A bactericidal composition containing bronopol

Through the combination of bronitol and plant extracts such as carvacrol and eugenol, a synergistic bactericidal composition is formed, which solves the problem of poor prevention and control of crop bacterial diseases in the prior art, and achieves the effect of efficient, low toxicity and low residue pesticide use.

CN116267928BActive Publication Date: 2025-04-08ZHEJIANG HISUN CHEM CO LTD
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Patent Information

Application Number
CN202211101480.1
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2022-09-09
Publication Date
2025-04-08
Estimated Expiration
2042-09-09

AI Technical Summary

Technical Problem

The prior art has failed to effectively solve the prevention and control of bacterial diseases in crops, and the long-term use of the same variety of bacterial agents has led to the improvement of pathogenic bacteria resistance.

Method used

Bromnol is combined with one of carvacrol, eugenol, styrene, resveratrol, 8-hydroxyquinoline or dichlorophenol to form a bactericidal composition. Through synergistic effects within a specific proportion range, the prevention and treatment effect of crop bacterial diseases is significantly improved.

Benefits of technology

This bactericidal composition not only has good effect on preventing and treating bacterial diseases in crops, but also can delay the generation of bacterial resistance, reduce the use of pesticides, reduce the cost of use and reduce environmental pollution.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention discloses a bactericidal composition containing bronopol, and a preparation method and application scheme thereof. The composition comprises a common adjuvant, bronopol and an active ingredient A, wherein the active ingredient A is selected from any one of carvacrol, eugenol, phenoxyproline, resveratrol, 8-hydroxyquinoline and dichlorophen, the weight ratio of bronopol to the active ingredient A is 599:1-1:40, and the weight percentage of the total weight of bronopol and the active ingredient A in the bactericidal composition is 1%-70%; the composition of the invention has high activity against a series of bacterial diseases on most crops, and has a significant synergistic effect, the invention is superior to a single agent in terms of quick-acting and lasting effect, and reduces the dosage of pesticides, reduces the cost of medication, and is beneficial to environmental protection and the comprehensive control of agricultural diseases.
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Description

Technical Field

[0001] The invention relates to a pesticide sterilization composition and its application field, in particular to a sterilization composition containing bronopol, which is used for preventing and controlling bacterial diseases of crops. Background Art

[0002] Bronopol (Chemical and Chemical Engineering Dictionary. Beijing: Chemical Industry Press, 2003), also known as Bronopol; English name: Bronopol; Chemical name: 2-bromo-2-nitro-1,3-propanediol; Molecular formula: C 3 H 6 BrNO 4 ; Relative molecular weight 199.9. Bronopol is a highly effective broad-spectrum fungicide, used to control bacterial soft rot of lotus, Pythium stem rot of ginger and white rot of konjac.

[0003] Carvacrol (Chemical and Chemical Engineering Dictionary. Beijing: Chemical Industry Press, 2003), English name: carvacrol; Chemical name: 2-methyl-5-isopropylphenol, Molecular formula: C 10 H 14 O; relative molecular weight: 150.22. Carvacrol is a plant extract. Studies have shown that this substance has antibacterial, bactericidal, and anti-tumor activities (Current Pharmaceutical Design, 2008, 14 (29): 3106-3119.).

[0004] Eugenol (Advances in Botanical Research, 2012), English name: Eugenol, chemical name: 1-allyl-3-methoxy-4-hydroxybenzene, molecular formula: C 10 H 12 O 2 , relative molecular weight: 164.1. Eugenol is a broad-spectrum fungicide that can quickly treat fungal and bacterial diseases of various crops and fruits, such as Botrytis cinerea, Fusarium, and Phytophthora.

[0005] Isobavachalcone [Biol Pharm Bull.2007.30(10)], CAS No.: 20784-50-3, English name: Isobavachalcone, molecular formula: C 20 H 20 O 4 , relative molecular weight: 324.37. Benthiocarb is a new type of botanical fungicide, which has different degrees of killing or inhibiting the growth and reproduction of pathogens that harm crops such as cucumber target spot disease, cucumber bacterial angular spot disease, and apple rot.

[0006] Resveratrol [Dose Response.2010,8(4)], English name: Resveratrol, molecular formula: C 14 H 12 O 3 , relative molecular weight: 228.25. Resveratrol is a plant antitoxin, which has antioxidant, anti-inflammatory, anti-cancer and cholesterol-lowering effects in medicine; in the field of pesticide application, studies have found that it has inhibitory activity against Ralstonia solanacearum and walnut bacterial black spot pathogens.

[0007] 8-Hydroxyquinoline [PLoS One.2010,5(9)], English name: 8-Hydroxyquinoline, molecular formula: C 9 H 7 NO, relative molecular weight: 145.16.

[0008] Dichlorophen (Chemicals & Chemistry. 2018), English name: Dichlorophen, chemical name: 2,2-dihydroxy-5,5-dichlorobiphenylmethane, molecular formula: C 13 H 10 Cl 2 O 2 , relative molecular weight: 269.12. Bichlorophene has a wide range of biological activities and is a compound that can expel tapeworms and resist microorganisms. It can be used as a fungicide in agriculture, medicine, and soap making.

