CN108271799B

CN108271799B - Bactericidal composition containing pyraclostrobin

Info

Publication number: CN108271799B
Application number: CN201810150398.5A
Authority: CN
Inventors: 陈少亭; 邵鸿鸣; 李乙军
Original assignee: ZHEJIANG YONGTAI TECHNOLOGY CO LTD
Current assignee: Shanghai yongkuo Biomedical Technology Co.,Ltd.
Priority date: 2018-02-13
Filing date: 2018-02-13
Publication date: 2021-01-29
Anticipated expiration: 2038-02-13
Also published as: CN108271799A

Abstract

The invention relates to a bactericidal composition, and active ingredients of the composition comprise pyraclostrobin and Changchun mycin, wherein the weight ratio of the pyraclostrobin to the Changchun mycin is 80: 1-2: 1. The invention also relates to a method and application of the composition for preventing and treating agricultural fungal diseases.

Description

Bactericidal composition containing pyraclostrobin

Technical Field

The invention belongs to the field of agriculture, and particularly relates to a pyraclostrobin-containing composition, and a method and application thereof for preventing and treating agricultural fungal diseases.

Background

Pyraclostrobin is pure white solid, is insoluble in water, is soluble in organic solvents such as dichloromethane, acetonitrile, ethyl acetate and acetone, belongs to a mitochondrial respiration inhibitor, has the functions of protection, treatment and leaf permeation and conduction, and has good control effects on powdery mildew, downy mildew, banana scab, leaf spot, sclerotinia sclerotiorum and the like of cucumbers.

The Changchuan mycin is white powder, is a biological bactericide developed by pesticide research institute in Shanghai, can be used for most organic solvents, such as methanol, acetone, acetonitrile, ethyl acetate and the like, and is slightly soluble in water. Can be used for preventing and treating gray mold of cucumber, tomato, strawberry and eggplant, and various fungal diseases such as corn small spot, sclerotinia rot and powdery mildew.

The Chinese patent application CN01126969.3 discloses an agricultural Changchuan mycin fungicide, which can be prepared into powder, wettable powder, granules, tablets, microcapsules and the like, and is used for preventing and treating various plant diseases such as gray mold, corn small spot, anthracnose wheat scab, cucumber downy mildew and the like.

Zhang Shuai et al (plant protection, 2013,39(6)) disclose combined toxicity and drug effect of a mixture of difenoconazole and pyraclostrobin on anthrax bacteria, and show that the mixture with the mass ratio of 2:1 of difenoconazole to pyraclostrobin has the most obvious synergistic effect on inhibiting hypha growth, and the synergistic coefficient is 2.41. In a field pesticide effect test, the two medicaments 2:1 are mixed to have obvious effect of controlling the anthracnose.

Chinese patent application CN201610404771.6 discloses a pesticide composition containing pyraclostrobin and boscalid, which comprises common auxiliaries, pyraclostrobin and boscalid, wherein the weight ratio of the pyraclostrobin in the composition is 10%, and the weight ratio of the boscalid in the composition is 20%; the suspension agent is prepared in actual use, has a synergistic effect on botrytis cinerea, is suitable for preventing and treating the gray mold of the watermelon, and has a synergistic effect on yield increase of the watermelon when the watermelon is used in a fruit swelling period.

The long-term use of a large amount of single pesticides, the drug resistance risk of the target is greatly increased, and then the control effect is reduced and the dosage is increased. In actual production, the objective requirement of the synergistic composition exists, and on one hand, the total application amount of pesticides can be reduced, the environmental pollution is reduced, and the cost is reduced; on the other hand, the pesticide effect can be improved, the drug resistance of the target can be delayed, and the long-term healthy development of agriculture is facilitated.

Summary of The Invention

Aiming at the general requirements of the current environment, the inventor finds that after long-term exploration, the pyraclostrobin and the Changchun mycin can generate obvious synergistic action so as to improve the pesticide effect and delay the development of the drug resistance of a target. Based on this, the present inventors have completed the present invention.

The invention relates to a bactericidal composition, wherein the active ingredients of the composition comprise pyraclostrobin and Changchun mycin, and the weight ratio of the pyraclostrobin to the Changchun mycin is 80: 1-2: 1.

