Aqueous suspension concentrate containing acequinocyl, and preparation method therefor and use thereof

Abstract

An aqueous suspension concentrate containing acequinocyl, and a preparation method therefor and a use thereof, relating to the field of pesticides. The aqueous suspension concentrate comprises the following raw materials in percentage by weight: 1-50% of acequinocyl, 0.5-25% of a polymeric carboxylic acid copolymer, 0-1.0% of an EO / PO block polyether, water, and a formulation excipient, wherein the formulation excipient is selected from one or more of an anti-freezing agent, a thickening agent, a defoaming agent, or a preservative. By means of a functional dispersant (the polymeric carboxylic acid copolymer, or the polymeric carboxylic acid copolymer and the EO / PO block polyether), after stored at 54°C for 14 days, the formulation has uniform and stable appearance and properties, has no caking, creaming or precipitate, and has all quality indexes meet national standards, and actual transportation, storage and use requirements.

Description

Aqueous suspensions containing acaricide quinone, their preparation methods and applications

[0001] Cross-referencing

[0002] This application claims priority to Chinese Patent Application No. 202410552800.8, filed on May 7, 2024, entitled "An Aqueous Suspension Containing Acaricide Quinone and Its Preparation Method and Application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of pharmaceutical technology, and in particular to an aqueous suspension containing acaricide quinone, its preparation method, and its application. Background Technology

[0004] Acaricide quinone, scientifically known as 2-(acetoxy)-3-dodecyl-1,4-naphthoquinone, is a contact-type quinone acaricide and nematicide. Its primary mode of action is contact, with some potential for oral inhalation. Due to its high efficacy and safety, the European Union has included it in Appendix I, granting it registration for use.

[0005] The pure acaricide quinone is a pale yellow powder with the molecular formula C24H. 32 O4, CAS No. 57960-19-7; relative molecular weight 384.51; melting point of pure product 59.6℃, melting point range of industrial grade technical grade is 50-60℃.

[0006] Aqueous suspension concentrates (SCs) of pesticides refer to multiphase dispersion systems formed by dispersing solid active ingredients (non-soluble in water) in water with a particle size of approximately 0-5 micrometers after processing using certain mechanical means (sand milling or ball milling). These concentrates are required to maintain a uniform appearance and flowability, small particle size, low viscosity, and high suspension rate even after storage and transportation at different temperatures. Active ingredients suitable for processing into aqueous suspension concentrates generally require stable content in water, water solubility of less than 100 mg / L, and a melting point greater than 60 degrees Celsius.

[0007] Since the melting point of the industrial-grade acaricide is between 50-60℃, it is prone to particle size growth and agglomeration during the processing and heating of the aqueous suspension, resulting in severe product deterioration and inability to be used normally. These conditions greatly limit the application of acaricide aqueous suspension. Summary of the Invention

[0008] Purpose of the invention

[0009] The purpose of this invention is to provide an aqueous suspension containing acaricide quinone, its preparation method and application, which solves the problem of acaricide quinone easily forming a paste and clumping when heated during the industrial development of aqueous suspensions. It can provide a storage-stable aqueous suspension of acaricide quinone. By introducing a shielding agent and a functional polymer dispersant, the phenomenon of acaricide quinone forming a paste and clumping after heating or hot storage can be effectively suppressed.

[0010] Solution

[0011] To achieve the purpose of this application, embodiments of the present invention provide an acaricide aqueous suspension, comprising the following raw materials in weight fractions: acaricide 1-50%, high molecular weight carboxylic acid copolymer 0.5-25%, EO-PO block polyether 0-1.0%, water, and formulation excipients; wherein the formulation excipients are selected from one or more of antifreeze, thickener, defoamer, and preservative.

[0012] Further, the weight ratio of acaricide to the high molecular weight carboxylic acid copolymer is (0.1-5):1, optionally (0.1-4.5):1, optionally (0.5-4.4):1, optionally (0.5-4):1, optionally (0.5-3):1.

[0013] Further, the weight ratio of the high molecular weight carboxylic acid copolymer to the EO-PO block polyether is (6.5-200):(0-1), optionally (6.5-200):1, optionally (7.5-200):1, optionally (7.5-60):1.

