Wettable powder containing stabilizer and application thereof

Abstract

The invention belongs to the field of agricultural fungicides, and relates to wettable powder containing a stabilizer and application of the wettable powder. The wettable powder containing the stabilizer is composed of active components and an auxiliary agent, the active components are fosetyl-aluminum and an amide fungicide (B), the auxiliary agent contains the stabilizer, the stabilizer is one or more of biphenyl substances with a 2, 2 '-dihydroxyl structure, and the adding amount of the stabilizer accounts for 0.1-30% of the mass of the preparation. The wettable powder provided by the invention is stable in sample, the raw materials generate an effective synergistic effect, and the problem that the suspension rate and the wettability are obviously reduced in different environments when the fosetyl-Al is mixed with other amide fungicides to prepare the wettable powder is solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of agricultural fungicides, and relates to a wettable powder containing a stabilizer and application thereof. BACKGROUND

[0002] Fosetyl-aluminum is a highly effective, low-toxic, broad-spectrum organophosphorus fungicide with good curative effect on plant downy mildew, anthracnose and other diseases, long persistence and safe use. The wettable powder has the advantages of simple processing and safety to crops. Therefore, it is well known in the art to prepare a wettable powder from fosetyl-aluminum or a composition containing fosetyl-aluminum, which has been widely used in agricultural production.

[0003] However, there are certain difficulties in preparing a wettable powder from fosetyl-aluminum or a composition containing fosetyl-aluminum. This is because the molecular structure of fosetyl-aluminum contains an aluminum ion core and multiple phosphonate groups. Although this strong polarity and multiple charge metal-organic framework provides good efficacy, it also leads to easy adsorption of water, forming liquid bridges between particles and causing caking; and the multiple charges lead to easy combination with insoluble charged particles in natural water bodies, resulting in flocculation. Therefore, current research mainly focuses on solving the above problems caused by fosetyl-aluminum itself.

[0004] Patent CN101606518A discloses a wettable powder of fosetyl-aluminum, which improves the caking phenomenon during storage of the preparation.

[0005] Patent CN114467964 discloses a wettable powder of propamocarb hydrochloride and fosetyl-aluminum, which improves the suspension rate of fosetyl-aluminum.

[0006] However, there are certain difficulties in preparing a wettable powder from fosetyl-aluminum or a composition containing fosetyl-aluminum. This is because the molecular structure of fosetyl-aluminum contains an aluminum ion core and multiple phosphonate groups. Although this strong polarity and multiple charge metal-organic framework provides good efficacy, it also leads to easy adsorption of water, forming liquid bridges between particles and causing caking; and the multiple charges lead to easy combination with insoluble charged particles in natural water bodies, resulting in flocculation. Therefore, current research mainly focuses on solving the above problems caused by fosetyl-aluminum itself.

[0007] The amide fungicides, including dimoxystrobin, flumorph, mandipropamid, and penflufen, have similar fungicidal spectrum and inhibitory activity, and have excellent protective and curative effects on plant diseases caused by most Oomycetes. At the same time, these fungicides have consistent inhibitory characteristics at different growth and development stages of the target fungi, and have positive cross-resistance and similar mechanisms of action. It has been found that fosetyl-aluminum has excellent efficacy when mixed with any of dimoxystrobin, flumorph, mandipropamid, and penflufen.

[0008] Patent CN107708421A reports the mixing of fosetyl-aluminum and dimoxystrobin for the prevention and treatment of grape downy mildew.

[0009] Patent CN115104621A reports that aluminum tris (ethylphosphine) and milneb are mixed to prevent and control cucumber downy mildew and tomato late blight.

[0010] Patent CN105794795A reports that aluminum tris (ethylphosphine) and flumorph are mixed to prevent and control cucumber downy mildew.

[0011] Patent CN103004862A reports that aluminum tris (ethylphosphine) and benzothiadinylamine are mixed to prevent and control grape downy mildew.

[0012] The above reports fully demonstrate that any one of aluminum tris (ethylphosphine), enaminomorpholine, flumorph, milneb and benzothiadinylamine mixed after mixing has good control effect on oomycetes pathogenic bacteria.

[0013] However, in the actual application process, when aluminum tris (ethylphosphine) is mixed with amide fungicides to prepare wettable powder, the suspension rate and wettability of the preparation will be significantly reduced, and this phenomenon will be further intensified in low temperature water and high hardness water.

[0014] The core of the problem is that the hydrophobic, non-polar and almost non-ionizable nature of amide fungicides is fundamentally in conflict with the hydrophilic, polar and ionizable nature of aluminum tris (ethylphosphine). When they are crushed and mixed into small solid particles and added with wetting dispersants, this conflict will be amplified in water and significantly affected by environmental conditions.

