CN116058381A - Sterilization composition containing benziothiazolinone and chlorpyrifos and application thereof - Google Patents

Sterilization composition containing benziothiazolinone and chlorpyrifos and application thereof Download PDF

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CN116058381A
CN116058381A CN202310024036.2A CN202310024036A CN116058381A CN 116058381 A CN116058381 A CN 116058381A CN 202310024036 A CN202310024036 A CN 202310024036A CN 116058381 A CN116058381 A CN 116058381A
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benziothiazolinone
chlorpyrifos
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cloxaprid
bactericidal composition
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CN116058381B (en
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霍树红
王倩
李景壮
崔继程
王鹏
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Huate Western Shaanxi Science And Technology Industrial Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, 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
    • A01N43/80Biocides, 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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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Abstract

The invention discloses a sterilization composition containing benziothiazolinone and chlorpyrifos and application thereof. The mass ratio of the benziothiazolinone to the chlorpyrifos is 20:1-1:20, and the balance is auxiliary components which are allowed to be used and accepted in pesticides. The composition has obvious synergistic effect and high control efficiency, and is mainly suitable for preventing and controlling rice blast, false smut of rice, anthracnose of melon, gray mold of tomato and the like.

Description

Sterilization composition containing benziothiazolinone and chlorpyrifos and application thereof
Technical Field
The invention relates to the technical field of pesticide compounding, in particular to a sterilization composition containing benziothiazolinone and cloxaprid and application thereof.
Background
The benziothiazolinone belongs to thiazole heterocyclic compounds, is a novel efficient, low-toxicity and broad-spectrum bactericide, and has the following action mechanism: the protein and cell membrane synthesis system is destroyed by the combination of anions on the cell membrane surfaces of bacteria and fungi or the reaction of the anions and sulfhydryl groups, so that the proliferation of the bacteria and fungi is inhibited, the metabolism of pathogenic bacteria cells is interfered, the physiological disturbance is caused, and the death of the pathogenic bacteria is caused. The compound has good control effect on rot, canker, anthracnose, pear scab, leaf spot, downy mildew and other diseases on crops, and is very safe to the crops.
The chloromycetin is N-methoxy-N- [2- [ (3, 5, 6-trichloro-2-pyridyloxy) yl ] phenyl ] methyl formate, and is a strobilurin high-efficiency broad-spectrum low-toxicity bactericide. The plant extract has excellent control effects on various diseases such as wheat powdery mildew, rice blast, false smut, melon powdery mildew, anthracnose, tomato powdery mildew, gray mold, apple rust, flower powdery mildew and the like caused by ascomycetes, basidiomycetes and fungi imperfecti, and has the characteristics of higher activity, good compatibility with nonstandard organisms and environment, long duration, safety to crops, preventive and therapeutic activity and the like.
In the actual process of agricultural production, chemical agents are the most effective means for preventing and controlling crop diseases and insect pests, but the problems that the use of single agents and common agents is most easy to generate are low sterilization efficiency and gradually enhanced drug resistance. And a single chemical bactericide is used continuously in high dosage for a long time, so that a series of problems such as medicament residue, environmental pollution and the like are easily caused. The novel medicament is reasonably used and reasonably compounded, so that the bactericidal composition has the positive characteristics of expanding a bactericidal spectrum, improving a control effect, prolonging a medicament application period, reducing the medicament consumption, reducing the medicament damage, reducing residues, delaying the occurrence and development of disease medicament resistance and the like, and the compounding or mixing use of the bactericidal composition is one of the most effective methods for solving the problems, and simultaneously, the medicament application cost of farmers can be saved to a greater extent.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a reasonable compound sterilization composition which can realize synergistic effect and enlarge the sterilization spectrum of the medicament, and can improve the quick acting property and the lasting period of the medicament, so that the use of the composition by a user is safe and environment-friendly, and the medication cost can be greatly reduced.
The inventor finds that the benziothiazolinone and the chlorpyrifos have obvious synergistic effect on diseases such as rice blast, false smut of rice, anthracnose of melon, gray mold of tomato and the like in a certain compounding proportion range through multiple indoor toxicity measurement and field pesticide effect experiments, and further research and development experiments prove that the result is achieved.
Another object of the present invention is to provide a formulation of a bactericidal composition containing benziothiazolinone and chlorpyrifos, and still another object is to provide an application of the bactericidal composition containing benziothiazolinone and chlorpyrifos in controlling plant diseases, especially in controlling diseases such as rice blast, false smut, melon anthracnose and tomato gray mold.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention relates to a sterilization composition containing benziothiazolinone and chlorpyrifos, wherein the active ingredients are benziothiazolinone and chlorpyrifos, the weight ratio of the benziothiazolinone to the chlorpyrifos is 20:1-1:20, and the most preferable weight ratio is 1:5.
