A bactericidal composition containing bromothalonil and pyrithione salt and application thereof

Abstract

The present application relates to the field of pesticides, in particular to a kind of containing bromothalonil and pyrithione salt fungicidal composition and application.The weight ratio of bromothalonil and pyrithione salt in the fungicidal composition of the present application is 9:1-1:9.The fungicidal composition of the present application has obvious synergistic effect, has better control effect, reduces the amount of drug, saves cost, improves the safety to environment.

Description

Technical Field

[0001] This invention relates to the field of pesticides, specifically to a fungicide composition containing bromodiphenyl ether and pyridinium thionate, which is mainly used for the prevention and control of diseases on crops. Background Technology

[0002] Pyridinethiones are primarily used as preservatives and antifungal agents in daily chemical products. They prevent product spoilage and mold growth, and also relieve itching and dandruff. They are used in building coatings, adhesives, sealants, textiles, leather products, pulp, and water treatment products for their antiseptic and antibacterial effects. The bactericidal mechanism of pyridinethiones on bacterial cells varies slightly depending on the pH of the external environment. In acidic or neutral environments, pyridinethiones readily bring H+ into the cell and remove K+ from the cell, resulting in an H+-K+ exchange. In alkaline environments, they readily bring Na+ into the cell and remove K+ and Mg2+ from the cell. This change in ion gradient deprives bacteria of nutrients, ultimately causing them to "starve," while the pyridinethiones themselves are not consumed during the bactericidal process.

[0003] Existing technology reports on the antibacterial effects of pyrithione or its salts primarily pertain to personal care formulations and skin and / or hair treatments. For example, patent document (CN106572655A) discloses that compositions comprising zinc pyrithione and zinc salts of pyridine carboxylic acid exhibit good antibacterial effects in personal care and paint formulations. However, there are very few prior art reports on the use of pyrithione salts for agricultural antibacterial applications. Patent document (CN105284813A) discloses a fungicide for controlling citrus Huanglongbing (HLB) and its uses, revealing that copper pyrithione, zinc pyrithione, or sodium pyrithione exhibit good control effects against HLB.

[0004] Bromhizobium is a broad-spectrum, highly effective, and low-toxicity fungicide that can inhibit and control the growth of fungi, bacteria, and algae. It has a good control effect on crop diseases and is widely used on various crops such as fruit trees, grapes, vegetables, cotton, peanuts, watermelons, tobacco, tea trees, and flowers. It has a good control effect on a variety of fungal and bacterial diseases such as black spot, powdery mildew, rust, damping-off, root and stem disease, gut ulcer, bacterial wilt, and angular leaf spot.

[0005] There are no reports in the existing technical literature regarding the use of bromodiphenyl ether and pyridinium thionate salt combinations in antibacterial compositions. Those skilled in the art know that in the field of pesticides, the combination of two active ingredients can result in additive, synergistic, or antagonistic effects, and whether synergistic effects are achieved is unpredictable. Through long-term research, the applicant unexpectedly discovered that the antibacterial composition of bromodiphenyl ether and pyridinium thionate salt exhibits a good synergistic effect in antibacterial activity, which can reduce dosage, reduce environmental risks, and delay the development of resistance. Summary of the Invention

[0006] The objective of this invention is to provide an antibacterial composition with synergistic effects. To achieve this objective, the invention provides a bactericidal composition comprising bromodiphenyl ether and pyrithione salt.

[0007] The present invention also provides a bactericidal composition formulation comprising the bactericidal composition described above and a suitable pesticide adjuvant.

[0008] The present invention also provides the above-mentioned bactericidal composition and bactericidal composition formulation for the prevention and control of various fungal and bacterial diseases on crops.

[0009] The present invention also provides a method for preventing and controlling fungal and bacterial diseases of crops, wherein the composition of the present invention or a formulation thereof is diluted and sprayed onto the crops that need to be controlled.

[0010] The beneficial effects of this invention are:

[0011] 1. The combination of bromodiphenyl ether and pyridinethione salt of the present invention has a significant synergistic effect, which reduces the amount of pesticide used while expanding the fungicidal spectrum compared with the use of single agents.

[0012] 2. The bromodiphenyl ether salt and pyridinethione salt in the composition of the present invention have different mechanisms of action, which can better delay the development of disease resistance and extend the application time of pesticides. Detailed Implementation

[0013] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. In addition, to better illustrate the present invention, numerous specific details are given in the following detailed embodiments. Those skilled in the art should understand that the present invention can be implemented without certain specific details. In some embodiments, raw materials, additives, methods, means, etc., well known to those skilled in the art, are not described in detail in order to highlight the main points of the present invention.