[0015] In summary, in the actual application process, the wettable powder prepared by mixing aluminum tris (ethylphosphine) with other amide fungicides has great physical property problems, which seriously affects its normal use and drug efficacy. Therefore, the present application provides a wettable powder containing a stabilizer, which can effectively solve the physical property problems generated when aluminum tris (ethylphosphine) is mixed with other amide fungicides to prepare wettable powder. SUMMARY

[0016] The present application provides a wettable powder containing a stabilizer and its application to solve the problems of the prior art.

[0017] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0018] A wettable powder containing a stabilizer is composed of active ingredients and adjuvants, the active ingredients are aluminum tris (ethylphosphine) and an amide fungicide (B), the adjuvants contain a stabilizer, the stabilizer is one or more of the biphenyl substances with 2,2'-dihydroxy structure, and the addition amount is 0.1-30% of the mass of the preparation.

[0019] The active component is aluminum trisethylphosphinate and an amide fungicide (B), which accounts for 2-90% of the mass of the preparation; wherein the amide fungicide (B) is selected from one of the following: dimoxystrobin (B1), mandipropamid (B2), flumorph (B3) and fenhexamid (B4).

[0020] The structure of the 2,2'-dihydroxy structure of biphenyl is as follows:

[0021]

[0022] In the formula, R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' may be the same or different and are selected from hydrogen, halogen, C1-C 12 alkyl which is unsubstituted or substituted by at least one halogen, C2-C 12 alkenyl, C2-C 12 alkynyl, aryl, benzyl.

[0023] The wettable powder contains, by weight percentage, 2-90% of active ingredient, 0.1-30% of stabilizer, 1-30% of wetting dispersant, 1-75% of filler, and 0-20% of other additives; wherein the active component contains 1-80% of aluminum trisethylphosphinate and 1-50% of amide fungicide (B) by mass of the preparation.

[0024] The other additives are selected from one or more of antifoaming agent, pH regulator, penetrant, synergist, spreading agent.

[0025] The wettable powder contains, by weight percentage, 10-85% of active ingredient, 0.1-20% of stabilizer, 1-20% of wetting dispersant, 1-60% of filler, and 0-10% of other additives.

[0026] The active component contains 5-70% of aluminum trisethylphosphinate and 5-30% of amide fungicide B by mass of the preparation.

[0027] The stabilizer is one or more of 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-2,2'-biphenol, 2,2'-dihydroxy-5,5'-dipropylbiphenyl, 5',5-diallyl-2,2'-biphenol, and the addition amount is 0.1-20% of the mass of the preparation.

[0028] The wetting dispersant is one or more of polycarboxylate, lignin sulfonate, lignin sulfate, alkyl naphthalene sulfonate, dodecyl sulfate, dodecyl benzene sulfonate, ethoxylated alcohol, polyoxyethylene ether;

[0029] The filler is one or more of kaolin, sericite powder, calcined kaolin, attapulgite, zeolite powder, pyrophyllite powder, magnesium stearate, meerschaum powder, light calcium carbonate, anhydrous sodium sulfate, diatomite, tricalcium phosphate, white carbon black, talc powder;

[0030] The wetting dispersant is one or more of polycarboxylate, lignin sulfate, dodecyl sulfate, ethoxylated alcohol, polyoxyethylene ether;

[0031] The filler is one or more of sericite powder, calcined kaolin, magnesium stearate, tricalcium phosphate, anhydrous sodium sulfate, white carbon black, talc powder.

[0032] Other auxiliary agents can also be added in the preparation, but not necessarily, selected from one or more of antifoaming agent, pH adjusting agent, penetrant, spreading agent.

[0033] The antifoaming agent can be one or more of polysiloxane, polyether modified silicon, fatty acid and fatty acid ester.

[0034] The pH adjusting agent can be one or more of potassium dihydrogen phosphonate, ammonium sulfate, fumaric acid, sodium hexametaphosphate, benzoic acid, sodium benzoate, sodium citrate, potassium citrate, citric acid, sodium bisulfate, oxalic acid.

[0035] The penetrant can be one or more of alkyl phenol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, alpha-alkenyl sulfonate, alkyl succinamide sulfonate, organosilicon polyether.

[0036] The spreading agent can be one or more of organosilicon grease, polyvinyl alcohol, modified silane.

[0037] The application of the wettable powder containing the stabilizer, and the application of the wettable powder containing the stabilizer in sterilization control of a site.