In the compound composition, the weight percentage of the benziothiazolinone is 1-30%, the weight percentage of the chlorpyrifos is 1-90%, and the balance is auxiliary agents which are allowed to be used and can be accepted in the pesticide science. Further, in the composition of the present invention, the sum of the weights of the benziothiazolinone and the cloxaprid is 1 to 80% by weight, preferably 1 to 65% by weight, of the composition.
The bactericidal composition can be prepared into any application dosage form suitable for agricultural production, such as suspending agents, wettable powder, water dispersible granules, aqueous emulsion, microemulsion or ultra-low volume liquid, and the like, wherein the preferable dosage form is suspending agent.
The bactericidal composition of the invention can be prepared into various application forms, besides the effective components, also comprises various auxiliary components which are allowed to be used and accepted in agriculture, including but not limited to: solvents, penetrants, dispersants, diffusers, disintegrants, emulsifiers, stabilizers, wetting agents, thickeners, defoamers, antifreeze agents, carriers or fillers, and the like.
The production processes of various application dosage forms in the compound composition of the invention belong to the prior known technology and are not described in detail herein.
The compound bactericidal composition of the benziothiazolinone and the cloxaprid is applied to preventing and controlling plant diseases, such as field crop diseases, melon and vegetable diseases and the like, and is preferably used for preventing and controlling rice blast, false smut of rice, anthracnose of melon, gray mold of tomato and the like.
Compared with the existing single preparation, the bactericidal composition containing the benziothiazolinone and the cloxaprid has the advantages of obviously improved bactericidal effect, long lasting period, safety to crops and popularization and application in agricultural production.
The invention has the following advantages:
1. the composition of the invention has good synergistic effect on the diseases within a certain proportion range, the sterilization effect of the composition is obviously higher than that of a single agent, and the co-toxicity coefficient is at least 120, so that the composition not only reduces the dosage and cost of pesticides, but also reduces pesticide residues and reduces the damage to the environment.
2. The two active ingredients in the invention have no interactive resistance with other bactericides, and the invention has the characteristics of low dosage, high activity, high permeability, strong systemic conductivity, rain wash resistance and long lasting period, is environment-friendly, is safe to bees, and accords with the expectation that plant protection products influence the safety of an ecosystem in the global market.
3. The composition has good control effects on rice blast, false smut of rice, melon anthracnose, tomato gray mold and the like, is safe and has no adverse effect, and meets the national green development requirement.
Detailed Description
The technical scheme and technical effects of the present invention are further described below with reference to specific experimental examples.
The percentages described herein are by weight and embodiments of the present invention are not limited to the ranges expressed by examples. The instruments, reagents, materials, etc. according to the following embodiments are conventional instruments, reagents, materials, etc. existing in the prior art, and are commercially available in a normal manner unless otherwise specified. The test methods, detection methods, and the like in the following embodiments are conventional test methods, detection methods, and the like that are known in the art unless otherwise specified. The active ingredients are calculated by the active ingredients. The experiment adopts a method combining indoor toxicity measurement and field test. Firstly, screening out proper proportion by indoor toxicity measurement, and then carrying out field test on the basis.
The invention will be described in further detail with reference to examples below:
1. formulation examples
Formulation example 1:20% of chlorpyrifos and 1% of benziothiazolinone, and a suspending agent.
Figure BDA0004043771230000041
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 2:15% of benziothiazolinone and 1% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000042
Figure BDA0004043771230000051
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 3:10% of benziothiazolinone and 1% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000052
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 4:10% of benziothiazolinone and 2% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000053
Figure BDA0004043771230000061
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 5:5% of benziothiazolinone and 5% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000062
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 6:2% of benziothiazolinone and 10% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000063
Figure BDA0004043771230000071
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 7:1% of benziothiazolinone and 10% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000072
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 8:1% of benziothiazolinone and 15% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000081
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
Formulation example 9:1% of benziothiazolinone and 20% of chlorpyrifos, and suspending agent.
Figure BDA0004043771230000082
Figure BDA0004043771230000091
The components are mixed in proportion, ground for a certain time or sheared at a high speed, and filtered to obtain the suspending agent.
2. Indoor bioassay Activity assay
Example 1: compound proportion screening of benziothiazolinone and chlorpyrifos for rice blast and determination of co-toxicity coefficient 1.1 test strain
Rice blast bacteria (Pyricularia oryzae ecav) were supplied by the institute of Chinese rice in Fuyang, hangzhou, zhejiang, 2021.
1.2 test Medium
AEA medium: yeast 5g, glycerin 20ml,MgSO4 0.25g,NaNO3 6g,KCl 0.5g,KH2PO4 1.5g, agar 20g, add deionized water to 1000ml.
1.3 reagents for test
95% of the chlorpyrifos, 95% of the benziothiazolinone (Jiangsu Baoling chemical Co., ltd.) and 95% of the benziothiazolinone (Shanxi Dahuat technology Co., ltd.). The raw material and 95% of the benziothiazolinone raw material are respectively prepared into mother liquor by using acetone, and the mother liquor is diluted by using sterile water containing 2% of Tween 80 when in use.