[0014] Further, the EO-PO block polyether is selected from one or more of ethylene oxide-propylene oxide block copolymers initiated by ethylenediamine, ethylene oxide-propylene oxide block copolymers initiated by hydroxystearic acid, ethylene oxide-propylene oxide block copolymers initiated by propylene glycol, and ethylene oxide-propylene oxide block copolymers initiated by butanol; optionally, the average molecular weight of the EO-PO block polyether is ≥4000, optionally 4000 to 20000. It includes, but is not limited to, one or more of PE10500 (BASF), Synperonic PE / P105 (CRODA), Synperonic T / 908 (CRODA), Atlox 4912 (CRODA), and Atlox 4914 (CRODA).

[0015] Furthermore, the high molecular weight carboxylic acid copolymer includes one or more of comb-grafted acrylic acid copolymers, maleic acid copolymers, and sorbitol-fatty acid copolymers.

[0016] Optionally, the functional monomers of the comb-grafted acrylic acid copolymer include carboxyl monomers, and optionally also include one or more of alkyl monomers, ether monomers, and sulfonic acid monomers; optionally, the average molecular weight of the high molecular weight carboxylic acid copolymer is ≥4000, and optionally is 4000-25000.

[0017] The chemical structure of the comb-grafted acrylic copolymer can optionally be as follows (including but not limited to):

[0018] In formula (1), a, b, c, and d represent the polymerization quantities of the corresponding monomers, which can be adjusted according to requirements. The above structural formula provides a possible structure for a comb-shaped grafted acrylic copolymer. Generally speaking, comb-shaped grafted acrylic copolymers with similar structures can meet the objectives of this invention.

[0019] Optionally, the high molecular weight carboxylic acid copolymer includes comb-grafted acrylic acid copolymer, and further includes one, two, or some of maleic acid copolymer and sorbitol-fatty acid copolymer; optionally, the comb-grafted acrylic acid copolymer includes, but is not limited to, Atlox 4917 (CRODA), Atlox 4916 (CRODA), T2612 (Indorama), Plexsurf 8000 (Solvay), Atlox 4913 (CRODA), GEROPON T / 36 (Solvay), and Agrilan 755 (nouryon). One or more of 2500 (HUNTSMAN), D205 (Dow Chemical), and TRN (Lamberti).

[0020] Optionally, when the content of acaricide quinone is ≥20% (e.g., 20-30%, 20-40%, or 20-25%), the content of the high molecular weight carboxylic acid copolymer is ≥6%.

[0021] Optionally, when the content of acaricide quinone is ≥30%, the content of the high molecular weight carboxylic acid copolymer is ≥7%.

[0022] Furthermore, the high molecular weight carboxylic acid copolymer includes comb-grafted acrylic acid copolymer, and also includes one or two of maleic acid copolymer and sorbitol-fatty acid copolymer.

[0023] Further, it includes the following raw materials in weight fractions: 1-50% miticide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, 0-1.0% EO-PO block polyether, water, and formulation excipients. Optionally, the amount of the high molecular weight carboxylic acid copolymer used is 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or any two of the above figures; optionally, the amount of EO-PO block polyether used is 0%, 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, or any two of the above figures.

[0024] Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients; optionally, the amount of high molecular weight carboxylic acid copolymer used is 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or any two of the above figures.

[0025] Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 6-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients. Optionally, the amount of the high molecular weight carboxylic acid copolymer used is 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or any two of the above figures.

[0026] Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 12-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients. Optionally, the amount of the high molecular weight carboxylic acid copolymer is 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or any two of the above figures.

[0027] Optionally, the raw materials may include the following weight fractions: 1-50% miticide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether, water, and formulation excipients.

[0028] Optionally, the raw materials include the following weight fractions: 5-50% miticide quinone, 4-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0029] Optionally, the raw materials include the following weight fractions: 5-40% miticide quinone, 5-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0030] Optionally, the raw materials include the following weight fractions: 10-20% miticide quinone, 6-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0031] Optionally, the raw materials include the following weight fractions: 10-20% miticide quinone, 6-10% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0032] Optionally, the raw materials include the following weight fractions: 20-40% miticide quinone, 6-25% (optionally 7-25%) high molecular weight carboxylic acid copolymer, 0.1-1.0% (optionally 0.5-1.0%) EO-PO block polyether, water, and formulation excipients.

[0033] Optionally, the raw materials include the following weight fractions: 20-40% miticide quinone, 8-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0034] Optionally, the raw materials include the following weight fractions: 30-40% miticide quinone, 8-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

[0035] Optionally, the content of EO-PO block polyether should not be too high, as excessive content may lead to paste formation.

[0036] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: 0-10% antifreeze, 0-2% thickener, 0-4% defoamer, and 0-5% preservative.