[0038] The application has the following advantages:

[0039] The application is directed to the preparation of a wettable powder by mixing aluminum trisethylphosphine and other amide bactericides, and adding 2,2'-dihydroxy structure biphenyl material as a stabilizer in the system, thereby solving the problem of significant reduction of suspension rate and wettability, and the problem of intensified reduction in low temperature water and high hardness water, greatly improving the physical properties of the preparation in different environments, and ensuring the normal use of the product and the exertion of the drug efficacy.

[0040] The active ingredient amide bactericide in the preparation has strong hydrophobicity, and hardly ionizes in water, while the aluminum trisethylphosphonate molecule has strong hydrophilicity and ionicity. In the mixing and crushing process, the fine particles of the two active ingredients will be in close contact to form composite particles. The surface of the composite particles is no longer a uniform hydrophobic surface or a uniform hydrophilic surface, but a highly heterogeneous surface, that is, the hydrophobic amide region and the hydrophilic aluminum trisethylphosphonate region are distributed alternately. After the formation of the composite particles, water molecules rapidly spread in the hydrophilic aluminum trisethylphosphonate region, but contract into beads in the hydrophobic amide region. The water film needs to repeatedly cross the hydrophobic-hydrophilic boundary, consuming additional energy and significantly prolonging the wetting time. At the same time, the surface tension of water increases with the decrease of temperature, the higher the surface tension, the weaker the ability of water to spontaneously spread and penetrate the surface of the solid, and the viscosity of water increases at low temperature, further hindering the penetration of water into the pores of the particles. Therefore, low temperature amplifies the wetting barrier caused by the surface heterogeneity of the two, further prolonging the wetting time. The biphenyl substance with 2,2'-dihydroxy structure has a hydrophobic biphenyl skeleton and two hydrophilic phenolic hydroxyl groups, and the hydrophobic region can be adsorbed on the hydrophobic surface of the amide through van der Waals force and π-π stacking. The hydrophilic phenolic hydroxyl group is exposed outside, covering the originally highly hydrophobic amide particle surface with a layer of hydrophilic groups, weakening the hydrophilic-hydrophobic heterogeneity of the mixed particle surface, converting it into a more uniform hydrophilic surface, reducing the water molecule spreading resistance, and further shortening the wetting time. At the same time, the biphenyl substance with 2,2'-dihydroxy structure molecules interspersed in the water molecule network can reduce the apparent viscosity of water at low temperature and improve the flowability. Therefore, using the biphenyl substance with 2,2'-dihydroxy structure as a stabilizer can greatly improve the wetting ability of the preparation in water at different temperatures.

[0041] Meanwhile, when the composite particles formed by aluminum trisethylphosphine and other amide bactericides are successfully wetted and dispersed in water, the molecules of the amide bactericides and the molecules of aluminum trisethylphosphine or its hydrolysis products all have multiple complementary hydrogen bonding sites, and interaction occurs through hydrogen bonding, which on the one hand weakens the effect of electrostatic repulsion of single particles, and on the other hand these hydrogen bonds can form a bridge between different particles to connect the particles, thereby causing flocculation. Meanwhile, this phenomenon is intensified in high-hardness water, because a large amount of calcium ions and magnesium ions in high-hardness water can further compress the double electric layer around the particles and reduce the electrostatic repulsion. The biphenyl substance with 2,2'-dihydroxy structure is used as a stabilizer. First, the biphenyl substance with 2,2'-dihydroxy structure has two phenolic hydroxyl groups, but the ortho structure promotes the formation of intramolecular hydrogen bonds, so when it is adsorbed on the surface of the amide compound by stacking, it will shield the original hydrogen bond donors and acceptors and prevent the formation of a hydrogen bond network. Meanwhile, the biphenyl skeleton of the biphenyl substance with 2,2'-dihydroxy structure has a large volume, and after being adsorbed on the surface of the particles, it forms a physical barrier to increase the steric resistance of the particles to approach each other, further preventing aggregation. When in a hard water environment, the biphenyl substance with 2,2'-dihydroxy structure can combine with calcium ions and magnesium ions to form stable complexes, reducing the amount of free calcium ions and magnesium ions and maintaining the electrostatic repulsion. Therefore, using the biphenyl substance with 2,2'-dihydroxy structure as a stabilizer can greatly improve the suspension rate of the preparation in water of different hardness.

[0042] In summary, the biphenyl substance with 2,2'-dihydroxy structure is selected as a stabilizer for the preparation of wettable powder by mixing aluminum trisethylphosphine with other amide bactericides, which can effectively solve the problems in the prior art. DETAILED DESCRIPTION

[0043] The specific embodiments of the present application are further described in conjunction with the examples below, and it should be noted that the specific embodiments described herein are only intended to illustrate and explain the present application, and are not limited to the present application. Those skilled in the art should recognize that any alternative, improvement, equivalent solution made without deviating from the spirit and principles of the present application all fall within the scope of the present application.