1.4 determination of indoor toxicity of Thiomolone and Chlorpyrifos for Rice blast
The test method comprises the following steps: referring to the national agricultural industry Standard NY/T1156.2-2006 of the people's republic of China, the hypha growth rate method.
Adding the prepared medicines with different proportions into AEA culture medium which is sterilized and can be cooled to 45-50 ℃, shaking uniformly, pouring into a culture dish, cooling to prepare a series of concentration gradient toxic culture medium plates, and taking a non-drug-containing culture medium as a control (sterile water containing 2% Tween 80 is used for replacing the medicines). Taking bacterial cakes with the diameter of 6mm from rice blast pathogenic bacteria for standby cultivation under the aseptic condition by using a puncher, inoculating the bacterial cakes to the center of a cooled toxic AEA culture medium plate, placing one bacterial strain on each dish, repeating the treatment for 3 times, placing the bacterial strain in an artificial incubator at 25 ℃, culturing for 9 days, taking out, and measuring the colony diameter by using a crisscross method. 3 replicates of each concentration were averaged. Then, EC of the medicaments with different proportions to pathogenic bacteria is calculated 50 The co-toxicity coefficient (CTC) of the mixture is calculated by adopting a co-toxicity coefficient method, and the synergy of the mixture is determined, wherein the specific calculation method is as follows:
taking a single agent in the mixture as a standard agent, and calculating:
measured virulence index (ATI) = (standard agent LC 50 Test efficacy LC 50 )*100
Theoretical Toxicity Index (TTI) =toxicity index of agent a the percentage of agent a in the mixture + the toxicity index of agent B the percentage of agent B in the mixture.
Co-toxicity coefficient (CTC) = [ mix actual virulence index (ATI)/mix theoretical virulence index (TTI) ]x100.
Dividing the standard according to the combined action of NY/TI1547.7-2006 pesticides; the co-toxicity coefficient (CTC) is more than or equal to 120, and the synergistic effect is shown; co-toxicity coefficient (CTC) less than or equal to 80 shows antagonism, and co-toxicity coefficient (CTC) less than 80 shows additive effect.
TABLE 1 indoor Combined toxicity determination of Thiomolone and Chlorpyrifos Complex against Rice blast
Medicament name and ratio Proportioning of EC50(mg/L) ATI TTI CTC
Benziothiazolinone (A) —— 17.42 4.36
Chlorodil (B) —— 0.76 100
A:B 20:1 6.47 11.75 8.91 131.77
A:B 15:1 4.95 15.35 10.34 148.52
A:B 10:1 3.86 19.69 13.05 150.82
A:B 5:1 2.57 29.57 20.30 145.67
A:B 1:1 0.98 77.55 52.18 148.62
A:B 1:5 0.54 140.74 84.06 167.43
A:B 1:10 0.50 152.00 91.31 166.47
A:B 1:15 0.53 143.40 94.02 152.51
A:B 1:20 0.56 135.71 95.45 142.19
As is clear from Table 1, EC of benziothiazolinone and cloxapyroxad against rice blast 50 17.42mg/L and 0.76mg/L respectively, the co-toxicity coefficient (CTC) of the benziothiazolinone and the chlorpyrifos is more than or equal to 120 when the ratio is 20:1-1:20, the synergistic effect on rice blast is excellent, especially when the ratio is 1:5, the synergistic effect is more obvious, the co-toxicity coefficient (CTC) is 167.43, and the reasonability and feasibility of the compounding of the benziothiazolinone and the chlorpyrifos are realized.
Example 2: indoor toxicity determination of benziothiazolinone and chlorpyrifos composition on rice false smut 2.1 test strain
Rice false smut (Ustilaginoidea oryzae) is preserved and cultured by Shaanxi Dahuat technology industries, inc. of Shaanxi.
2.2 test Medium
Potato sucrose solid medium (PSA) was used: 300g of potato, 20g of sucrose and 15g of agar, and adding deionized water to 1000ml.
2.3 reagents for test
95% of the chlorpyrifos, 95% of the benziothiazolinone (Jiangsu Baoling chemical Co., ltd.) and 95% of the benziothiazolinone (Shanxi Dahuat technology Co., ltd.). The raw material and 95% of the benziothiazolinone raw material are respectively prepared into mother liquor by using acetone, and the mother liquor is diluted by using sterile water containing 2% of Tween 80 when in use.
2.4 indoor toxicity determination of Thiomolone and Chlorpyrifos for Rice false smut
The test method comprises the following steps: referring to the national agricultural industry Standard NY/T1156.2-2006 of the people's republic of China, the hypha growth rate method.