[0037] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: 3-10% antifreeze, 0.3-2% thickener, 0.3-4% defoamer, and 0.5-5% preservative.

[0038] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: 3-10% antifreeze, 0.3-2% thickener, 0.3-4% defoamer, and 0.5-5% preservative.

[0039] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: 5-10% antifreeze, 0.8-2% thickener, 0.5-4% defoamer, and 0.5-5% preservative.

[0040] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: xanthan gum 0-0.5%, magnesium aluminum silicate 0.5-2.0%, silica 0-10%, isothiazolinone 0-10%, antifreeze 0-10%, and defoamer 0-10%.

[0041] Furthermore, the aqueous suspension contains the following dosage form excipients by weight: xanthan gum 0.3-0.5%, magnesium aluminum silicate 0.5-2.0%, silica 0-10%, isothiazolinone 0.5-10%, antifreeze 5-10%, and defoamer 0.5-10%;

[0042] Furthermore, the antifreeze is selected from one or more of ethylene glycol, propylene glycol, and urea.

[0043] Furthermore, the defoamer is dimethyl silicone oil and / or polyether silicone.

[0044] Furthermore, the formulation may contain 0-2.0% dye, optionally an azo dye or a triphenylmethane dye.

[0045] Furthermore, it also includes other pesticide active ingredients, optionally including spirodiclofen.

[0046] Furthermore, the water level was replenished to 100%.

[0047] In a second aspect, a method for preparing the aqueous suspension agent described in the first aspect is provided, comprising: firstly mixing the acaricide technical, the high molecular weight carboxylic acid copolymer, the EO-PO block polyether, water, and formulation excipients in a certain proportion, then shearing and milling to obtain an aqueous suspension agent that is dispersible in water; optionally, milling to a particle size of less than 5 micrometers.

[0048] Thirdly, the application of the acaricide quinone aqueous suspension described in the first aspect in the control of plant pests is provided.

[0049] Further, the plant pests are mites, aphids, or nematodes. Optionally, the mites are selected from one or more of spider mites and rust mites; optionally, the spider mites include one or more of the following: carmine spider mite, hawthorn spider mite, oval short-haired mite, and citrus spider mite; optionally, the rust mites include one or more of the following: citrus leaf gall mite, rust mite, and rust spider mite.

[0050] The equipment used in the processing of the formulations of this invention is all publicly known. Beneficial effects

[0051] The acaricide quinone aqueous suspension of the present invention, by introducing or combining a functional dispersant—comb-grafted acrylic acid copolymer—ensures that the formulation exhibits uniform and stable appearance after storage at 54°C for 14 days, without clumping, paste formation, or precipitation, and meets all quality indicators of national standards, actual transportation, storage, and use requirements. Attached Figure Description

[0052] One or more embodiments are illustrated by way of example with reference to the accompanying drawings, and these illustrative examples are not intended to limit the embodiments. The term "illustrative" as used herein means "serving as an example, embodiment, or illustration." Any embodiment illustrated herein as "illustrative" is not necessarily to be construed as superior to or better than other embodiments.

[0053] Figure 1 shows the appearance of the miticide preparation after 14 days of heat storage at 54°C. A, B, C, D, and E are the appearance of the miticide preparations after 14 days of heat storage at 54°C in Examples 2, 4, 7, 13, and 28, respectively; F and G are the appearance of the miticide preparations after 14 days of heat storage at 54°C in Examples 30 and 41, respectively. Detailed Implementation

[0054] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0055] Furthermore, to better illustrate this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented without certain specific details. In some embodiments, materials, methods, techniques, etc., well-known to those skilled in the art, are not described in detail in order to highlight the main points of this application.

[0056] 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 elements or components without excluding other elements or other components.

[0057] The acaricide quinone of the present invention can be obtained commercially.

[0058] In the following examples, the preparation method of the aqueous suspension is as follows: First, the acaricide technical, dispersant, water, excipients, etc. are weighed and mixed, and then sheared and mixed for a certain period of time. Then, the slurry is ground to a particle size of less than 5 micrometers to obtain an aqueous suspension with uniform appearance and dispersibility in water.

[0059] Example 1:

[0060] A water suspension was prepared by grinding the following ingredients: 10% miticide quinone, 5% styrene phenol polyether phosphate, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0061] Example 2:

[0062] A water suspension was prepared by grinding 10% miticide quinone, 3% polyphenol sulfonate, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water in a sand mill.