The bactericidal composition provided by the invention is characterized in that the active ingredients of the composition only consist of pyraclostrobin and Changchun mycin.

The bactericidal composition provided by the invention is characterized in that the weight ratio of pyraclostrobin to Changchun mycin is 40: 1-8: 1.

The bactericidal composition further comprises agriculturally acceptable auxiliaries and/or carriers, and is prepared into agriculturally usable dosage forms.

The bactericidal composition provided by the invention is characterized in that the weight percentage of active ingredients in the composition is 1% -80%.

The bactericidal composition provided by the invention is characterized in that the weight percentage of active ingredients in the composition is 5% -60%.

The bactericidal composition can be prepared into dosage forms of missible oil, wettable powder, granules, aqueous emulsion, microemulsion, suspending agent and water dispersible granules.

In another aspect, the invention relates to a method for controlling agricultural fungal diseases by using the bactericidal composition, wherein the bactericidal composition is contacted with the agricultural pathogenic fungi.

In a further aspect, the invention relates to the use of the fungicidal composition for controlling agricultural fungal diseases, wherein the fungicidal composition is contacted with an agricultural pathogenic fungus.

Detailed Description

The two medicaments are known medicaments in the prior art, wherein the pyraclostrobin is a strobilurin bactericide developed by BASF corporation; changchuan mycin is a macrolide microbial metabolite developed by Shanghai pesticide research institute.

In a preferred embodiment of the invention, the weight ratio of pyraclostrobin to changcin is 40:1 to 8:1, preferably 20:1 to 10:1, such as 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10: 1.

In a preferred embodiment of the invention, the active ingredients of the composition only consist of pyraclostrobin and Changchun mycin. That is, the germicidal composition of the present invention preferably does not contain other active ingredients, but does not exclude other ingredients such as various adjuvants and the like, which the germicidal composition of the present invention may contain.

In a preferred embodiment of the present invention, wherein the composition further comprises agriculturally acceptable adjuvants and/or carriers, the composition is prepared into an agriculturally acceptable dosage form. The composition can be prepared into dosage forms including but not limited to missible oil, wettable powder, granules, aqueous emulsion, microemulsion, suspending agent and water dispersible granules.

In a preferred embodiment of the present invention, the content of the active ingredient in the composition is 1% to 80% by weight, preferably 5% to 60% by weight.

During the preparation of the dosage forms of the present invention, agriculturally acceptable adjuvants and/or carriers are used including, but not limited to: solvents, emulsifiers, dispersants, wetting agents, binders, disintegrants, thickeners, antifreeze agents, defoamers, stabilizers, fillers and/or carriers and the like.

Wherein the content of the first and second substances,

the solvent can be selected from: one or more of acetonitrile, dichloromethane, acetone, ethyl acetate, trichloromethane, benzene, toluene, xylene, dimethylformamide, dimethyl sulfoxide, cyclohexane, cyclohexanone, N-methylpyrrolidone, methyl glycol ether, petroleum ether, paraffin and isophorone;

the emulsifier can be selected from: one or more of lignosulfonate, oleamide sulfonate, diisopropyl naphthalene sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, phenyl phenol polyoxyethylene ether phosphate, styrene polyoxyethylene ether ammonium sulfate, magnesium alkyldiphenyl ether disulfonate, triphenyl phenol polyoxyethylene ether phosphate amine salt, polyoxyethylene fatty amide naphthalene sulfonate formaldehyde condensate, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene sorbitol fatty acid ester, sorbitan monostearate and sorbitan fatty acid ester polyoxyethylene ether;

the dispersing agent can be selected from one or more of nonylphenol polyoxyethylene ether, naphthalene sulfonic acid formaldehyde condensate, sodium salt of naphthalene sulfonic acid formaldehyde condensate, ethoxylated nonylphenol phosphate, sodium lignosulfonate, calcium lignosulfonate, sodium p-hydroxyphenyl lignosulfonate, dodecyl trimethyl ammonium salt, glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene glyceryl monofatty acid ester, sodium p-methoxyfatty acid amido benzene sulfonate, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene alkylamine;