Adding the prepared medicines with different proportions into a sterilized PSA culture medium which can be cooled to 45-50 ℃, shaking uniformly, pouring into a culture dish, cooling to prepare a series of concentration gradient toxic culture medium plates, and taking a non-drug-containing culture medium as a control (sterile water containing 2% Tween 80 is used for replacing the medicines). Taking bacterial cakes with the diameter of 6mm from the pathogenic bacteria of the false smut of the rice for later use under the aseptic condition, inoculating the bacterial cakes to the center of a cooled toxic PSA culture medium plate, placing one bacterial strain on each tray, repeating the treatment for 3 times, culturing the bacterial strain in an artificial incubator at 28 ℃ for 12d, and measuring the colony diameter by adopting a crisscross method. 3 replicates of each concentration were averaged. And then, calculating EC50 of the medicaments with different proportions on pathogenic bacteria, calculating a co-toxicity coefficient by adopting a co-toxicity coefficient method (the same as before), and determining the synergy of the mixed medicament.
TABLE 2 indoor Combined toxicity determination of Thiomolone and Chlorpyrifos Complex on Rice false smut
Figure BDA0004043771230000111
Figure BDA0004043771230000121
As is clear from Table 2, the EC of benziothiazolinone and chlorpyrifos against false smut of rice 50 15.68mg/L and 0.57mg/L respectively, the co-toxicity coefficient (CTC) of the buprofezin and the chlorpyrifos is more than or equal to 120 when the ratio is 20:1-1:20, the synergistic effect on the false smut of rice is excellent, the synergistic effect is more obvious particularly when the ratio is 1:5, the co-toxicity coefficient (CTC) is 154.33, and the reasonability and feasibility of the compounding of the buprofezin and the chlorpyrifos are realized.
Example 3: indoor toxicity determination of benziothiazolinone and chloropyrifos-methyl composition on melon anthracnose 3.1 test strain
Melon anthracnose (Colletorichum orbiculare) is stored and cultured by Shaanxi Dahuat technology industries, inc. of life testing laboratory.
3.2 test Medium
Potato sucrose solid medium (PSA) was used: 200g of potato, 20g of sucrose and 20g of agar, and adding deionized water to 1000ml.
3.3 test agent:
95% of the original drug of the benziothiazolinone (purchased in the conventional market) and 92% of the original drug of the chloropyrifos (purchased in the conventional market). The mother liquor is prepared from 95% of the original pesticide of the benziothiazolinone and 92% of the original pesticide of the chloropyridine fungus ester by acetone, and the mother liquor is diluted by sterile water containing 2% of Tween 80 when in use.
3.4 indoor toxicity determination of Thiomolone and Chlorodil on melon anthracnose
The test method comprises the following steps: referring to the national agricultural industry Standard NY/T1156.2-2006 of the people's republic of China, the hypha growth rate method.
Adding the prepared medicines with different proportions into a sterilized PSA culture medium which can be cooled to 45-50 ℃, shaking uniformly, pouring into a culture dish, cooling to prepare a series of concentration gradient toxic culture medium plates, and taking a non-drug-containing culture medium as a control (sterile water containing 2% Tween 80 is used for replacing the medicines). Taking bacterial cakes with the diameter of 6mm from t melon anthracnose pathogenic bacteria for later use under the aseptic condition, inoculating the bacterial cakes to the center of a cooled toxic PSA culture medium plate, repeating the treatment for 3 times, and then placing the bacterial cakes in an artificial incubator at 25 ℃ for 15 days, and measuring the colony diameter by adopting a crisscross method. 3 replicates of each concentration were averaged. And then, calculating EC50 of the medicaments with different proportions on pathogenic bacteria, calculating a co-toxicity coefficient by adopting a co-toxicity coefficient method (the same as before), and determining the synergy of the mixed medicament.
TABLE 3 indoor Combined toxicity determination of Thiomolone and Chlorpyrifos Complex on melon anthracnose
Medicament name and ratio Proportioning of EC50(mg/L) ATI TTI CTC
Benziothiazolinone (A) —— 31.28 1.98
Chlorodil (B) —— 0.62 100
A:B 20:1 7.51 8.26 6.65 124.19
A:B 15:1 5.82 10.65 8.11 131.42
A:B 10:1 4.22 14.69 10.89 134.90
A:B 5:1 2.47 25.10 18.32 137.04
A:B 1:1 0.96 64.58 50.99 126.66
A:B 1:5 0.49 126.53 83.66 151.24
A:B 1:10 0.46 134.78 91.09 147.97
A:B 1:15 0.48 129.17 93.87 137.60
A:B 1:20 0.51 121.57 95.33 127.52
From Table 3, it can be seen that the EC of benziothiazolinone and cloxapyroxad against melon anthracnose 50 31.28mg/L and 0.62mg/L respectively, the co-toxicity coefficient (CTC) of the buprofezin and the chlorpyrifos is more than or equal to 120 when the ratio is 20:1-1:20, the synergistic effect on melon anthracnose is excellent, the synergistic effect is more obvious particularly when the ratio is 1:5, the co-toxicity coefficient (CTC) is 151.24, and the reasonability and feasibility of the compounding of the buprofezin and the chlorpyrifos are realized.