[0044] The technical materials in the examples and the remaining materials are all commercially available, and all the examples are prepared according to the following preparation process. First, according to the requirements of the formula, the active ingredients and adjuvants except the stabilizer are weighed and mixed. Then the mixed materials are respectively subjected to primary pulverization using a hammer-type ultrafine pulverizer. Then the primary pulverized materials are subjected to secondary pulverization using a disc-type air flow pulverizer. Finally, the stabilizer is added to the secondary pulverized materials in proportion, and the disc-type air flow pulverizer is used again to uniformly mix them, thereby obtaining the wettable powder sample.

[0045] The formulation recipe is implemented as follows:

[0046] Example 1 : 80% aluminum phosphonate · maleic hydrazide wettable powder

[0047] Aluminum phosphonate 70%, maleic hydrazide 10%, 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenol 5%, 2,2'-dihydroxybiphenyl 1%, Morwet EFW 1%, Ultrazine NA 6%, G-920BQ 0.1%, white carbon black to 100%.

[0048] Example 2: 70% aluminum phosphonate · maleic hydrazide wettable powder

[0049] Aluminum phosphonate 50%, maleic hydrazide 20%, 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenol 2%, 2,2'-dihydroxy-5,5'-dipropylbiphenyl 1%, 5',5-diallyl-2,2'-biphenyldiol 2%, Borresperse NA 3%, Ultrazine NA 5%, G-920BQ 0.1%, white carbon black 3%, sericite powder to 100%.

[0050] Example 3: 50% aluminum phosphonate · maleic hydrazide wettable powder

[0051] Aluminum phosphonate 45%, maleic hydrazide 5%, 2,2'-dihydroxybiphenyl 4%, LX Special 3%, D900 5%, G-920BQ 0.1%, sericite powder to 100%.

[0052] Example 4: 30% aluminum phosphonate · maleic hydrazide wettable powder

[0053] Aluminum phosphonate 10%, maleic hydrazide 20%, 2,2'-dihydroxy-5,5'-dipropylbiphenyl 4%, sodium dodecylbenzenesulfonate 2%, D900 3%, Tensiofix-CJK 0.2%, sodium citrate 1%, calcined kaolin 10%, sericite powder to 100%.

[0054] Example 5: 10% aluminum phosphonate · maleic hydrazide wettable powder

[0055] Aluminum phosphonate 5%, maleic hydrazide 5%, 2,2'-dihydroxy-5,5'-dipropylbiphenyl 2%, 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenol 1%, sodium dodecyl sulfate 2%, D900 2%, Tensiofix-CJK 0.2%, sodium citrate 2%, sericite powder to 100%.

[0056] Example 6: 80% aluminum phosphonate · dimetan wettable powder

[0057] aluminium phosphite 70%, milneb 10%, 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenol 5%, PICO-U100 2%, Greensperse CA-N 5%, Tensiofix-CJK 0.1%, talc to 100%.

[0058] Example 7: 70% aluminium phosphite · milneb wettable powder

[0059] aluminium phosphite 50%, milneb 20%, 2,2'-dihydroxybiphenyl 5%, LX Special 3%, Ultrazine NA 5%, THIX-258 0.1%, talc 1%, sericite powder to 100%.

[0060] Example 8: 50% aluminium phosphite · milneb wettable powder

[0061] aluminium phosphite 45%, milneb 5%, 2,2'-dihydroxy-5,5'-dipropylbiphenyl 2%, 5',5-diallyl-2,2'-biphenyldiol 3%, Ufoxane 3A 2%, Borresperse NA 5%, G-920BQ 0.1%, talc 1%, sericite powder to 100%.

[0062] Example 9: 30% aluminium phosphite · milneb wettable powder

[0063] aluminium phosphite 10%, milneb 20%, with 5',5-diallyl-2,2'-biphenyldiol 4%, Ufoxane 3A 2%, Borresperse NA 4%, sericite powder 5%, anhydrous sodium sulphate to 100%.

[0064] Example 10: 10% aluminium phosphite · milneb wettable powder

[0065] aluminium phosphite 5%, milneb 5%, 3,3',5,5'-tetramethyl-2,2'-biphenyldiol 2%, sodium dodecylbenzenesulphonate 2%, Borresperse NA 3%, Tensiofix-CJK 0.2%, tribasic calcium phosphate to 100%.

