prevention protective effect; Can penetrate cured matter layer and epidermis again or enter in the body by pore; suppress to have invaded the germ growth, make the mycelia atrophy, suppress to produce spore; the spore that has produced can not be sprouted; reach the treatment eradicant action, have the protection activity and can be used as control therapeutic agent and eradicant, fungicidal spectrum is wide; has very high activity; most of fungies are extremely sensitive to it, and powdery mildew, anthracnose, scab are had special efficacy, and can prevent and treat leaf spot, ring spot, downy mildew, eqpidemic disease etc.After the use, there is the crop leaf of promotion to enlarge afforested area, increases effects such as photosynthesis.Being mixed property is good, can use with other insecticidal bactericide; Different fully with modes of action such as conventional amino formyl imidazole class medicaments, there is not cross resistance.To crop safety, florescence and fruit phase use and can not produce poisoning.Be applicable to various vegetables, fruit and flowers use.

Summary of the invention

The present invention be directed to the problems referred to above a bactericidal composition that contains phonetic phenol of second and kresoxim-methyl applied widely, that cost is low, effective is provided.

A further object of the invention provides the purposes of this bactericidal composition.

A kind of bactericidal composition, it contains phonetic phenol of second and kresoxim-methyl, and wherein the weight ratio of phonetic phenol of second and kresoxim-methyl is 0.1～50: 0.1～60.

Described bactericidal composition, wherein the more excellent weight ratio of phonetic phenol of second and kresoxim-methyl is 1～40: 1～50.

Described bactericidal composition, wherein active ingredient accounts for the weight ratio of preparation and is: 2～70%.

Described bactericidal composition, phonetic phenol of second and kresoxim-methyl and auxiliary agent, carrier etc. are processed into any one formulation that allows on the agricultural chemicals.

Described bactericidal composition is characterized in that the formulation that can be processed into is missible oil, suspending agent, aqueous emulsion, microemulsion, microcapsule formulations, wetting powder and water dispersible granules.

The application of described bactericidal composition aspect the multiple diseases of control cereal class and fruit tree, melon, vegetables etc.

Microbicide compositions with synergistic effect takes following measure to realize:

Contain two kinds of active components of phonetic phenol of second and kresoxim-methyl in the composition, wherein the weight ratio of phonetic phenol of second and kresoxim-methyl is 0.1～50: 0.1～60, more excellent weight ratio is 1～40: 1～50, and the active ingredient of composition adds auxiliary agent and filler can be processed into missible oil, aqueous emulsion, suspending agent, microcapsule formulations, wetting powder and water dispersible granules.

Specific embodiments of the present invention is as follows:

One of technical scheme of the present invention, described Pesticidal combination are cream preparation, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Conventional emulsifier 10～30%

Conventional solvent 20～50%

Conventional synergist 1～5%

The concrete production stage of this cream preparation adds emulsifier, the synergist back that stirs after the dissolving fully again and becomes the oily liquids of transparent and homogeneous for earlier the phonetic phenol of second, kresoxim-methyl being added in the solvent, can promptly makes the cream preparation that contains the bactericidal composition of phonetic phenol of second and kresoxim-methyl of the present invention.

Two of technical scheme of the present invention, described bactericidal composition are aqueous emulsion, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Emulsifier 3～30%

Solvent 5～15%

Stabilizing agent 2～15%

Antifreezing agent 1～5%

Defoamer 0.1～8%

Thickener 0.2～2%

Water surplus

The concrete production stage of this aqueous emulsion is: at first the phonetic phenol of former medicine second is added with kresoxim-methyl, solvent and emulsifier, cosolvent and be in the same place, make and be dissolved into uniform oil phase; With part water, antifreeze, other insecticides adjuvant such as antimicrobial mixes into uniform water; When the reactor high speed stirs, oil phase is added water, slowly add water, open clipper and carry out high speed shear, and add remaining water, shear half an hour approximately, form the aqueous emulsion of oil-in-water type until reaching the phase inversion point.Promptly make the aqueous emulsion of the bactericidal composition that contains phonetic phenol of second and kresoxim-methyl.

Three of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Dispersant 5～20%

Antifreezing agent 1～5%

Thickener 0.1～2%

Defoamer 0.1～0.8%

Water surplus

The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed, mix through high speed shear, add phonetic phenol of second and kresoxim-methyl, abrading-ball is 2～3 hours in ball crusher, make a diameter all below 5mm, make the suspending agent preparation that contains the bactericidal composition of phonetic phenol of second and kresoxim-methyl of the present invention.