[0009] Patent CN114766483A reported that a combination of bronopol and fluopicolide, pyraclostrobin or fluopicolide has a good control effect on Fusarium graminearum and Fusarium moniliforme. Patent CN110150332B reported that a combination of carvacrol and wild chrysanthemum essential oil has a good control effect on tobacco bacterial wilt and black shank. Patent CN104472484B reported that a combination of eugenol and propanamidine has a good control effect on crop diseases caused by pathogenic fungi. Patent CN101971812B reported that a combination of eugenol and a methoxyacrylate fungicide can control diseases such as gray mold, downy mildew, anthracnose, etc. and is safe for crops. Patent CN112772680A reported that a combination of fluopicolide and psoralea corylifolia seed extract has a good control effect on plant fungi, a long lasting effect and is safe for crops. Patent CN0506788A reports that a compound preparation of resveratrol and pyraclostrobin is used in the postharvest preservation of bananas, pitaya, citrus and other fruits, which is safe for fruits and has a good preservation effect. The above reports are all about the preventive effect on specific crops or diseases under specific active ingredients, and the effects are different. So far, there is no report on the combination of bronopol and one of carvacrol, eugenol, phenoxytocin, resveratrol, 8-hydroxyquinoline and dichlorophenol for the prevention and treatment of bacterial diseases.

[0010] Agricultural bacterial diseases refer to diseases caused by bacterial pathogens, such as bacterial leaf streak, canker, bacterial wilt, etc. Bacterial diseases are important diseases that affect agricultural production in my country. The inventor takes cucumber bacterial angular leaf spot as an example to illustrate the application advantages of the present invention in cucumber bacterial diseases.

[0011] Bacterial angular leaf spot of cucumber is a bacterial disease caused by Pseudomonas syringae pv. cucumber. The disease can occur in both cucumber seedlings and adult plants, mainly harming leaves, petioles, tendrils and fruits. Under suitable conditions, it can cause leaf dryness and fruit rot. In severe cases, it can cause a loss of more than 50% in cucumber yield.

[0012] Long-term use of the same type of fungicide will lead to increased resistance of pathogens, reduced effectiveness of the fungicide against diseases, and the development of new fungicides is expensive and time-consuming. In contrast, the development and research of high-efficiency, low-toxic, low-residue compound or mixed products has the characteristics of low investment, short development cycle, and slow growth of resistance, and has attracted the attention of domestic and foreign companies.

[0013] The inventors have conducted in-depth research on the compounding of bronopol with carvacrol, eugenol, phenoxyproline, resveratrol, 8-hydroxyquinoline and dichlorophen on the basis of a large number of indoor toxicity, preparation dosage forms and field efficacy tests, and found that the compounding of bronopol with one of carvacrol, eugenol, phenoxyproline, resveratrol, 8-hydroxyquinoline and dichlorophen has a significant synergistic effect within a certain proportion range, which not only has a good control effect on bacterial diseases of crops, but also is safe for agricultural products. After further research, the present invention has been completed. Summary of the invention

[0014] The object of the present invention is to provide a fungicide composition having a significant synergistic control effect on crop diseases.

[0015] The purpose of the present invention is to apply the bactericidal composition to crop bacterial diseases.

[0016] The object of the present invention is to provide a more efficient bacterial disease control solution.

[0017] The present invention is achieved through the following technical solutions:

[0018] The present invention provides a bactericidal composition containing bronopol, comprising bronopol and an active ingredient A, wherein the active ingredient A is selected from one of carvacrol, eugenol, phenoxyproline, resveratrol, 8-hydroxyquinoline and dichlorophen. The weight ratio of the bronopol to the active ingredient A is 599:1-1:40, and the weight percentage of the total weight of the bronopol and the active ingredient A in the bactericidal composition is 1%-70%.

[0019] The bactericidal composition of the present invention can be formulated into wettable powders, soluble powders, water-dispersible granules, soluble granules, aqueous emulsions, microemulsions, emulsifiable concentrates, suspensions, dispersible oil suspensions, microcapsule suspensions, soluble solutions, suspoemulsions, suspension-microcapsule suspensions, aqueous emulsions-microcapsule suspensions and other application forms suitable for agricultural use according to actual needs.

[0020] The fungicidal composition of the present invention also contains common adjuvants required for preparing pesticide preparations. Common adjuvants are one or a mixture of several of solvents, emulsifiers, wetting agents, stabilizers, dispersants, thickeners, pH regulators, defoamers, antifreeze agents, fillers, etc., all of which are known substances and are various adjuvants commonly used in pesticide preparations. They may vary according to different situations and are not particularly limited.

[0021] The fungicide composition of the present invention can be used to prevent and control crop diseases, and the crops are selected from food crops, cash crops and fruits and vegetables. Food crops include corn, rice and wheat, etc., cash crops include peanuts, cotton, beets, tea and medicinal materials, etc., and fruits and vegetables include citrus, apples, grapefruit, pears, walnuts, mangoes, eggplants, peppers, cabbages and ginger, etc.