[0066] Example 11 : 80% aluminium phosphite · flumorph wettable powder

[0067] Aluminium phosphonate triethyl 70%, flumorph 10%, 2,2'-dihydroxydiphenyl 4%, 2,2'-dihydroxy-5,5'-dipropyl-diphenyl 1%, Morwet EFW 1%, YUS-NV1420 5%, THIX-258 0.1%, calcined kaolin 2%, diatomite 1%, talcum powder up to 100%.

[0068] Example 12: 70% aluminium phosphonate triethyl · flumorph wettable powder

[0069] Aluminium phosphonate triethyl 50%, flumorph 20%, 2,2'-dihydroxy-5,5'-dipropyl-diphenyl 5%, YUS-NV12032 8%, Ufoxane 3A 5%, Tensiofix-CJK 0.1%, magnesium stearate 2%, sericite powder up to 100%.

[0070] Example 13: 50% aluminium phosphonate triethyl · flumorph wettable powder

[0071] Aluminium phosphonate triethyl 45%, flumorph 5%, 3,3',5,5'-tetramethyl-2,2'-diphenol 4%, YUS-NV12032 8%, YUS-NV1420 3%, Tensiofix-CJK 0.1%, citric acid 2%, calcined kaolin up to 100%.

[0072] Example 14: 30% aluminium phosphonate triethyl · flumorph wettable powder

[0073] Aluminium phosphonate triethyl 10%, flumorph 20%, 3,3',5,5'-tetramethyl-2,2'-diphenol 4%, Ufoxane 3A 2%, Borresperse NA 4%, citric acid 2%, tricalcium phosphate 1%, calcined kaolin up to 100%.

[0074] Example 15: 10% aluminium phosphonate triethyl · flumorph wettable powder

[0075] Aluminium phosphonate triethyl 5%, flumorph 5%, 2,2'-dihydroxydiphenyl 2%, sodium dodecylbenzenesulfonate 3A 2%, Ufoxane 3A 3%, G-920BQ 0.1%, citric acid 3%, calcined kaolin up to 100%.

[0076] Example 16: 80% aluminium phosphonate triethyl · benthival wettable powder

[0077] Aluminium phosphonate triethyl 70%, benthival 10%, 5',5-diallyl-2,2'-diphenol 1%, 2,2'-dihydroxy-5,5'-dipropyl-diphenyl 5%, YUS-SXC 2%, Borresperse NA 6%, G-920BQ 0.1%, magnesium stearate up to 100%.

[0078] Example 17: 70% fosetyl-Al + benthival wettable powder

[0079] Fosetyl-Al 50%, benthival 20%, 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenyl 5%, YUS- NV1203 4%, YUS-NV1420 4%, Tensiofix-CJK 0.1%, diatomaceous earth to 100%.

[0080] Example 18: 50% fosetyl-Al + benthival wettable powder

[0081] Fosetyl-Al 45%, benthival 5%, 5',5-diallyl-2,2'-dihydroxybiphenyl 4%, LX Special 4%, YUS-NV1420 4%, THIX-258 0.1%, sericite powder to 100%.

[0082] Example 19: 30% fosetyl-Al + benthival wettable powder

[0083] Fosetyl-Al 10%, benthival 20%, 5',5-diallyl-2,2'-dihydroxybiphenyl 4%, sodium dodecylbenzenesulfonate 2%, D900 3%, Tensiofix-CJK 0.2%, magnesium stearate 2%, sericite powder 5%, diatomaceous earth to 100%.

[0084] Example 20: 10% fosetyl-Al + benthival wettable powder

[0085] Fosetyl-Al 5%, benthival 5%, 2,2'-dihydroxy-5,5'-dipropylbiphenyl 2%, PICO-NW 12%, D900 2%, benzoic acid 0.5%, diatomaceous earth to 100%.

[0086] Comparative Example 1: 80% fosetyl-Al + dimoxystrobin wettable powder

[0087] Fosetyl-Al 70%, dimoxystrobin 10%, Morwet EFW 1%, Ultrazine NA 6%, G-920BQ 0.1%, white carbon to 100%.

[0088] Comparative Example 2: 70% fosetyl-Al + dimoxystrobin wettable powder

[0089] Fosetyl-Al 50%, dimoxystrobin 20%, Borresperse NA 3%, Ultrazine NA 5%, G-920BQ 0.1%, white carbon 3%, sericite powder to 100%.

[0090] Comparative Example 3: 50% aluminum trisethylphosphonate · maleic hydrazide wettable powder

[0091] aluminum trisethylphosphonate 45%, maleic hydrazide 5%, LX Special 3%, D900 5%, G-920BQ 0.1%, sericite powder to make up to 100%.