Four of technical scheme of the present invention, described bactericidal composition are microcapsule formulations, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Urea 5～20%

Formaldehyde 5～20%

Emulsifying dispersant 5～20%

Antifreezing agent 1～5%

Thickener 0.1～2%

Defoamer 0.1～0.8%

Water surplus

In the there-necked flask of agitating device is housed, add urea and formaldehyde (amount of substance ratio be about 1: 1.5～2.0), about pH value to 8～9, be warming up to 70～80 ℃ then, react and obtain stable urea resin prepolymer with the sodium hydroxide solution regulator solution.The former medicine of getting phonetic phenol of a certain amount of second and kresoxim-methyl is dissolved in the cyclohexane, and adds emulsifying dispersant in solution, follows vigorous stirring, and being made into the aqueous solution that contains emulsifying dispersant is the O/W type stable emulsion of water.Above-mentioned urea resin prepolymer is added in the emulsion, regulate the pH value, polymerization reaction take place under the acid catalysis condition is wrapped oil phase substance, forms microcapsule granule.Slowly heat up, solidify, temperature is controlled at 40～50 ℃, hardening time 1h.Select to add an amount of auxiliary agent, the microcapsule suspending agent that gets final product stablely.

Five of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Dispersant 3～20%

Wetting agent 3～10%

Filler 10～70%

The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned prescription with the phonetic phenol of second and kresoxim-methyl and dispersant, wetting agent and filler mixing, in stirred tank, evenly stir, behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.

Six of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:

The phonetic phenol 0.1～50% of second

Kresoxim-methyl 0.1～60%

Dispersant 3～20%

Wetting agent 3～10%

Disintegrant 2～5%

Filler 10～70%

The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned prescription the phonetic phenol of second, kresoxim-methyl and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis makes the water dispersible granules that contains the bactericidal composition of phonetic phenol of second and kresoxim-methyl of the present invention.

Described conventional emulsifier is selected from any one or more mixtures formed with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styryl phenol APEO, polyoxyethylene nonylphenol ether, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, the polyoxyethylene aliphatic alcohol ether.

Described conventional solvent is any one or more mixed solvents formed with arbitrary proportion in dimethylbenzene or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine oil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), the water equal solvent.

Described conventional synergist is meant to have the medicament of enhancing penetration, wetting extended capability, knock down insect speed, improve the resistance of rainwater washing against power of agricultural chemicals, thereby improve a class safety, environmental protection of agricultural insecticide, bactericidal effect, the New-type adjuvant of nontoxic, noresidue, optional in organic silicon pesticide synergist ZC-650 or organic silicon pesticide bleeding agent spreading agent Agrowet810c, agricultural organic silicon pesticide synergist Silwet408, azone any.

Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.

Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX., among the wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, soapberry powder one or more.

Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, the sodium bicarbonate.

Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, the polyvinyl alcohol.

Described stabilizing agent is selected from: a kind of in sodium citrate, the resorcinol.

Described antifreeze is selected from: one or more in ethylene glycol, propane diols, the glycerine.

Described defoamer is selected from: silicone oil, silicone compound, C _10-20Saturated fat acid compounds, C _8-10In the aliphatic alcohols compound one or more.

Described emulsifying dispersant comprises: wetting agent, dispersant, stabilizing agent, thickener, defoamer and antifreezing agent etc.

Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.

The invention has the beneficial effects as follows:

1, two kinds of compound effects mechanism differences involved in the present invention, being mixed mutually can not produce conflict, but Synergistic reduces dosage, reduces cost.And phonetic phenol of second and kresoxim-methyl composite do not have report as yet.

2, the pathogen that produces resistance is still had very high drug effect, but suspension of pesticide resistance generation.

3, reduced the agricultural chemicals usage amount, strengthened friendly environment.

Specific embodiment

The different proportioning co-toxicities of kresoxim-methyl with the phonetic phenol of second

1 materials and methods

The design 1.1 material and medicament are mixed

Test medicine is 90% kresoxim-methyl dry suspending agent, Basf China Co., Ltd's product, the phonetic phenol SC of 95% second (Zhejiang standing grain benefit farmingization Co., Ltd provides).For the examination pathogen is banana tail spore bacterium (Cercosporamusae).Examination is made as 30% kresoxim-methyl according to kresoxim-methyl and the phonetic phenol of second total active constituent content that is mixed: the phonetic phenol of second was established 1: 1,1: 2,1: 2.75,1: 3.29,1: 4 by former medicine mass ratio, and promptly 5 ratios such as 15%+15%, 10%+20%, 8%+22%, 7%+23%, 6%+24% are mixed.

1.2 experimental scheme

Take by weighing the combination that is mixed of the phonetic phenol of an amount of second, the former medicine of kresoxim-methyl, 5 phonetic phenol of kresoxim-methyl second respectively, fully vibration makes its dissolving in the sterilization triangular flask that adds 3mL watery hydrochloric acid in advance, and adding an amount of sterile water, to make 500 each 50mL of μ g/mL mother liquor standby.On the basis of preliminary experiment, respectively be mixed combination and kresoxim-methyl, the phonetic phenol of second of the phonetic phenol of kresoxim-methyl second respectively to be established 5 concentration gradients such as 2.5,5,10,20 and 40 μ g/g, and make blank with the watery hydrochloric acid of same concentrations, each is handled and repeats 3 times.

1.3 synergistic effect is measured

The employing growth rate method is measured, and every processing repeats 3 times, calculates relative inhibition, virulence regression equation, EC50 that each is handled, obtains the coefficient of synergism (SR) that each is handled with the Wadley method, carries out the synergistic effect evaluation.Data see Table 1.