[0022] The bactericidal composition provided by the present invention can be used for preventing and controlling bacterial diseases of crops, and the bacterial diseases are rice bacterial leaf streak, corn stalk rot, potato bacterial wilt, citrus canker, walnut black spot, pepper leaf spot and the like.

[0023] The bactericidal composition provided by the present invention is usually used by spraying, and other application techniques used in agriculture can also be used as needed.

[0024] Compared with the prior art, the advantages of the present invention are:

[0025] 1. The combination of bronopol and one of carvacrol, eugenol, phenoxyproline, resveratrol, 8-hydroxyquinoline or dichlorophen has an unexpected synergistic effect, which improves the control effect of pathogens compared with the use of a single agent alone;

[0026] 2. The mechanism of action of bronopol and one of carvacrol, eugenol, phenacyl pyraclostrobin, resveratrol, 8-hydroxyquinoline or dichlorophen is different from each other. Mixing them can delay the development of drug resistance in bacteria.

[0027] 3. The combination of bronopol and one or two active ingredients of carvacrol, eugenol, phenoxyethanol, resveratrol, 8-hydroxyquinoline or dichlorophenol reduces the amount of pesticide used, reduces the cost of use and alleviates pollution to the environment. DETAILED DESCRIPTION

[0028] In order to better understand the essence of the present invention, the content of the present invention is further described below in conjunction with the examples, but it cannot be regarded as limiting the present invention. The content mentioned in the examples is not limiting the present invention. The material formula selection can be adapted to local conditions and has no substantial effect on the results. In these examples, unless otherwise specified, all percentages are weight percentages.

[0029] Toxicity verification test example: The test was conducted with reference to the agricultural industry standard of the People's Republic of China NY / T 1156.16-2008 "Turbidimetric method for testing the inhibition of bacterial growth by fungicides":

[0030] 1. Experimental purpose: Indoor toxicity screening of different compound combinations against bacterial pathogens;

[0031] 2. Experimental conditions

[0032] 2.1. Test target: Pseudomonas syringae pv.

[0033] 2.2. Culture conditions: LB liquid medium, temperature 28.0-30.0℃;

[0034] 2.3. Experimental instruments: electronic balance, oscillating incubator, culture dish, conical flask, pipette, applicator, constant temperature incubator;

[0035] 3. Test methods

[0036] 3.1. Prepare the mother solution and adjust the treatment concentration according to each treatment for standby use;

[0037] 3.2. According to the experimental design, 3.00 mL of drug solution was taken from low concentration to high concentration and added to 27.0 mL of LB liquid culture medium, with 3 replicates for each treatment; and the final concentration of each treatment was the required concentration;

[0038] 3.3. Take 100.0 μL of the activated fresh bacterial solution and add it to the LB liquid culture medium;

[0039] 3.4. Before starting the culture, take 3.00 mL from one of the replicates in each treatment and measure its OD 600 Values ​​were used as drug controls for each treatment;

[0040] 3.5. Place in 28.0℃ constant temperature shaking (180rpm) and culture for 24h.

[0041] 4. Experimental investigation and calculation method:

[0042] The turbidity of each treatment was measured before the start of cultivation. When the control treatment reached the logarithmic growth phase, the turbidity of each treatment was measured and recorded.

[0043]

[0044]

[0045] TTI=TI A ×P A +TI B ×P B

[0046]

[0047] ATI: Actual Toxicity Index of Mixture:

[0048] S: EC of standard fungicide 50 :

[0049] M: EC of the mixture 50 :

[0050] TTI: Theoretical Toxicity Index of Mixture:

[0051] TI A :A drug toxicity index:

[0052] P A :The percentage of A agent in the mixture:

[0053] TI B :B Agent Toxicity Index:

[0054] P B :The percentage of B agent in the mixture:

[0055] CTC: Co-toxicity coefficient.

[0056] The theoretical toxicity index of the mixture is equal to the sum of the toxicity indices of each single agent and the product of their contents in the mixture. A co-toxicity coefficient greater than 120 indicates a synergistic effect, a co-toxicity coefficient greater than or equal to 80 and less than or equal to 120 indicates an additive effect, and a co-toxicity coefficient less than 80 indicates an antagonistic effect.

[0057] Indoor Activity Assay Example 1: Bronopol and Carvacrol

[0058] According to the verification of a large number of mixing tests by the inventor, 5 classic combinations of 99:1, 59:1, 39:1, 9:1 and 1:9 were taken for toxicity testing and reported. After preliminary testing, the test dosage design is shown in Table 1:

[0059] Table 1 Experimental dosage design of bronopol and carvacrol

[0060]

[0061]

[0062] Toxicity test The turbidity test was carried out at the doses shown in Table 1, and the OD of each plot was counted. 600 The growth inhibition rate of each plot was obtained by data analysis. The growth inhibition rate of bronopol and eugenol was analyzed to infer the toxicity baseline and EC of bronopol and eugenol. 50 The values ​​are shown in Table 2:

[0063] Table 2 Indoor toxicity test of bronopol and carvacrol against the pathogens of cucumber bacterial angular leaf spot

[0064]

[0065] As shown in Table 2, bronopol and carvacrol have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot, among which bronopol has an antibacterial activity of EC 50 The EC value of carvacrol against the pathogenic bacteria of cucumber bacterial angular leaf spot was 23.97 mg / L. 50 It is 34.61mg / L.