[0092] Comparative Example 4: 30% aluminum trisethylphosphonate · maleic hydrazide wettable powder

[0093] aluminum trisethylphosphonate 10%, maleic hydrazide 20%, sodium dodecylbenzenesulfonate 2%, D900 3%, Tensiofix-CJK 0.2%, sodium citrate 1%, calcined kaolin 10%, sericite powder to make up to 100%. Comparative Example 5: 10% aluminum trisethylphosphonate · maleic hydrazide wettable powder

[0094] aluminum trisethylphosphonate 5%, maleic hydrazide 5%, sodium dodecylsulfate 2%, D900 2%, Tensiofix-CJK 0.2%, sodium citrate 2%, sericite powder to make up to 100%.

[0095] Comparative Example 6: 80% aluminum trisethylphosphonate · dimethomorph wettable powder

[0096] aluminum trisethylphosphonate 70%, dimethomorph 10%, PICO-U100 2%, Greensperse CA-N 5%, Tensiofix-CJK 0.1%, talc to make up to 100%.

[0097] Comparative Example 7: 70% aluminum trisethylphosphonate · dimethomorph wettable powder

[0098] aluminum trisethylphosphonate 50%, dimethomorph 20%, LX Special 3%, Ultrazine NA 5%, THIX-25 0.1%, talc 1%, sericite powder to make up to 100%.

[0099] Comparative Example 8: 50% aluminum trisethylphosphonate · dimethomorph wettable powder

[0100] aluminum trisethylphosphonate 45%, dimethomorph 5%, Ufoxane 3A 2%, Borresperse NA 5%, G-920BQ 0.1%, talc 1%, sericite powder to make up to 100%.

[0101] Comparative Example 9: 30% aluminum trisethylphosphonate · dimethomorph wettable powder

[0102] aluminum trisethylphosphonate 10%, dimethomorph 20%, Ufoxane 3A 2%, Borresperse NA 4%, sericite powder 5%, anhydrous sodium sulfate to make up to 100%.

[0103] Example 10: 10% fentin acetate + dimetnam + spirodiclofen WP

[0104] Fentin acetate 5%, dimetnam 5%, sodium dodecylbenzenesulfonate 2%, Borresperse NA 3%, Tensiofix-CJK 0.2%, tricalcium phosphate to 100%.

[0105] Example 11: 80% fentin acetate + dimetnam + flumorph WP

[0106] Fentin acetate 70%, dimetnam 10%, Morwet EFW 1%, YUS-NV1420 5%, THIX-258 0.1%, calcined kaolin 2%, diatomite 1%, talc powder to 100%. Example 12: 70% fentin acetate + dimetnam + flumorph WP

[0107] Fentin acetate 50%, dimetnam 20%, YUS-NV1203 2%, Ufoxane 3A 5%, Tensiofix-CJK 0.1%, magnesium stearate 2%, sericite powder to 100%.

[0108] Example 13: 50% fentin acetate + dimetnam + flumorph WP

[0109] Fentin acetate 45%, dimetnam 5%, YUS-NV1203 2%, YUS-NV1420 3%, Tensiofix-CJK 0.1%, citric acid 2%, calcined kaolin to 100%.

[0110] Example 14: 30% fentin acetate + dimetnam + flumorph WP

[0111] Fentin acetate 10%, dimetnam 20%, Ufoxane 3A 2%, Borresperse NA 4%, citric acid 2%, tricalcium phosphate 1%, calcined kaolin to 100%.

[0112] Example 15: 10% fentin acetate + dimetnam + flumorph WP

[0113] Fentin acetate 5%, dimetnam 5%, sodium dodecylbenzenesulfonate 3A 2%, Ufoxane 3A 3%, G-920BQ 0.1%, citric acid 3%, calcined kaolin to 100%.

[0114] Example 16: 80% fentin acetate + ethaboxam WP

[0115] Aluminum phosphonate triethyl 70%, benthival 10%, YUS-SXC 2%, Borresperse NA 6%, G-920BQ 0.1%, magnesium stearate to 100%.

[0116] Comparative Example 17: 70% aluminum phosphonate triethyl · benthival wettable powder

[0117] Aluminum phosphonate triethyl 50%, benthival 20%, YUS-NV1203 4%, YUS-NV1420 4%, Tensiofix-CJK 0.1%, diatom earth to 100%.

[0118] Comparative Example 18: 50% aluminum phosphonate triethyl · benthival wettable powder

[0119] Aluminum phosphonate triethyl 45%, benthival 5%, LX Special 4%, YUS-NV1420 4%, THIX-258 0.1%, sericite powder to 100%.