[0014] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated active ingredients or components, without excluding other active ingredients or other components.

[0015] Specifically, the present invention provides a bactericidal composition comprising bromodiphenyl ether and pyridinium thionate.

[0016] Furthermore, the salt of pyrithione is one of sodium pyrithione, copper pyrithione, or zinc pyrithione.

[0017] Furthermore, in the above-mentioned bactericidal composition, the weight ratio of bromodimethicone to pyridinethione salt is 9:1 to 1:9.

[0018] Furthermore, when the pyridinethione salt in the above-mentioned bactericidal composition is sodium pyridinethione, the weight ratio of bromodimethicone to sodium pyridinethione is 9:1-1:9, preferably 9:1-3:7, most preferably 9:1, 7:3, 1:1, and 3:7.

[0019] Furthermore, when the pyridinethione salt in the bactericidal composition is zinc pyridinethione, the weight ratio of bromodimethicone to zinc pyridinethione is 9:1-1:9, preferably 9:1, 1:1-1:9, and most preferably 9:1, 1:1, 3:7 and 1:9.

[0020] Furthermore, when the pyridinethione salt in the above-mentioned bactericidal composition is copper pyridinethione, the weight ratio of bromodimethicone to copper pyridinethione is 9:1-1:9, preferably 7:3-1:9, and most preferably 7:3, 1:1, 3:7 and 1:9.

[0021] The present invention also provides a bactericidal composition formulation comprising the bactericidal composition described above and a suitable pesticide adjuvant.

[0022] Furthermore, the above-mentioned bactericidal composition can be formulated into a suitable dosage form, which is a suspension, wettable powder, or water-dispersible granule.

[0023] The aforementioned additives include one or more of the following: dispersants, wetting agents, antifreeze agents, stabilizers, preservatives, thickeners, binders, defoamers, acid-adjusting media, and solid inert carriers.

[0024] Optionally, the dispersant is selected from one or more of alkyl naphthalene sulfonates, calcium alkylbenzene sulfonates, fatty amine polyoxyethylene ethers, bis(alkyl)naphthalene sulfonate formaldehyde condensates, naphthalene sulfonate formaldehyde condensates, sodium naphthalene sulfonate formaldehyde condensates, alkylphenol polyoxyethylene ethers, arylphenol polyoxyethylene succinate sulfonates, octylphenol polyoxyethylene ether sulfates, polycarboxylates, sodium lignosulfonates, alkylphenol polyoxyethylene ether formaldehyde condensates sulfates, fatty acid polyoxyethylene esters, and fatty acid polyoxyethylene ethers, preferably one or more of arylphenol polyoxyethylene succinate sulfonates, sodium naphthalene sulfonate formaldehyde condensates, polycarboxylates, and sodium lignosulfonates.

[0025] Optionally, the wetting agent is selected from one or more of the following: BX (a type of sizing agent), sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, agricultural emulsion 2000# series, sodium dioctyl succinate sulfonate, and soapberry powder. Preferably, it is selected from one or more of the following: sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and sodium dioctyl succinate sulfonate.

[0026] Optionally, the antifreeze can be one or more of ethylene glycol, 1,2-propanediol, glycerol and urea, preferably ethylene glycol.

[0027] Optionally, the binder may be one or more of starch, gypsum, glucose, polyvinyl alcohol, gum arabic, and dextrin, with starch being preferred.

[0028] Optionally, the thickener may be one or more of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin, preferably one or more of magnesium aluminum silicate and xanthan gum.

[0029] Optionally, the solid inert carrier can be one or more of clay, silica, diatomaceous earth, kaolin, attapulgite, montmorillonite, bentonite, talc, and light calcium carbonate, preferably one or more of silica, diatomaceous earth, and kaolin.

[0030] Optionally, the defoamer is selected from silicone, C 8-10 fatty alcohols, C 10-20 One or more of saturated fatty acids (such as decanoic acid) and amides, silicone oils, and silicone compounds. Organosilicon defoamers are preferred.

[0031] Optionally, the acid-adjusting medium is selected from one or more of ammonium sulfate, ammonium nitrate, ammonium chloride, hydrochloric acid, citric acid, and acetic acid.

[0032] Optionally, the preservative may be selected from sodium benzoate. Stabilizers may be substances commonly used in the art, which are well known to those skilled in the art and will not be described further here.

[0033] Furthermore, appropriate additives can be added according to the needs of preparing the dosage form.

[0034] Furthermore, in the above-described bactericidal composition formulation, bromodimethicone and pyridinethione salt account for 1%-70% of the total weight of the formulation, preferably 5%-60%.

[0035] In this invention, there are no special requirements for the preparation methods of various dosage forms; various methods known in the art can be used, which will not be elaborated here.