[0066] The turbidity test was carried out using the dosages shown in Table 1 to obtain the growth inhibition rates of the five ratios of bronopol and carvacrol on the pathogenic bacteria of cucumber bacterial angular leaf spot. The toxicity baseline and EC of each ratio were analyzed and inferred. 50 The value results are shown in Table 3:

[0067] Table 3 Toxicity determination of five compound ratios of bronopol and carvacrol against bacterial angular leaf spot of cucumber

[0068]

[0069] As shown in Table 3, the compound agents of bronopol and carvacrol had significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot. 50 The activity is between 16.42-30.63 mg / L, and the ratio of 39:1 is the best.

[0070] From Table 3, the EC of each group of compound preparations 50 The combined effects of 5 compound ratios of bronopol and carvacrol on the pathogenic bacteria of cucumber bacterial angular leaf spot were analyzed and evaluated as shown in Table 4:

[0071] Table 4 Evaluation of the combined effects of five compound ratios of bronopol and carvacrol on the pathogens of cucumber bacterial angular leaf spot

[0072]

[0073] As shown in Table 4, the co-toxicity coefficients of the five ratios of bronopol and carvacrol were between 99.27 and 147.11. Different ratios had different combined effects on the pathogenic bacteria of cucumber bacterial angular leaf spot. Among them, the most significant synergistic effect value of 39:1 for bronopol: carvacrol was 147.11.

[0074] The above tests on the mixture of bronopol and carvacrol showed that the two had significant synergistic effects, and their combined use could delay drug resistance of cucumber bacterial angular leaf spot and improve prevention effectiveness.

[0075] Indoor Activity Assay Example 2: Bronopol and Eugenol

[0076] According to the verification of a large number of mixing tests by the inventor, 5 classic combinations of 99:1, 59:1, 39:1, 9:1 and 1:19 were taken for toxicity testing and reported. After preliminary testing, the test dosage design is shown in Table 5:

[0077] Table 5 Design of experimental dosage of bronopol and eugenol

[0078]

[0079] Toxicity test The turbidity test was carried out at the doses shown in Table 5, and the OD of each plot was counted. 600 The growth inhibition rate of each plot was obtained by data analysis. The growth inhibition rate of bronopol and eugenol was analyzed to infer the toxicity baseline and EC of bronopol and eugenol. 50 The values ​​are shown in Table 6:

[0080] Table 6 Indoor toxicity test of bronopol and eugenol against cucumber bacterial angular leaf spot pathogens

[0081]

[0082] As shown in Table 6, bronopol and eugenol have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot, among which bronopol has an antibacterial activity EC 50 The EC value of eugenol against the pathogenic bacteria of cucumber bacterial angular leaf spot was 23.09 mg / L. 50 It is 35.03mg / L.

[0083] The turbidity test was carried out by using the dosages shown in Table 5 to obtain the growth inhibition rates of the five ratios of bronopol and eugenol on the pathogenic bacteria of cucumber bacterial angular leaf spot. The toxicity baseline and EC of each ratio were analyzed and inferred. 50 The value results are shown in Table 7:

[0084] Table 7 Toxicity test of 5 compound ratios of bronopol and eugenol against bacterial angular leaf spot of cucumber

[0085]

[0086] As shown in Table 7, the compound preparations of bronopol and eugenol have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot. 50 The activity is between 18.62-34.62 mg / L, and the ratio of 39:1 is the best.

[0087] From Table 7, the EC of each group of compound preparations 50 The combined effects of 5 compound ratios of bronopol and eugenol on the pathogenic bacteria of cucumber bacterial angular leaf spot were analyzed and evaluated as shown in Table 8:

[0088] Table 8 Evaluation of the combined effects of bronopol and eugenol in five compound ratios on the pathogens of cucumber bacterial angular leaf spot

[0089]

[0090]

[0091] It can be seen from Table 8 that the co-toxicity coefficients of the five ratios are between 81.01 and 125.07. Different ratios have different combined action modes on the pathogenic bacteria of cucumber bacterial angular leaf spot. Among them, the most significant synergistic effect of the bronopol: eugenol ratio of 39:1 is 125.07.

[0092] The above tests on the mixture of bronopol and eugenol showed that the two had significant synergistic effects, and their combined use could delay the drug resistance of cucumber bacterial angular leaf spot and improve the prevention effect.

[0093] Indoor Activity Assay Example 3: Bronopol and Propylene Glycol

[0094] According to the verification of a large number of mixing tests by the inventor, 5 classic combinations of 599:1, 499:1, 399:1, 299:1 and 199:1 were taken for toxicity testing and reported. After preliminary testing, the test dosage design is shown in Table 9:

[0095] Table 9 Design of dosage for bronopol and fenpropimorph test

[0096]

[0097] Toxicity test The turbidity test was carried out at the doses shown in Table 9, and the OD of each plot was counted. 600 The growth inhibition rate of each plot was obtained by data analysis. The growth inhibition rate of bronopol and fenpropicyclopyralid was analyzed to infer the toxicity baseline and EC of bronopol and fenpropicyclopyralid. 50 The values ​​are shown in Table 10:

[0098] Table 10 Indoor toxicity determination of bronopol and phenylpropenil against the pathogenic bacteria of cucumber bacterial angular leaf spot

[0099]

[0100] As shown in Table 10, bronopol and phenacylpyridinone have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot, among which bronopol has an antibacterial activity EC 50 The EC value of phenylpropenamide against the pathogenic bacteria of cucumber bacterial angular leaf spot was 33.27 mg / L. 50 It is 47.33mg / L.