the wetting agent can be selected from one or more of calcium dodecyl benzene sulfonate, sodium lignosulfonate, isooctyl alcohol succinate sodium sulfonate, tristyrene phenol sulfate, polyoxyethylene lauryl ether carboxylic acid sodium salt, polyoxyethylene alkyl aryl ether phosphate salt, trisiloxane polyoxyethylene ether, tristyrene phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dioctyl sulfosuccinate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dibutyl naphthalene sulfonate, dodecyl diphenyl ether sulfonate and isotridecyl sulfate;

the binder may be selected from one or more of polyvinylpyrrolidone, carboxymethylcellulose, starch, sucrose, dextrin, carboxyethylcellulose, gelatin, gum arabic, xanthan gum;

the disintegrant can be one or more selected from urea, sodium bicarbonate, sodium sulfate, calcium sulfate, magnesium chloride, ammonium sulfate and sodium chloride;

the thickener can be one or more selected from xanthan gum, gelatin, polyvinyl alcohol, magnesium aluminum silicate, hydroxymethyl cellulose, hydroxyethyl cellulose, acacia, guar gum, sodium carboxymethylcellulose, etc.;

the antifreeze can be one or more selected from glycerol, propylene glycol, ethylene glycol, polyethylene glycol or sorbitol;

the defoaming agent can be selected from one or more of polysiloxane, butyl phosphate, n-octanol, isobutyl phosphate and the like;

the stabilizer can be selected from one or more of N-soybean oil-based trimethylene diamine, triphenyl phosphite, dialkyl succinate sulfonate and butyl glycidyl ether;

the filler and/or carrier may be selected from one or more of bentonite, montmorillonite, kaolin, attapulgite, clay, talc, diatomaceous earth, montmorillonite, pumice, and the like.

Another aspect of the invention relates to a method for controlling an agricultural fungal disease by the fungicidal composition, wherein the fungicidal composition is contacted with an agricultural pathogenic fungus, for example, the fungicidal composition is applied to the locus of a crop disease, by any method known in the art, preferably by spraying. The specific application rate can be adjusted according to the disease condition of crops, such as 0.1-100 g/mu, preferably 1-50 g/mu.

Another aspect of the invention relates to the use of the fungicidal composition for the control of agricultural fungal diseases, wherein the fungicidal composition is contacted with an agricultural pathogenic fungus, e.g. the fungicidal composition is applied to the locus of a crop disease, by any method known in the art, preferably by spraying. The specific application rate can be adjusted according to the disease condition of crops, such as 0.1-100 g/mu, preferably 1-50 g/mu.

The fungicidal compositions of the present invention may be used in a variety of crops, including but not limited to: corn, rice, wheat, barley, sorghum, cotton, soybean, kidney bean, peanut, beet, rape, sunflower, sugarcane, tobacco, eggplant, tomato, potato, cucumber, pumpkin, watermelon, white gourd, cabbage, sweet potato, and the like. For controlling various fungal diseases of the above crops, it is preferably used for controlling rice sheath blight disease (Rhizoctonia solani), wheat scab (Fusarium graminearum), and potato late blight (Phytophthora infestans), more preferably used for controlling rice sheath blight (Rhizoctonia solani) and potato late blight (Phytophthora infestans).

Aiming at the general requirements of the current environment, the synergistic combination of pyraclostrobin and Changchun mycin is developed, so that the pesticide effect can be improved, the total application amount of pesticides can be reduced, the environmental pollution can be reduced, the cost can be reduced, and the development of the drug resistance of a target can be delayed.

Detailed Description

The present invention will be further described with reference to the following examples and applications, wherein the percentages given in the following examples are by weight unless otherwise specified. However, the present invention is not limited to the following examples.

(I) laboratory biological experiments

1. The fungicidal compositions of the present invention were tested for their fungicidal effects against Rhizoctonia solani (Rhizoctonia solani).