[0036] The present invention also provides the application of the above-mentioned bactericidal composition and / or formulations of the bactericidal composition in the prevention and control of crop pathogens.

[0037] The application mentioned above in the prevention and control of crop pathogens refers to its use in the prevention and control of fungal and bacterial diseases in crops.

[0038] Furthermore, the crop pathogens are fungal and / or bacterial diseases. Preferably, the pathogen is anthracnose, for example, *Anthracnose causal agent*, the causal agent of strawberry anthracnose. The fungicide in this invention can be diluted as needed during actual use.

[0039] The following examples further illustrate the content of the present invention, but should not be construed as limiting the present invention.

[0040] The bactericidal composition of the present invention can be provided in the form of a finished product, i.e., the components in the composition have been mixed; or it can be provided in the form of a separate formulation of each component, which can be mixed evenly before use.

[0041] Formulation Examples

[0042] Example 1

[0043] Preparation of 10% bromodiphenyl ether·10% sodium pyrithione suspension

[0044] The components, by mass percentage, are: 10% bromocyanidin, 10% sodium pyrithione, 5% sodium naphthalenesulfonic acid formaldehyde condensate, 2% sodium dodecyl sulfate, 4% ethylene glycol, 0.2% xanthan gum, 0.5% magnesium aluminum silicate, 0.2% citric acid, 0.2% sodium benzoate, 0.2% silicone defoamer, with water to make up the balance. After thorough mixing and grinding, the product is obtained.

[0045] Example 2

[0046] Preparation of 18% bromodiphenyl ether·2% sodium pyrithione wettable powder

[0047] The components are allocated as follows by mass percentage: 18% bromocyanidin, 2% sodium pyrithione, 6% sodium lignosulfonate, 1.5% sodium dioctyl succinate sulfonate, 5% silica, 0.2% citric acid, 0.2% silicone defoamer, and diatomaceous earth to make up the balance. The mixture is then thoroughly mixed, pulverized, and the product is obtained.

[0048] Example 3

[0049] Preparation of 3% bromodiphenyl ether·27% copper pyrithione wettable powder

[0050] By mass percentage, the composition of each group is: 3% bromocyanuric acid, 27% copper pyridinium thionate, 10% sodium naphthalenesulfonic acid formaldehyde condensate, 4% sodium dodecyl sulfate, 5% silica, 0.3% citric acid, and 0.5% C. 8-10 Fatty alcohol defoamer and kaolin are added as supplements. The mixture is thoroughly mixed, pulverized, and the final product is obtained.

[0051] Example 4

[0052] Preparation of 3% bromodiphenyl ether·7% copper pyrithione water-dispersible granules

[0053] The components, by mass percentage, are: 3% bromocyanuric acid, 7% copper pyridinium ketone, 8% sodium dodecylbenzene sulfonate, 3% sodium dioctyl succinate sulfonate, 5% silica, 5% starch, 0.3% citric acid, 0.5% silicone defoamer, and diatomaceous earth to make up the difference. After thorough mixing, the mixture is pulverized, granulated, and dried to obtain the final product.

[0054] Example 5

[0055] Preparation of 18% bromodiphenyl ether·2% zinc pyrithione suspension

[0056] The components, by weight percentage, are: 18% bromocyanuric acid, 2% zinc pyrithione, 5% sodium lignosulfonate, 2% sodium dodecyl sulfate, 4% silica, 5% ethylene glycol, 0.2% xanthan gum, 0.2% acetic acid, 0.2% sodium benzoate, 0.2% silicone defoamer, and water to make up the balance. Mix thoroughly and grind to obtain the product.

[0057] Example 6

[0058] Preparation of 9% bromodiphenyl ether·9% zinc pyrithione wettable powder

[0059] The components, by mass percentage, are: 9% bromocyanidin, 9% zinc pyrithione, 8% sodium naphthalenesulfonic acid formaldehyde condensate, 4% BX defoamer, 3% silica, 0.3% citric acid, 0.4% silicone defoamer, and kaolin to make up the balance. Mix thoroughly, then pulverize to obtain the product.

[0060] II. Bioassay Example

[0061] 1. Materials and Methods

[0062] 1.1 Test strains, reagents, and culture media, etc.

[0063] Test strain: Strawberry anthracnose fungus (preserved in the laboratory).

[0064] Test equipment: clean bench, sterilizer, incubator, etc.

[0065] Test reagents: 98% bromodiphenyl ether technical grade (laboratory storage), sodium pyrithione, zinc pyrithione, copper pyrithione.

[0066] PDA medium: 3g potato extract powder, 20g glucose, 15-20g agar, 1L deionized water. Mix well and sterilize at high temperature for later use.