The phonetic phenol mixture of the kresoxim-methyl second of the different proportionings of table 1 suppresses virulence and synergistic effect to banana tail spore bacterium

2 results and analysis

Each mixture synergism coefficient that the phonetic phenol of kresoxim-methyl and second is mixed is all greater than 1, but kresoxim-methyl: 1: 2 combination S R value that is mixed of the phonetic phenol of second is up to 1.95, greater than 1.5, shows as synergistic function, remaining 4 be mixed combination S R value all less than 1.5 greater than 1, show as summation action.

3 field trials are surveyed alternaria leaf spot of apple and sigatoka

3.1 test method

3.1.1 application method

Test dispenser twice altogether, contrast orchard spray equivalent clear water.When making up a prescription, after with low amounts of water medicament fully being dissolved earlier, add suitable quantity of water again and carry out complete stool spraying processing, tree crown even spraying.All adopting power driven sprayer, operating pressure during the spray medicine is 2.0～2.3kg/cm ², shower nozzle aperture 1.2mm.The about 3.0kg of every strain tree spraying volume is with the following droplet degree of being not of soup on moistening blade of soup and the branch.

3.1.2 investigation method

Alternaria leaf spot of apple: fixing investigation three strains of every sub-district, every strain from East, West, South, North, five directions fix 3 branches, its whole blades of periodic investigation, write down total number of sheets, the sick number of sheets at different levels, calculate the blade incidence of disease, disease index, refer to comparison, calculate relative control effect with the contrast disease.

State of an illness grade scale (is unit with the blade)

0 grade: no scab;

1 grade: the sick area of scab accounts for whole leaf area below 10%;

3 grades: the sick area of scab accounts for whole leaf area 11%～25%;

5 grades: the sick area of scab accounts for whole leaf area 26%～40%;

7 grades: the sick area of scab accounts for whole leaf area 41%～65%;

9 grades: the sick area of scab accounts for whole leaf area more than 65%.

Sigatoka disease: every sub-district fixing investigation 3 strains, every strain banana is down investigated 5-13 leaves (not opening lobus cardiacus disregards) from top, and total number of sheets, the sick number of sheets at different levels of record investigation are calculated the blade incidence of disease, disease index, refer to comparison with the contrast disease, calculate relative control effect.

State of an illness grade scale (is unit with the blade)

0 grade: no scab;

1 grade: the sick area of scab accounts for whole leaf area below 5%;

3 grades: the sick area of scab accounts for whole leaf area 6%～10%;

5 grades: the sick area of scab accounts for whole leaf area 11%～25%;

7 grades: the sick area of scab accounts for whole leaf area 26%～50%;

9 grades: the sick area of scab accounts for whole leaf area more than 50%.

3.1.3 control time and number of times

Test is investigated 4 times altogether, radix investigation before the medicine, behind the medicine 5 days for the first time, behind the medicine 5 days and carried out the 4th investigation for the second time behind the medicine in 18 days for the second time.

3.1.4 drug effect computational methods

Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100

Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100

Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100

3.1.5 poisoning investigation method

Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.

3.2 result of the test and analysis

3.2.1 each handles the effect (seeing Table 2) of control alternaria leaf spot of apple

Each handles the effect of control alternaria leaf spot of apple table 2

As can be seen from Table 2,30% kresoxim-methyl: the phonetic phenol of second is better than 50% kresoxim-methyl list agent with the effect of 1: 1 the combination control alternaria leaf spot of apple that is mixed, and also is better than the agent of the phonetic phenol list of 25% second; And it has good quick-acting and lasting effect, and 18 days the highest preventive effect can reach 85.07% behind its 2 medicines, is higher than the preventive effect of 50% kresoxim-methyl list agent and the agent of the phonetic phenol list of 25% second far away.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to apple all do not occur, illustrates that it is safe to apple.

3.2.1 each handles the effect (seeing Table 3) of preventing and treating sigatoka

Each handles the effect of preventing and treating sigatoka table 3

As can be seen from Table 3,30% kresoxim-methyl: the phonetic phenol of second also has good control efficiency with 1: 1 the combination that is mixed to sigatoka, and its effect is better than 50% kresoxim-methyl list agent and the agent of the phonetic phenol list of 25% second; Have good quick-acting and lasting effect, 18 days preventive effect is higher than the preventive effect 63.77% of 50% kresoxim-methyl list agent and the preventive effect 56.72% of the phonetic phenol list of 25% second agent at 71.92%-80.73% behind its 2 medicines, can well control the generation of sigatoka.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to banana all do not occur, illustrates that it is safe to banana.

In sum, the present invention contains the Bactericidal composite thing of kresoxim-methyl and the phonetic phenol of second, alternaria leaf spot of apple, sigatoka and powdery mildew etc. there are better prevention and result for the treatment of, and it is compared with single dose the target crop safety, and Bactericidal composite thing of the present invention has the advantage that quick-acting is good, the lasting period long, do not pollute the fruit face, dosage is low, environmental pollution is few, is difficult for producing poisoning

So research and development of the present invention and popularization are of great significance social tool.