Test pathogenic fungi: rhizoctonia solani (Rhizoctonia solani);

reagent to be tested: pyraclostrobin, chanchwan mycin;

the test method comprises the following steps: the combined toxicity of the medicament is determined by a growth rate method. Preparing the medicaments into mother solution, mixing a proper amount of the mother solution according to the set proportion in the following table 1, preparing 5 concentration gradients by using 1% of Tween 80 aqueous solution, adding the mixture into PDA culture medium at the temperature of about 50 ℃, quickly shaking up the mixture, pouring the mixture into a sterilized culture dish, and cooling to form a culture medium plane with toxicity. Pure PDA medium plates were used as blank control. Each concentration was repeated 3 times. Then, 0.5cm piece of Rhizoctonia solani was inoculated into a petri dish and cultured in an incubator at 25 ℃ and a humidity of 80% for 120 hours. Then, the petri dish was taken out, the colony diameter was measured, the growth inhibition rate against pathogenic bacteria by each drug treatment was calculated by the following formula, and the EC against pathogenic bacteria by each treatment was determined₅₀。

Then, the measured EC of each treatment was measured by the Sun cloud method₅₀Conversion to Actual Toxicity Index (ATI); theoretical Toxicity Index (TTI) is calculated according to the mixture ratio of the mixture, and the co-toxicity coefficient (CTC) of the mixture is calculated according to the following formula, and the result is shown in the following table 1.

Theoretical (mix) virulence index (TTI) ═ a virulence index x a content (%) of a + B virulence index x B content (%) of B in the mix

If the co-toxicity coefficient is more than 120, the synergistic effect is shown; the co-toxicity coefficient is less than 80, which shows antagonism; the co-toxicity coefficient was between 100-120, indicating additive effect.

TABLE 1 test results of combined virulence of Pyricularia oryzae

Medicament	EC₅₀(mg/L)	ATI	TTI	Co-toxicity coefficient CTC
					Pyraclostrobin (A)	0.78	100.00	/	/
Changchuan mycin (B)	4.21	18.53	/	/
					A:B＝10:1	0.59	132.20	92.59	142.78
A:B＝12:1	0.62	125.81	93.73	134.22
					A:B＝15:1	0.49	159.18	94.91	167.72
A:B＝18:1	0.57	136.84	95.71	142.97
					A:B＝20:1	0.55	141.82	96.12	147.54

As can be seen from Table 1, the composition of pyraclostrobin and Changchun mycin has obvious synergistic effect on Pyricularia oryzae in the range of 10:1 to 20: 1.

2. The bactericidal composition of the invention is tested for its bacteriostatic effect on potato late blight (Phytophthora infestans).

The measurement method was the same as that described above for Pyricularia oryzae, and the measurement results are shown in Table 2 below.

TABLE 2 determination of potato late blight bacterium combined virulence

Medicament	EC₅₀(mg/L)	ATI	TTI	Co-toxicity coefficient CTC
					Pyraclostrobin (A)	1.05	100.00	/	/
Changchuan mycin (B)	5.33	19.70	/	/
					A:B＝10:1	0.92	114.13	92.70	123.12
A:B＝12:1	0.69	152.17	93.82	162.19
					A:B＝15:1	0.85	123.53	94.98	130.06
A:B＝18:1	0.97	108.25	95.77	113.02
					A:B＝20:1	0.71	147.89	96.18	153.77

As can be seen from Table 2, the composition of pyraclostrobin and Changchun mycin shows an obvious synergistic effect on potato late blight basically in the range of 10:1 to 20: 1.

3. The fungicidal compositions of the present invention were tested for their bacteriostatic effects against Fusarium graminearum.

TABLE 3 measurement results of combined virulence of wheat scab germ

Medicament	EC₅₀(mg/L)	ATI	TTI	Co-toxicity coefficient CTC
					Pyraclostrobin (A)	2.88	100.00	/	/
Changchuan mycin (B)	3.15	91.43	/	/
					A:B＝10:1	2.84	101.41	99.22	102.20
A:B＝12:1	2.55	112.94	99.34	113.69
					A:B＝15:1	2.69	107.06	99.46	107.64
A:B＝18:1	2.52	114.29	99.55	114.80
					A:B＝20:1	2.65	108.68	99.59	109.12

As can be seen from Table 3, the composition of pyraclostrobin and Changchun mycin has good bacteriostatic effect on wheat scab germs within the range of 10:1 to 20: 1.