[0067] 1.2 Test Methods

[0068] The mycelial growth rate method was used to detect the growth effects of single and compound agents on the pathogen. Preliminary experiments were conducted to determine different concentration gradients (five gradients per ratio) of bromodiphenyl ether and three pyridinethione salts against strawberry anthracnose pathogens. Bromodiphenyl ether and the three pyridinethione salts were pre-prepared into five different ratios of stock solutions (9:1, 7:3, 1:1, 3:7, and 1:9). These stock solutions were mixed with PDA (polydimethyl ether) to prepare culture media with final concentrations corresponding to each ratio. Strawberry anthracnose mycelial cakes (5 mm in diameter) were inoculated onto these drug-containing PDA culture media and incubated at 25°C for 4 days. Three culture dishes were used for each concentration, and the experiment was repeated twice. The inhibition rate and EC (excessive chromatogram) of different concentrations of the agents on strawberry anthracnose mycelial growth were calculated. 50 .

[0069] 1.3 Statistical and Analytical Methods

[0070] Perform data analysis using SPSS 20 and calculate the regression equation, correlation coefficient r, and EC. 50 The Wadley method was used to evaluate the synergistic effect. A synergistic effect was defined as SR > 1.5, an additive effect as 0.5 ≤ SR ≤ 1.5, and an antagonistic effect as SR < 0.5.

[0071]

[0072]

[0073]

[0074] In the formula: A and B represent two agents respectively, a and b represent the proportions of the two agents in the mixture respectively, obs is the measured value, and EXP is the theoretical value.

[0075] Table 1. Results of bromodiphenyl nitrile:sodium pyrithione toxicity testing and synergistic effect evaluation on strawberry anthracnose toxicity at different ratios.

[0076]

[0077] As can be seen from the results in Table 1, the weight ratio of bromodiphenyl ether to sodium pyrithione exhibits a good synergistic effect in the range of 9:1 to 1:9, especially in the range of 9:1 to 3:7, with the optimal ratios being 9:1, 7:3, 1:1 and 3:7.

[0078] Table 2. Results of bromodimethoprim:zinc pyrithione ratio on the toxicity of strawberry anthracnose and evaluation of synergistic effects.

[0079]

[0080] The results in Table 2 show that the weight ratio of bromodiphenyl ether to zinc pyrithione exhibits a good synergistic effect in the range of 9:1 to 1:9, especially in the range of 9:1, 1:1 to 1:9, with the optimal ratios being 9:1, 1:1, 3:7 and 1:9.

[0081] Table 3. Results of bromodiphenyl ether:copper pyrithione ratio on the toxicity of strawberry anthracnose and evaluation of synergistic effects.

[0082]

[0083]

[0084] The results in Table 3 show that bromodiphenyl ether and copper pyrithione exhibit good synergistic effects in the weight ratio range of 9:1 to 1:9, especially in the range of 7:3 to 1:9, with 7:3, 1:1, 3:7 and 1:9 being the most preferred.

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A bactericidal composition, characterized in that, Includes bromodiphenyl nitrile and pyridinethione salt, wherein the pyridinethione salt is one of sodium pyridinethione salt and copper pyridinethione salt; The weight ratio of bromodiphenyl ether and sodium pyrithione is 9:1-3:7; The weight ratio of bromodiphenyl ether and copper pyrithione is 7:3-1:

9.

2. A bactericidal composition formulation, characterized in that, It comprises the bactericidal composition of claim 1 and a suitable pesticide adjuvant.

3. The bactericidal composition formulation according to claim 2, characterized in that, Prepare a suitable dosage form, wherein the dosage form is one of suspension, wettable powder or water-dispersible granules.

4. The bactericidal composition formulation according to claim 2 or 3, characterized in that, Bromhizobium and pyridinethione salts account for 1%-70% of the total weight of the formulation.

5. The bactericidal composition formulation according to claim 4, characterized in that, Bromhizobium and pyrithione salt account for 5%-60% of the total weight of the formulation.

6. The application of the bactericidal composition of claim 1 and / or the bactericidal composition formulation of any one of claims 2-5 in the prevention and control of fungal and bacterial diseases on crops.

7. The application according to claim 6, characterized in that, The pathogens that cause the disease are fungi and / or bacteria.

8. The application according to claim 7, characterized in that, The pathogen mentioned is anthrax bacteria.

9. The application according to claim 8, characterized in that, The pathogen mentioned is the strawberry anthracnose bacterium.

10. A method for preventing and controlling fungal and bacterial diseases of crops, characterized in that, Apply the composition of claim 1 or the fungicidal composition formulation of any one of claims 2-5 to the plants that need to be controlled.

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