Example 4: indoor toxicity determination of benziothiazolinone and chloropyrifos-methyl composition on tomato gray mold 4.1 test strain
Tomato gray mold (Botrytis cinerea) is provided by plant protection institute of the agricultural academy of sciences in Shandong province and then stored and cultured by Shanxi Dahua Tex technology laboratory of Shanxi Utility.
4.2 test Medium
Potato dextrose agar medium (PDA) was used: 200g of potato, 20g of glucose and 20g of agar, and adding deionized water to 1000ml.
4.3 reagents for test
95% of the chlorpyrifos, 95% of the benziothiazolinone (Jiangsu Baoling chemical Co., ltd.) and 95% of the benziothiazolinone (Shanxi Dahuat technology Co., ltd.). The raw material and 95% of the benziothiazolinone raw material are respectively prepared into mother liquor by using acetone, and the mother liquor is diluted by using sterile water containing 2% of Tween 80 when in use.
4.4 indoor toxicity determination of Thiomolone and Chlorpyrifos for Botrytis cinerea
The test method comprises the following steps: referring to the national agricultural industry Standard NY/T1156.2-2006 of the people's republic of China, the hypha growth rate method.
Adding the prepared medicines with different proportions into sterilized PDA culture medium which can be cooled to 45-50 ℃, shaking uniformly, pouring into a culture dish, cooling to prepare a series of concentration gradient toxic culture medium plates, and taking a non-drug-containing culture medium as a control (sterile water containing 2% Tween 80 is used for replacing the medicines). Taking bacterial cakes with the diameter of 6mm from the tomato gray mold pathogenic bacteria for standby culture under the aseptic condition, inoculating the bacterial cakes to the center of a cooled toxic PDA culture medium plate, repeating the treatment for 3 times, and culturing the bacterial cakes in an artificial incubator at 21 ℃ for 4 days, and then measuring the colony diameter by adopting a crisscross method. 3 replicates of each concentration were averaged. And then, calculating EC50 of the medicaments with different proportions on pathogenic bacteria, calculating a co-toxicity coefficient by adopting a co-toxicity coefficient method (the same as before), and determining the synergy of the mixed medicament.
Table 4 indoor Combined toxicity determination of Thiomolone and Chlorpyrifos Compound against Botrytis cinerea
Medicament name and ratio Proportioning of EC50(mg/L) ATI TTI CTC
Benziothiazolinone (A) —— 23.79 4.50
Chlorodil (B) —— 1.07 100
A:B 20:1 9.12 11.73 9.05 129.67
A:B 15:1 7.25 14.76 10.47 140.98
A:B 10:1 5.49 19.49 13.18 147.86
A:B 5:1 3.43 31.20 20.42 152.79
A:B 1:1 1.29 82.95 52.25 158.75
A:B 1:5 0.78 137.18 84.08 163.15
A:B 1:10 0.75 142.67 91.32 156.23
A:B 1:15 0.79 135.44 94.03 144.04
A:B 1:20 0.81 132.10 95.45 138.39
As can be seen from Table 4, the EC of benziothiazolinone and cloxapyroxad on tomato gray mold 50 23.79mg/L and 1.07mg/L respectively, the co-toxicity coefficient (CTC) of the benziothiazolinone and the chlorpyrifos is more than or equal to 120 when the ratio is 20:1-1:20, the benziothiazolinone and the chlorpyrifos show excellent synergistic effect on the gray mold of tomatoes, especially when the ratio is 1:5, the synergistic effect is more remarkable, the co-toxicity coefficient (CTC) is 163.15, and the reasonability and feasibility of the compounding of the benziothiazolinone and the chlorpyrifos are realized.
2. Field efficacy test
Example 1: field efficacy test of benziothiazolinone and chlorpyrifos composition preparation on rice blast
Overview of the experiment: the test field is selected from Anhui and Guangde calendar year rice blast region with 4500m 2 The cultivation management and fertilization levels are moderate, and the relative conditions are consistent. The rice variety to be tested is Xiang Liang you 68.