[0120] Comparative Example 19: 30% aluminum phosphonate triethyl · benthival wettable powder

[0121] Aluminum phosphonate triethyl 10%, benthival 20%, sodium dodecylbenzenesulfonate 2%, D900 3%, Tensiofix-CJK 0.2%, magnesium stearate 2%, sericite powder 5%, diatom earth to 100%. Comparative Example 20: 10% aluminum phosphonate triethyl · benthival wettable powder

[0122] Aluminum phosphonate triethyl 5%, benthival 5%, PICO-NW1 2%, D900 2%, benzoic acid 0.5%, diatom earth to 100%.

[0123] Comparative Example 21: 50% aluminum phosphonate triethyl wettable powder

[0124] Aluminum phosphonate triethyl 70%, Morwet EFW 1%, Ultrazine NA 6%, G-920BQ 0.1%, white carbon to 100%.

[0125] Comparative Example 22: 10% dimethomorph wettable powder

[0126] Dimethomorph 10%, Morwet EFW 1%, Ultrazine NA 6%, G-920BQ 0.1%, white carbon to 100%.

[0127] Comparative Example 23: 10% mandipropamid wettable powder

[0128] Amicarbalide 10%, PICO-U100 2%, Greensperse CA-N 5%, Tensiofix-CJK 0.1%, talcum to 100%.

[0129] Comparative Example 24: 10% flumorph WP

[0130] Flumorph 10%, Morwet EFW 1%, YUS-NV1420 5%, THIX-258 0.1%, calcined kaolin 2%, diatomite 2%, talcum to 100%.

[0131] Comparative Example 25: 10% ethaboxam WP

[0132] Ethaboxam 10%, YUS-SXC 2%, Borresperse NA 6%, G-920BQ 0.1%, magnesium stearate to 100%.

[0133] Examples 1-20 are wettable powder formulations of different content of aluminum tris (ethylphosphonate) and another amide fungicide with the addition of a stabilizer;

[0134] Comparative Examples 1-20 are wettable powder formulations of different content of aluminum tris (ethylphosphonate) and another amide fungicide without the addition of a stabilizer;

[0135] Comparative Examples 21-25 are wettable powder formulations of aluminum tris (ethylphosphonate) or amide fungicide as a single agent;

[0136] The samples of the formulations obtained in the above examples and comparative examples were tested for wetting and suspension rate:

[0137] 1) Wetting test: According to the method specified in GB / T 5451-2001, first the wetting of the sample in the examples and comparative examples under standard conditions was tested; then the water in the above method was replaced with water at 15°C or 10°C, and the wetting of the sample in the examples and comparative examples under special conditions was tested (the results are shown in Table 1).

[0138] 2) Suspension rate test: According to the method specified in GB / T 14825-2023, the suspension rate of the active ingredient in the formulation under standard conditions was tested; then the standard hard water in the above method was replaced with water with 1.5 times or 3 times hardness, and the suspension rate of the sample in the examples and comparative examples under special conditions was tested (the results are shown in Table 2).

[0139] Table 1. Wetting of the sample in the examples and comparative examples in water at different temperatures

[0140]

[0141]

[0142] As shown in the data in Table 1, the single dose of each of them has good wetting property (Comparative Examples 21-25), but the wetting property is significantly reduced after mixing without adding the stabilizer, and is obviously affected by the water temperature, while the stabilizer with the biphenyl substance having the 2,2'-dihydroxy structure can significantly improve the wetting property of the mixed sample at different temperatures. In the standard 25℃ water, the examples 1-20 with the added stabilizer show shorter wetting time and faster wetting speed; when the temperature is lowered to 15℃, the wetting time of the comparative examples 1-20 without the added stabilizer is significantly increased and is much greater than that of the examples 1-20 (all less than 30s); when the water temperature is further lowered to 10℃, the wetting time of the comparative examples 1-20 without the added stabilizer is all greater than 120s, and some even reach more than 180s (Comparative Example 1, Comparative Example 2, Comparative Example 6, Comparative Example 11, Comparative Example 12, Comparative Example 16), while the wetting time of the examples 1-20 can still be controlled within 30s. The above experiments fully show that the stabilizer with the biphenyl substance having the 2,2'-dihydroxy structure can effectively solve the problem of difficult wetting of the mixed sample in water at different temperatures.