(II) formulation examples

EXAMPLE 1 suspending agent

15% of pyraclostrobin, 1% of Changchuan mycin, 4% of sodium p-hydroxyphenyl lignin sulfonate, 5% of trisstyrol sulfate, 3% of xanthan gum, 4% of glycerol, 0.5% of butyl phosphate and the balance of water to 100%.

The preparation method comprises the following steps: the components are mixed with water, and a suspension system is formed after high-speed shearing dispersion and sanding by a sand mill to prepare the suspending agent.

EXAMPLE 2 suspending agent

10% of pyraclostrobin, 1% of Changchun mycin, 3% of fatty alcohol-polyoxyethylene ether phosphate, 5% of trisiloxane polyoxyethylene ether, 3% of magnesium aluminum silicate, 5% of propylene glycol, 0.5% of butyl phosphate and water, wherein the balance is up to 100%.

The preparation method is the same as that of example 1.

Example 3 aqueous emulsion

6% of pyraclostrobin, 0.5% of Changchuan mycin, 8% of dichloromethane, 3% of sodium dodecyl benzene sulfonate, 4% of fatty alcohol-polyoxyethylene ether, 5% of Arabic gum, 0.5% of n-octanol, 4% of glycerol and the balance of water to 100%. The preparation method comprises the following steps: dissolving the effective components with solvent to prepare oil phase, adding other components into water, stirring to prepare water phase, adding the oil phase into the water phase while stirring, and stirring to obtain the aqueous emulsion.

Example 4 aqueous emulsion

8% of pyraclostrobin, 0.4% of Changchuan mycin, 9% of ethyl acetate, 5% of sodium dodecyl benzene sulfonate, 5% of polyoxyethylene alkyl aryl ether, 6% of Arabic gum, 0.5% of n-octanol, 5% of polyethylene glycol and the balance of water to 100%.

The preparation method is the same as example 3.

EXAMPLE 5 wettable powder

36% of pyraclostrobin, 2% of Changchun mycin, 6% of naphthalene sulfonic acid formaldehyde condensate, 5% of polyoxyethylene lauryl ether sodium carboxylate and the balance of solid carrier to 100%. The preparation method comprises the following steps: the components are mixed, ground and crushed to prepare the wettable powder.

Example 6 Water dispersible granules

16% of pyraclostrobin, 1% of Changchuan mycin, 5% of polyoxyethylene sorbitan fatty acid ester, 7% of trisiloxane polyoxyethylene ether, 6% of sodium chloride, 4% of carboxymethyl cellulose and the balance of solid carrier to 100%. The preparation method comprises the following steps: the components are uniformly mixed, and are crushed and granulated to prepare the water dispersible granule.

(III) field test

Test agents: the preparation of the invention, examples 1-6, is a 30% pyraclostrobin emulsion in water and 1% Changchuan mycin emulsifiable concentrate

Test work: potato

Control target: late blight of potato

The treatment of the test agent, the control agent and the blank control cell adopts random block arrangement, the area of the cell is 20 square meters, the cell is repeated for 3 times, and the cultivation conditions of all the cells are consistent. The test was administered 3 times, each time 7 days apart, using a nebulizer spray. Investigation was performed 7 days after the last dose. The results are shown in Table 4 below.

Table 4 results of field test

As can be seen from the above table 4, compared with 30% pyraclostrobin emulsion in water and 1% Changchun mycin emulsifiable concentrate, the preparation of the embodiments 1-6 of the invention can obviously increase the field control effect on potato late blight and generate a synergistic effect.

The invention has been described with reference to specific embodiments. Those skilled in the art can make appropriate changes based on the contents of the present invention, and all changes that are relevant are considered to be included in the scope of the present invention when they do not depart from the contents of the present invention.

Claims

1. The bactericidal composition is characterized by comprising the following components in percentage by weight: 15% of pyraclostrobin, 1% of Changchuan mycin, 4% of sodium p-hydroxyphenyl lignin sulfonate, 5% of trisstyrol sulfate, 3% of xanthan gum, 4% of glycerol, 0.5% of butyl phosphate and the balance of water to 100%.

2. Use of the fungicidal composition according to claim 1 for controlling agricultural fungal diseases, characterized in that the fungicidal composition is brought into contact with an agricultural pathogenic fungus.