Test treatment: the test agent was (2+10)% of the benziothiazolinone-chloromycetin suspension of formulation example 6, the control agent was 5% of the benziothiazolinone suspension (commercially available from the Kiku technology Co., dahua in Shanxi, shanshui, inc., 20% of the chloromycetin suspension (commercially available from Jiangsu Baoling chemical Co., ltd.) and the blank control was sprayed with an equal amount of clear water, the test was conducted in a random block design, 4 treatments were applied in total, and each treatment was repeated 3 times in total, 12 cells were each 22m long, 16m wide, and an area of 350m 2 The cell is provided with 0.3m walkways, the repeat is provided with 0.5m walkways, and the periphery of the repeat is provided with protection rows. The test is carried out for 2 times, the first time is applied to the break period of rice (when 10% of rice plants in the whole field are half of leaf sheaths are pulled out), and the second time is applied for Yu Jisui time (80% of rice plants are pulled out). The specific time is, respectively, 2021, 9, 10 and 9, 17. Spraying evenly by using HD-400 manual sprayer with water consumption of 450kg/hm 2
The investigation method comprises the following steps: the control effect was investigated in the stationary phase of the disease, the specific investigation time was 2021, 10 months and 2 days (15 d after the second administration), and 1 total investigation was performed. Sampling at 5 points in each cell, investigating 25 ears (tillers) at each point, investigating 1500 ears in total, investigating the occurrence condition of the ear plague of each cell, and calculating the ear disease rate and the ear disease prevention effect. The classification criteria for rice blast are as follows:
spike blast classification (in spike):
level 0: no disease;
stage 1: less than 5% loss per ear (individual stalk onset);
3 stages: 6% -20% of loss per ear (about 1/3 of the branches are ill);
5 stages: 21% -50% of loss per ear (incidence of neck or main axis of ear, half-shrunken grain);
7 stages: loss of 51% -70% per ear (neck disease, mostly shrunken grain);
stage 9: loss of 71-100% per spike (neck disease, white spike).
The drug effect calculation method comprises the following steps: calculating according to the method of national standard pesticide field efficacy test criterion (I); calculating disease index and preventing and treating effect.
Disease index (%) =100×Σ (number of ears at each stage×representative value at each stage)/(total ears investigated×highest representative value)
Control effect (%) = (CK 1-P1)/CK 1×100
P1: disease index after treatment zone control
CK1: disease index after control in the control area;
the results are shown in Table 5:
TABLE 5 test results of the treatment agents for controlling Pyricularia oryzae
Figure BDA0004043771230000161
Figure BDA0004043771230000171
As can be seen from Table 5, (2+10)% of the suspension concentrate of the buprofezin and the chlorpyrifos had a better effect of controlling rice blast after the suspension concentrate was applied.
Example 2: field efficacy test of benziothiazolinone and chlorpyrifos composition preparation on rice false smut
Overview of the experiment: the test land is selected from Anhui-jing county, the previous stubble of the selected test paddy field is rape, the topography is flat, the soil is purple sand mud field, the cultivation is good, the organic matter content is medium, the fertility is uniform and consistent, the water retention performance is good, the drainage and irrigation are convenient, and the paddy field is a field block which is frequently developed by false smut in the past year. Test field area 3500m 2 Cultivation, water and fertilizer management, weed control and the like are consistent with local rice production. The rice variety to be tested is Y two-excellent 957, and is in the early stage of break.
Test treatment: the test agent was (2+10)% of the benziothiazolinone-cloxapride suspension of formulation example 6, the control agent was 5% of the benziothiazolinone suspension (commercially available from the Kiku-Tech Co., ltd., shanxi, dahut technology Co., ltd., jiangsu Baoling) and the blank control was clear water of the same amount sprayed, the test was conducted using a random block design, 4 treatments were staggered, and each treatment was repeated 4 times, 1 total6 cells, each cell having an area of 18-24 m 2 Ridge building is carried out among all the communities, each small ridge is covered by a plastic film, and irrigation and drainage are carried out independently, so that the influence of medicament serial irrigation on the test effect is prevented. And the conventional cultivation management is carried out, and the bactericide is not sprayed in the whole growth period of the rice. The application times are 2 times, the first application is about 10d before the break of the rice, the specific application time is 2021, 8 months and 16 days, the second application is 7d after the first application, and the time is 2021, 8 months and 23 days. Spraying uniformly with HD-400 manual sprayer with water consumption of 450kg/hm 2, And (5) uniformly spraying manually.
The investigation method comprises the following steps: the control effect was investigated at the stationary phase of the disease, the specific investigation time was 2021, 9 months and 6 days (15 d after the second administration), and 1 total investigation was performed. Sampling at 5 points in each cell, investigating 20 clusters at each point, investigating 1600 clusters altogether, investigating the number of disease ears and the number of disease grains in each cell, and calculating the disease ear rate and the disease ear prevention and treatment effect. The classification standard of the false smut of rice is as follows:
level 0: the method comprises the steps of carrying out a first treatment on the surface of the The disease spike rate is less than 1 percent, and the resistance (HR) is high;
stage 1: the disease spike rate is 0.1-3.0%, and the resistance (R);
3 stages: the disease spike rate is 3.1-7.0%, and the Medium Resistance (MR);
5 stages: the disease spike rate is 7.1-15.0%, and the sense of middle-jiao (MS);
7 stages: the ear disease rate is 15.1-25.0%, sense (S);
stage 9: the disease spike rate is more than or equal to 25.1 percent, and the sense of High (HS) is high.
Then, the disease index and the prevention and treatment effect of each treatment are calculated, and the calculation method is the same as the previous method.