[0143] Table 2. Suspension rate of the example and comparative example samples in water with different hardness

[0144]

[0145]

[0146]

[0147] As shown in the data in Table 2, the single dose of each of them has good suspension rate (Comparative Examples 21-25), but the suspension rate is significantly reduced after mixing without adding the stabilizer, and is obviously affected by the hardness of the water, while the stabilizer with the biphenyl substance having the 2,2'-dihydroxy structure can significantly improve the suspension rate of the mixed sample in water with different hardness. In the standard hard water, the suspension rate of the two active components in the examples 1-20 with the added stabilizer can all be maintained at more than 95%, which is significantly better than that of the comparative examples 1-20 without the added stabilizer; and when the hardness is increased to 1.5 times and 3 times of the standard, the suspension rate of the two active components in the comparative examples 1-20 is further reduced, but the examples 1-20 still show good suspension rate under the action of the stabilizer.

[0148] As shown above, the present application effectively solves the pain point problem of the sample in the actual application process, improves the suspension rate and wetting property of the mixed sample in water with different hardness and temperature, and effectively guarantees the play of the drug efficacy, so that the formulation is more reliable and easy to use than the original drug and the conventional sample.

[0149] And, the stabilizer added in the present application is suitable for the ratio combination in all content ranges in the claims, and is not limited to the above examples.

Claims

1. A wettable powder containing a stabilizer, consisting of an active ingredient and an adjuvant, characterized in that: The active component is aluminum trisethylphosphinate and an amide bactericide (B), the auxiliary agent contains a stabilizer, the stabilizer is one or more of biphenyl substances with 2,2'-dihydroxy structure, and the addition amount is 0.1-30% of the mass of the preparation.

2. The wettable powder containing stabilizer according to claim 1, characterized in that: The active component is aluminum trisethylphosphinate and an amide bactericide (B), which accounts for 2-90% of the mass of the preparation; wherein the amide bactericide (B) is selected from one of the following: dimoxystrobin (B1), mandipropamid (B2), flumorph (B3) and fenhexamid (B4).

3. The wettable powder containing stabilizer according to claim 1, characterized in that: The biphenyl substances with 2,2'-dihydroxy structure have the following structural formula: wherein R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' may be the same or different and are selected from the group consisting of hydrogen, halogen, C1-C 12 alkyl, C2-C 12 alkenyl, C2-C 12 alkynyl, aryl, benzyl, which are unsubstituted or substituted by at least one halogen.

4. The wettable powder containing stabilizers according to any one of claims 1 to 3, characterized in that: The wettable powder contains, by weight percentage, 2-90% of the active ingredient, 0.1-30% of the stabilizer, 1-30% of the wetting dispersant, 1-75% of the filler, and 0-20% of other auxiliary agents; wherein the aluminum trisethylphosphinate in the active component accounts for 1-80% of the mass of the preparation, and the amide bactericide (B) accounts for 1-50% of the mass of the preparation.

5. The wettable powder containing stabilizer according to claim 4, characterized in that: The other auxiliary agents are selected from one or more of the following: antifoaming agents, pH regulators, penetrants, synergists, and spreading agents.

6. The wettable powder containing stabilizer according to claim 4, characterized in that: The wettable powder contains, by weight percentage, 10-85% of the active ingredient, 0.1-20% of the stabilizer, 1-20% of the wetting dispersant, 1-60% of the filler, and 0-10% of other auxiliary agents.

7. The wettable powder containing stabilizer according to claim 6, characterized in that: The active component aluminum trisethylphosphinate accounts for 5-70% of the mass of the preparation, and the amide bactericide B accounts for 5-30% of the mass of the preparation. The stabilizer is one or more of the following: 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-2,2'-biphenol, 2,2'-dihydroxy-5,5'-dipropylbiphenyl, and 5',5-diallyl-2,2'-biphenyldiol, and the addition amount is 0.1-20% of the mass of the preparation.

8. The wettable powder containing stabilizer according to claim 6, characterized in that: The wetting dispersant is one or more of the following: polycarboxylate, lignin sulfonate, lignin sulfate, alkyl naphthalene sulfonate, dodecyl sulfate, dodecyl benzene sulfonate, ethoxylated alcohol, and polyoxyethylene ether. The filler is one or more of the following: kaolin, sericite powder, calcined kaolin, attapulgite, zeolite powder, pyrophyllite powder, magnesium stearate, meerschaum powder, light calcium carbonate, anhydrous sodium sulfate, diatomite, tricalcium phosphate, white carbon black, and talc powder.

9. The wettable powder containing stabilizer according to claim 6, characterized in that: The wetting dispersant is one or more of the following: polycarboxylate, lignin sulfate, dodecyl sulfate, ethoxylated alcohol, and polyoxyethylene ether. The filler is one or more of the following: sericite powder, calcined kaolin, magnesium stearate, tricalcium phosphate, anhydrous sodium sulfate, white carbon black, and talc powder.

10. Use of the wettable powder containing stabilizer according to claim 1, characterized in that: The wettable powder containing the stabilizer is applied in sterilization control in places.

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