[0101] The turbidity test was carried out by using the dosages shown in Table 9 to obtain the growth inhibition rates of the five ratios of bronopol and phenylpropenazole on the pathogenic bacteria of cucumber bacterial angular leaf spot. The toxicity baseline and EC of each ratio were analyzed and inferred. 50 The value results are shown in Table 11:

[0102] Table 11 Toxicity test of 5 compound ratios of bronopol and fenpropimorph against bacterial angular leaf spot of cucumber

[0103]

[0104] As shown in Table 11, the compound agents of bronopol and phenoxyprofen have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot. 50 The activity is between 24.05-40.41 mg / L, among which the ratio of 399:1 has the best activity.

[0105] From Table 11, the EC of each group of compound preparations 50 The combined effects of 5 compound ratios of bronopol and phenylpropenamide on the pathogenic bacteria of cucumber bacterial angular leaf spot were evaluated by analyzing the value data as shown in Table 12:

[0106] Table 12 Evaluation of the combined effects of 5 compound ratios of bronopol and fenpropimorph on the pathogens of cucumber bacterial angular leaf spot

[0107]

[0108]

[0109] As shown in Table 12, the co-toxicity coefficients of the five ratios of bronopol and fenpropicyclopyralid ranged from 82.45 to 138.44. Different ratios had different combined effects on the pathogenic bacteria of cucumber bacterial angular leaf spot. Among them, the synergistic effect of the ratio of bronopol:fenpropicyclopyralid of 399:1 was the most significant, and the co-toxicity index was 138.44.

[0110] The above tests on the mixture of bronopol and phenoxyacetin showed that the two had significant synergistic effects, and their combined use could delay the drug resistance of cucumber bacterial angular leaf spot and improve the prevention effect.

[0111] Indoor Activity Assay Example 4: Bronopol and Veratridine

[0112] According to the verification of a large number of mixing tests by the inventor, 5 classic combinations of 99:1, 59:1, 39:1, 9:1 and 1:1 were taken for toxicity testing and reported. After preliminary testing, the test dosage design is shown in Table 13:

[0113] Table 13 Bronopol and Veratrum alkaloid test dosage design

[0114]

[0115] Toxicity test The turbidity test was carried out at the doses shown in Table 13, and the OD of each plot was counted. 600 The growth inhibition rate of each plot was obtained by data analysis. The growth inhibition rate of bronopol and narvatrine was analyzed to infer the toxicity baseline and EC of bronopol and narvatrine. 50 The values ​​are shown in Table 14:

[0116] Table 14 Indoor toxicity test of bronopol and veratridine against cucumber bacterial angular leaf spot pathogens

[0117]

[0118] As shown in Table 14, bronopol and chloranthine have significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot, among which bronopol has an antibacterial activity EC 50 The EC value of veratrine against the pathogenic bacteria of cucumber bacterial angular leaf spot was 21.67 mg / L. 50 It is 47.57mg / L.

[0119] The turbidity test was performed using the dosages shown in Table 13 to obtain the growth inhibition rates of the five ratios of bronopol and veratrine on the pathogenic bacteria of cucumber bacterial angular leaf spot. The toxicity baseline and EC of each ratio were analyzed and inferred. 50 The value results are shown in Table 15:

[0120] Table 15 Toxicity determination of 5 compound ratios of bronopol and veratridine against bacterial angular leaf spot of cucumber

[0121]

[0122] As shown in Table 15, the compound preparations of bronopol and veratrine had significant antibacterial activity against the pathogenic bacteria of cucumber bacterial angular leaf spot. 50 The activity is between 10.99-30.41 mg / L, and the ratio of 39:1 is the best.

[0123] From Table 15, the EC of each group of compound preparations 50The combined effect evaluation of 5 compound ratios of bronopol and veratrine on the pathogenic bacteria of cucumber bacterial angular leaf spot was obtained by analyzing the value data as shown in Table 16:

[0124] Table 16 Evaluation of the combined effects of 5 compound ratios of bronopol and veratridine on the pathogens of cucumber bacterial angular leaf spot

[0125]

[0126] As shown in Table 16, the co-toxicity coefficients of the five ratios ranged from 92.64 to 199.90. Different ratios had different combined effects on the pathogenic bacteria of cucumber bacterial angular leaf spot. Among them, the most significant synergistic effect of the bronopol:veratrine ratio of 39:1 was 199.90.

[0127] The above experiments on the mixture of bronopol and veratridine showed that the two had significant synergistic effects, and their combined use could delay the drug resistance of cucumber bacterial angular leaf spot and improve the prevention effect.