The results are shown in Table 6:
table 6 test results of treatment agents for controlling false smut of Rice
Figure BDA0004043771230000181
As can be seen from Table 6, the (2+10)% of the suspension concentrate has better control effect on false smut of rice after being applied.
Example 3: field efficacy test of benziothiazolinone and chloropyrifos composition preparation on melon anthracnose
Overview of the experiment: the test field is selected from sunlight greenhouse of Shandong Shouguang Tian Mazhen, and the area of test field is 1500m 2 Sandy soil with pH of 6.5 has rich organic matter content, is fertile and has good ventilation. "Jingtian 208" was planted 25 days 2 months 2021, and watered 6 times during the test. The cultivation conditions and management measures of all the cells are uniform, and the growth vigor of the melons is basically uniform.
Test treatment: the test agent was a (2+10)% of the buprofezin and chlorpyrifos suspension of formulation example 6, the control agent was a 5% of the buprofezin suspension (commercially available from the company of the technology and technology, inc. of the large, shanxi, and Walter, inc.), and the blank was a clear water spray of the same amount. The test adopts a random block design, 4 treatments are arranged in a staggered way, each treatment is repeated 4 times, 16 cells are arranged in total, and the area of each cell is 72m 2 The rated spraying dosage per cell is 5kg. The first spraying of the melon anthracnose in the early onset stage of the melon anthracnose in 5 months of 2021, wherein the average number of the melon leaves is 15 during the application; spraying for the second time in 2021, 5 and 24 days; the third spraying is performed on 31 days 5 months 2021, the medicine is sprayed three times in the experiment, and the medicine machine is a compression sprayer and is sprayed evenly manually.
The investigation method comprises the following steps: the control effect was investigated in the stationary phase of the disease, the specific investigation time was 2021, 6, 7 days (7 d after the third administration), 1 total time. During investigation, 5 samples are taken from each cell, 10 vines are investigated from each cell, 5 leaves are investigated from each vine (i.e. 5 th to 9 th leaves counted from the top of the vine), 50 leaves are investigated from each cell, and 250 leaves are investigated from each cell. And counting the ratio of the area of each leaf spot to be investigated, and carrying out grading record according to the damage degree and the disease condition so as to calculate the disease index and the prevention and treatment effect of the medicament. The grading criteria are as follows:
level 0: no disease spots;
stage 1: the area of the disease spots accounts for less than 5% of the whole leaf area;
3 stages: the area of the lesion accounts for 6-10% of the whole leaf area;
5 stages: the area of the lesion accounts for 11% -25% of the whole leaf area;
7 stages: the area of the lesion accounts for 25% -50% of the whole leaf area;
stage 9: the area of the disease spots accounts for more than 50% of the whole leaf area.
Then, the disease index and the prevention and treatment effect of each treatment are calculated, and the calculation method is the same as the previous method.
The results are shown in Table 7:
TABLE 7 test results of the control of melon anthracnose by the treatment agents
Figure BDA0004043771230000191
As can be seen from Table 7, (2+10)% of the suspension concentrate of the buprofezin and the chlorpyrifos has better control effect on melon anthracnose after being applied.
Example 4: field efficacy test of benziothiazolinone and cloxaprid composite preparation on tomato gray mold
Overview of the experiment: the test land is selected from Shandong and chat, is an old vegetable area, has flat topography and rich soil, is a alluvial loam with partial viscosity, and has gray mold in the past year in the test area. High-furrow plastic film mulching cultivation is adopted, double rows are adopted in each furrow, the density is 4000 plants/667 m < 2 >, and '02, jin Di and 688' red-fruit tomatoes are planted in the late 2 months. The specification length x width x height of the greenhouse is 42.0m x 7.8m x 3.2m, and the greenhouse is covered for warming about 10 days before field planting. The test period was watered 5 times. The cultivation conditions and management measures of all the cells are uniform and consistent, and the local production habit is followed.
Test treatment: the test agent was (2+10)% of the benziothiazolinone-chloromycetin suspension of formulation example 6, the control agent was 5% of the benziothiazolinone suspension (commercially available from the company of the technology and technology, inc. of Dahua Tex, shanxi, and the blank control was clear water of the same amount sprayed, the test was a random block design, 4 treatments were performed in total, and the treatment was repeated 3 times in total, 12 cells were each with a cell area of 50m 2 The rated spraying dosage per cell is 3kg. The early stage of the occurrence of gray mold of tomato in 2021, 4 and 15 days is the flowering period of tomato. After 7 days (2)021, 4 th and 22 th), 2021, 4 th and 29 th, the experiment was performed three times with a 15L (HD-400) knapsack sprayer as a drug.
The investigation method comprises the following steps: the control effect was investigated at the stationary phase of the disease, the specific investigation time was 2021, 5 months, 6 days (7 d after the third administration), 1 total time. Five-point sampling is adopted in each district, all fruits of 5 plants are investigated at each point, and grading record is carried out according to the degree of harm and the condition of symptoms by taking single fruits as a unit, so that the disease index and the prevention and treatment effect of the medicament are calculated.
Level 0: no disease spots;
stage 1: residual petals or stigmas;
3 stages: sepal rot or stigma disease spreads to the fruit umbilical region;
5 stages: the navel part is provided with a macula-infiltrating mildew-free layer;
7 stages: the umbilicus has a mould layer but does not spread to other parts;
stage 9: the mold layer spreads to other parts of the fruit.
Then, the disease index and the prevention and treatment effect of each treatment are calculated, and the calculation method is the same as the previous method.
The results are shown in Table 8:
table 8 test results of treatment agents for controlling Botrytis cinerea
Figure BDA0004043771230000211
As can be seen from Table 8, (2+10)% of the suspension concentrate of the buprofezin and the chlorpyrifos has better control effect on the gray mold of the tomato after the suspension concentrate is applied.
The synergistic composition containing the buprofezin and the cloxaprid can be prepared into any dosage form suitable for agriculture by a known method, the suspension is preferably selected through experiments, and the synergistic composition has obvious synergistic effects on rice blast, false smut of rice, melon anthracnose and tomato gray mold when the ratio of the buprofezin to the cloxaprid is 20:1-1:20, especially when the composition contains the buprofezin: when the ratio of the chlorpyrifos to the chlorpyrifos is equal to 1:5, the control effect on the four diseases is optimal, and the synergistic effect is obvious.
With respect to the above ideal embodiment according to the present invention as a case, by the description of the above case, the related person can make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims, and more suitable dosage forms and optimal formulations should be selected.

Claims (9)

1. A bactericidal composition containing benziothiazolinone and cloxaprid, which is characterized in that: the active ingredients contained in the composition are benziothiazolinone and chlorpyrifos, wherein the weight ratio of the benziothiazolinone to the chlorpyrifos is 20:1-1:20.
2. The bactericidal composition containing benziothiazolinone and cloxaprid as set forth in claim 1, wherein: the bactericidal composition comprises the following components in percentage by weight: 1-30% of benziothiazolinone, 1-90% of chlorpyrifos and the balance of auxiliary agents which are allowed to be used and can be accepted in the pesticide science.
3. The bactericidal composition containing benziothiazolinone and cloxaprid as set forth in claim 2, wherein: the sum of the weights of the benziothiazolinone and the chlorpyrifos is 1-80% of the weight of the composition.
4. A composition comprising a benziothiazolinone and a cloxaprid according to claim 3, characterized in that: the sum of the weights of the benziothiazolinone and the cloxaprid is preferably 1-65% by weight of the composition.
5. The bactericidal composition containing benziothiazolinone and cloxaprid as set forth in claim 2, wherein: the auxiliary agents which are allowed to be used and can be accepted in the agrology are selected from solvents, penetrating agents, dispersing agents, disintegrating agents, emulsifying agents, stabilizing agents, wetting agents, thickening agents, antifoaming agents and antifreezing agents.
6. The bactericidal composition containing benziothiazolinone and cloxaprid as set forth in claim 2, wherein: the bactericidal composition can be prepared into any dosage form suitable for agricultural production, such as suspending agents, wettable powder, water dispersible granules, aqueous emulsion, microemulsion or ultra-low volume liquid and the like.
7. The bactericidal composition containing benziothiazolinone and cloxaprid as set forth in claim 4, wherein: the bactericidal composition is preferably prepared into a suspending agent.
8. Use of the fungicidal composition as claimed in any one of claims 1 to 7 for controlling plant diseases.
9. The use according to claim 8, characterized in that: the plant diseases comprise rice blast, false smut of rice, melon anthracnose and tomato gray mold.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102172240A (en) * 2011-03-01 2011-09-07 陕西西大华特科技实业有限公司 Bactericidal composition containing benziothiazolinone and methoxyl acrylic ester type bactericides
CN107771827A (en) * 2016-08-31 2018-03-09 海利尔药业集团股份有限公司 A kind of bactericidal composition containing benziothiazolinone and fluoxastrobin
CN109303060A (en) * 2018-12-06 2019-02-05 陕西西大华特科技实业有限公司 A kind of combination germicide and application containing benziothiazolinone and pyraoxystrobin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102172240A (en) * 2011-03-01 2011-09-07 陕西西大华特科技实业有限公司 Bactericidal composition containing benziothiazolinone and methoxyl acrylic ester type bactericides
CN107771827A (en) * 2016-08-31 2018-03-09 海利尔药业集团股份有限公司 A kind of bactericidal composition containing benziothiazolinone and fluoxastrobin
CN109303060A (en) * 2018-12-06 2019-02-05 陕西西大华特科技实业有限公司 A kind of combination germicide and application containing benziothiazolinone and pyraoxystrobin

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