[0128] Preparation excipient example 1: 20% bronopol·carvacrol soluble solution (19.5:0.5)

[0129] The composition of 20% bronopol·carvacrol soluble solution is shown in Table 17:

[0130] Table 17 20% Bronopol·Carvacrol Soluble Solution Ingredients

[0131]

[0132] According to the details of each component in Table 17, the active ingredient 2, the cosolvent, and the emulsifier are put into the stirring kettle in order and mixed for 10 minutes. After the material is evenly clarified, the active ingredient 1, the solvent, the antifreeze agent and the defoamer are added and stirred for 10 minutes until the material is completely evenly clarified. The bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention can be prepared. The test results of the bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention are shown in Table 18:

[0133] Table 18 Detailed test results of 20% bronopol·carvacrol soluble solution

[0134]

[0135] According to Table 18, the bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention meets all product standards and is a qualified product.

[0136] Preparation excipient example 2: 20% bronopol·carvacrol soluble solution (18:2)

[0137] The composition of 20% bronopol·carvacrol soluble solution is shown in Table 19:

[0138] Table 19 20% Bronopol·Carvacrol Soluble Solution Ingredients

[0139]

[0140]

[0141] According to the details of each component in Table 19, the active ingredient 2, the cosolvent, and the emulsifier are put into the stirring kettle in order and mixed for 10 minutes. After the material is evenly clarified, the active ingredient 1, the solvent and the defoamer are added and stirred for 10 minutes until it is completely evenly clarified to obtain the bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention. The test results of the bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention are shown in Table 20:

[0142] Table 20 Detailed test results of various indicators of 20% bronopol·carvacrol soluble solution

[0143]

[0144] According to Table 20, the bactericidal composition 20% bronopol·carvacrol soluble solution of the present invention meets all product standards and is a qualified product.

[0145] Preparation excipient example 3: 20% bronopol eugenol soluble solution (19.5:0.5)

[0146] The composition of 20% bronopol·carvacrol soluble solution is shown in Table 21:

[0147] Table 21 20% Bronopol·Eugenol Soluble Solution Ingredients

[0148]

[0149] According to the details of each component in Table 21, the active ingredient 2, the cosolvent and the emulsifier are put into the stirring kettle in order and mixed for 10 minutes. After the material is evenly clarified, the active ingredient 1, the defoamer and the solvent are added, and stirring is continued for 10 minutes until it is completely evenly clarified. The bactericidal composition 20% bronopol eugenol soluble solution of the present invention can be prepared. The test results of the bactericidal composition 20% bronopol eugenol soluble solution of the present invention are shown in Table 22:

[0150] Table 22 Detailed test results of various indicators of 20% bronopol·eugenol soluble solution

[0151]

[0152] According to Table 22, the bactericidal composition 20% bronopol·eugenol soluble solution of the present invention meets all product standards and is a qualified product.

[0153] Preparation excipient example 4: 60% bronopol·eugenol water dispersible granules (59:1)

[0154] The composition of 60% bronopol·carvacrol water dispersible granules is shown in Table 21:

[0155] Table 23 Components of 60% Bronopol·Eugenol Water Dispersible Granules

[0156]

[0157] According to the detailed description of each component in Table 23, the active ingredient 1, active ingredient 2, dispersant, wetting agent, defoamer and filler are put into a screw mixer and mixed for 10 minutes, the above materials are subjected to air flow pulverization to D90≤25μm, the above pulverized materials are mixed with water (70-75kg of deionized water is used per ton of materials) by a mixer to make the materials plastic, the mixed materials are extruded into columnar particles with a diameter of 1.0mm and dried with 90℃ hot air until the moisture is less than 3%, and the bactericidal composition 60% bronopol·eugenol water dispersible granules of the present invention can be obtained. The bactericidal composition 60% bronopol·eugenol water dispersible granules of the present invention are tested by product standards as shown in Table 24:

[0158] Table 24 Details of various indicators tested for 60% bronopol·eugenol water dispersible granules

[0159]

[0160]

[0161] According to Table 24, the bactericidal composition 60% bronopol·eugenol water dispersible granules of the present invention meets all product standards and is a qualified product.

[0162] Preparation excipient example 5: 20% bronopol·propenil wettable powder (19.95:0.05)

[0163] The composition of 20% bronopol·propenylcyclohexanone wettable powder is shown in Table 25:

[0164] Table 25 Components of 20% bronopol·propenclorac wettable powder

[0165]

[0166] According to the details of each component in Table 25, the carrier and the active ingredient 2 were mixed for 10 minutes using a zero-gravity mixer, and the active ingredient 1, the wetting agent, the dispersant and the filler were added in sequence. After mixing for 10 minutes, the mixed material was subjected to air flow pulverization until D90 was ≤ 35 μm, and the bactericidal composition 20% bronopol·bencarbamide wettable powder of the present invention was obtained. The test results of the bactericidal composition 20% bronopol·bencarbamide wettable powder of the present invention according to the product standard are shown in Table 26:

[0167] Table 26 Detailed test results of various indicators of 20% bronopol·benclorac oxadiazine soluble solution

[0168]

[0169]

[0170] According to Table 26, the fungicidal composition 20% bronopol·propenazole wettable powder of the present invention meets all product standards and is a qualified product.

[0171] Preparation excipient example 6: 20% bronopol·resveratrol soluble solution (19.5:0.5)

[0172] The composition of 20% bronopol·resveratrol soluble solution is shown in Table 27:

[0173] Table 27 20% Bronopol·Resveratrol Soluble Solution Ingredients

[0174]

[0175] According to the details of each component in Table 27, the active ingredient 2, the cosolvent and the emulsifier were put into the stirring kettle in order and mixed for 10 minutes. After the material was evenly clarified, the active ingredient 1, the solvent and the defoamer were added and stirred for 10 minutes until it was completely evenly clarified. The bactericidal composition 20% bronopol·resveratrol soluble solution of the present invention can be prepared. The test results of the bactericidal composition 20% bronopol·resveratrol soluble solution of the present invention are shown in Table 28:

[0176] Table 28 Detailed test results of various indicators of 20% bronopol·resveratrol soluble solution

[0177]

[0178] According to Table 28, the bactericidal composition 20% bronopol·resveratrol soluble solution of the present invention meets all product standards and is a qualified product.

[0179] Preparation excipient example 7: 30% bronopol·resveratrol wettable powder (29.5:0.5)

[0180] The composition of 30% bronopol·resveratrol soluble solution is shown in Table 29:

[0181] Table 29 Components of 30% Bronopol·Resveratrol Wettable Powder

[0182]

[0183] According to the details of each component in Table 29, the carrier and the active ingredient 2 were mixed for 10 minutes using a zero-gravity mixer, and the active ingredient 1, the wetting agent, the dispersant and the filler were added in sequence. After mixing for 10 minutes, the mixture was subjected to air flow pulverization until D90 was ≤ 35 μm, and the bactericidal composition 30% bronopol·resveratrol wettable powder of the present invention was obtained. The test results of the bactericidal composition 30% bronopol·resveratrol wettable powder of the present invention according to the product standard are shown in Table 30:

[0184] Table 30 Details of various indicators tested for 30% bronopol·resveratrol wettable powder

[0185]

[0186] According to Table 30, the bactericidal composition 30% bronopol·resveratrol wettable powder of the present invention meets all product standards and is a qualified product.

[0187] According to the product formulation excipient example, the inventors conducted field efficacy tests on the above formulations. The product field efficacy standards are described as follows:

[0188] The inventors have verified the control effects of the agents of the embodiments of the present invention on a large number of targets. This section uses some formulation example products on cucumber bacterial angular spot as an example to demonstrate the control effects of the composition of the present invention.

[0189] The test was conducted with reference to the National Standard of the People's Republic of China GB / T17980.110-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 110: Fungicides for Control of Cucumber Bacterial Angular Leaf Spot":

[0190] 1. Experimental purpose: To investigate the field control effect of different compound combinations on bacterial angular leaf spot of cucumber;

[0191] 2. Target of prevention and control: Pseudomonas syringae pv. lachrymans, the pathogen of cucumber bacterial angular leaf spot

[0192] 3. Application method and water consumption: spray method, water consumption per hectare is 1125L (75L / 667㎡)

[0193] 4. Plot arrangement, area and repetition:

[0194] The plots are arranged in random blocks, depending on the site, about every 25m 2 For 1 cell, repeat 4 times.

[0195] 5. Experimental investigation and calculation method:

[0196] 5.1. Investigation time: Investigation shall be conducted on the 10th day after the last application of pesticide.

[0197] 5.2. Survey Methods:

[0198] The open field plot was sampled at five points along the diagonal line, with five plants at each point. All leaves were investigated and graded based on the percentage of the diseased area of ​​each leaf to the total leaf area.

[0199] Grading Standard:

[0200] Level 0: no lesions;

[0201] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0202] Level 3: The lesion area accounts for 6%-10% of the entire leaf area;

[0203] Level 5: The lesion area accounts for 11%-25% of the entire leaf area;

[0204] Level 7: The lesion area accounts for 26%-50% of the entire leaf area;

[0205] Level 9: The lesion area accounts for more than 51% of the total leaf area.

[0206] 5.3. Calculation method of drug efficacy

[0207]

[0208]

[0209] The experiment was conducted on greenhouse cucumbers in Chuzhuang, Huaisi Town, Hanjiang District, Yangzhou City from September 20 to November 15, 2021. The cucumber variety is "Jinlu No. 11". The cucumbers were sown in mid-August, the on-site management level was relatively consistent, and the cucumbers grew relatively consistently. During the experiment, bacterial angular spot disease of cucumbers was in the early stages of the disease. The inventor designed to apply the drug once on September 28, 2021, October 7, 2021, October 16, 2021, and October 27, 2021 according to Tables 31, 33, 35, and 37, for a total of four applications, and the blank control was sprayed with an equal amount of clean water:

[0210] Product Field Efficacy Example 1: Application of Bronopol and Carvacrol

[0211] Table 31 Test design of test agents

[0212]

[0213]

[0214] According to the experimental design in Table 31, on November 10, 2021, the inventors calculated the disease index and analyzed the prevention and treatment effects according to the above experimental investigation and calculation method. The results are shown in Table 32:

[0215] Table 32 Test results of each preparation for preventing and treating bacterial angular spot of cucumber

[0216]

[0217] As shown in Table 32, the field control effect of bronopol and carvacrol preparations in different proportions on cucumber bacterial angular leaf spot is significantly better than that of single preparations of bronopol and carvacrol. 2 The effect is best when the average protection rate is 85.27%.

[0218] Product Field Efficacy Example 2: Application of Bronopol and Eugenol

[0219] Table 33 Test design of test drugs

[0220]

[0221] According to the experimental design in Table 33, on November 10, 2021, the inventors calculated the disease index and analyzed the prevention and treatment effects according to the above experimental investigation and calculation method. The results are shown in Table 34:

[0222] Table 34 Test results of each preparation for preventing and treating cucumber bacterial angular spot

[0223]

[0224] As shown in Table 34, the field control effect of bronopol and eugenol preparations in different proportions on cucumber bacterial angular leaf spot is significantly better than that of single agents of bronopol and carvacrol. The dosage of product preparation excipient Example 3 is 150g / mu, and the dosage of active ingredient is 450g ai / hm 2 The effect is best when the average protection rate is 88.24%.

[0225] Product Field Efficacy Example 3: Application of Bronopol and Propylene Glycol

[0226] Table 35 Test design of test drugs

[0227]

[0228] According to the experimental design in Table 35, on November 10, 2021, the inventors calculated the disease index and analyzed the prevention and treatment effects according to the above experimental investigation and calculation method. The results are shown in Table 36:

[0229] Table 36 Test results of each preparation for preventing and treating bacterial angular spot of cucumber

[0230]

[0231] As shown in Table 36, the field control effect of bronopol and fenpropimorph preparation products in different proportions on cucumber bacterial angular leaf spot is significantly better than that of bronopol and carvacrol alone. The dosage of product preparation excipient example 5 is 150g / mu, and the dosage of active ingredient is 450g ai / hm 2 The effect is best when the average protection rate is 87.32%.

[0232] Product Field Efficacy Example 4: Application of Bronopol and Veratrum Aldrin

[0233] Table 37 Test design of test drugs

[0234]

[0235]

[0236] According to the experimental design in Table 37, on November 10, 2021, the inventors calculated the disease index and analyzed the prevention and treatment effects according to the above experimental investigation and calculation method. The results are shown in Table 38:

[0237] Table 38 Test results of each preparation for preventing and treating bacterial angular spot of cucumber

[0238]

[0239] As shown in Table 38, the field control effect of bronopol and chloranthine preparation products with different ratios on cucumber bacterial angular leaf spot is significantly better than that of bronopol and chloranthine alone. The dosage of product preparation excipient Example 6 is 150g / mu, and the dosage of active ingredient is 450g ai / hm 2 The effect is the best, with an average protection rate of 89.03%.

[0240] In summary, the present invention adopts a bronopol bactericidal composition containing antibiotic active ingredients. Compared with the existing preparations, it not only has obvious synergistic effect, but also has good prevention and control effect, long lasting effect, safety to crops, and can slow down the development of bacterial disease resistance. It is worthy of promotion and application in agricultural production.

[0241] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A bactericidal composition containing bronopol, characterized in that: The bactericidal composition comprises bronopol and an active ingredient A, wherein the active ingredient A is selected from one of fenpropicyclopyralid and resveratrol, the weight ratio of the active ingredient A fenpropicyclopyralid to bronopol is 1:399, the weight ratio of the active ingredient A resveratrol to bronopol is 1:39-1:59, and the total weight percentage of the active ingredient A and bronopol in the bactericidal composition is 1%-70%.

2. The bactericidal composition according to claim 1, characterized in that The bactericidal composition can be formulated into one of wettable powder, soluble powder, water dispersible granules, soluble granules, aqueous emulsion, microemulsion, emulsifiable concentrate, suspension, dispersible oil suspension, microcapsule suspension, soluble solution, suspoemulsion, suspension-microcapsule suspension, and aqueous emulsion-microcapsule suspension.

3. The bactericidal composition according to claim 2, characterized in that The bactericidal composition also contains common adjuvants required for preparing pesticide preparations, and the common adjuvants are one or more of solvents, emulsifiers, wetting agents, stabilizers, dispersants, thickeners, pH regulators, defoamers, antifreeze agents, and fillers.

4. The bactericidal composition according to claim 1, characterized in that The bactericidal composition is used in preventing and controlling bacterial diseases of crops.

5. The bactericidal composition according to claim 4, characterized in that The crops are selected from food crops, cash crops and fruits and vegetables.

6. The bactericidal composition according to claim 1, characterized in that The fungicidal composition acts on plant pathogenic bacteria and / or their environment.

7. The bactericidal composition according to claim 1, characterized in that The bactericidal composition acts on plants or their cultivation media.

8. The method for using the bactericidal composition according to claim 1, characterized in that: The fungicidal composition according to claim 1 is applied to plants or their cultivation media by seed treatment, foliar application or stem application.

Citation Information

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