[0063] Example 3:

[0064] A water suspension was prepared by grinding 10% miticide quinone, 5% succinic anhydride, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water in a sand mill.

[0065] Example 4:

[0066] A water suspension was prepared by grinding the following ingredients: 10% miticide quinone, 5% polyphenol sulfonate, 5% propylene glycol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0067] Example 5:

[0068] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 5% tristyrene phenol polyether phosphate, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0069] Example 6:

[0070] A water suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 5% polyphenol sulfonate, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0071] Example 7:

[0072] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 5% succinic anhydride, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0073] Example 8:

[0074] A water suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0075] Example 9:

[0076] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 5% propylene glycol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0077] Example 10:

[0078] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 2% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0079] Example 11:

[0080] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 0.5% comb-grafted acrylic acid copolymer, 2% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0081] Example 12:

[0082] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0083] Example 13:

[0084] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 7.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0085] Example 14:

[0086] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 0.1% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0087] Example 15:

[0088] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 0.5% butanol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0089] Example 16:

[0090] A water suspension was prepared by grinding the following components: 15% miticide quinone, 1% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0091] Example 17:

[0092] A water suspension was prepared by grinding the following components: 15% miticide quinone, 2% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0093] Example 18:

[0094] A water suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0095] Example 19:

[0096] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 2.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0097] Example 20:

[0098] The aqueous suspension was prepared by grinding the following components: 15% acaricide, 4% comb-grafted acrylic acid copolymer, 1.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0099] Example 21:

[0100] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 1.5% butanol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0101] Example 22:

[0102] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 2.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0103] Example 23:

[0104] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 2% propylene glycol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0105] Example 24:

[0106] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 1.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0107] Example 25:

[0108] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 1.5% propylene glycol-initiated EO-PO block polyether, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0109] Example 26:

[0110] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 4% comb-grafted acrylic acid copolymer, 2.0% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0111] Example 27:

[0112] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 7% comb-grafted acrylic acid copolymer, 2.0% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0113] Example 28:

[0114] The aqueous suspension was prepared by grinding the following components: 15% acaricide, 6% comb-grafted acrylic acid copolymer, 2.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0115] Example 29:

[0116] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 6% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0117] Example 30:

[0118] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 10% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0119] Example 31:

[0120] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 8% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 2% maleic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0121] Example 32:

[0122] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 8% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 2% sorbitol-fatty acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0123] Example 33:

[0124] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 6.5% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0125] Example 34:

[0126] The aqueous suspension was prepared by grinding the following components: 15% miticide quinone, 7.3% comb-grafted acrylic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0127] Example 35:

[0128] The aqueous suspension was prepared by grinding the following components: 20% acaricide, 8.0% comb-grafted acrylic acid copolymer, 2.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0129] Example 36:

[0130] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0131] Example 37:

[0132] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 8.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0133] Example 38:

[0134] The aqueous suspension was prepared by grinding the following components: 20% acaricide, 6.0% comb-grafted acrylic acid copolymer, 3% sorbitol-fatty acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0135] Example 39:

[0136] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 3% sorbitol-fatty acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0137] Example 40:

[0138] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0139] Example 41:

[0140] The acaricide is prepared by grinding the following components: 20% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0141] Example 42:

[0142] The acaricide is prepared by grinding the following components: 20% miticide quinone, 6% polyphenol sulfonate, 3% maleic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0143] Example 43:

[0144] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 6% polyphenol sulfonate, 3% sorbitol-fatty acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0145] Example 44:

[0146] The aqueous suspension is prepared by grinding the following components: 20% miticide quinone, 6% polyphenol sulfonate, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0147] Example 45:

[0148] The aqueous suspension was prepared by grinding the following components: 20% miticide quinone, 6% polyphenol sulfonate, 3% sorbitol-fatty acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0149] Example 46:

[0150] The aqueous suspension is prepared by grinding the following components: 30% miticide quinone, 3% tristyrene phenol polyether phosphate, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0151] Example 47:

[0152] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 2.0% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0153] Example 48:

[0154] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 6.8% comb-grafted acrylic acid copolymer, 2.0% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0155] Example 49:

[0156] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 9.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0157] Example 50:

[0158] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 10.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0159] Example 51:

[0160] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 3% sorbitol-fatty acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0161] Example 52:

[0162] The acaricide is prepared by grinding the following components: 30% miticide quinone, 6.0% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0163] Example 53:

[0164] The aqueous suspension was prepared by grinding the following components: 30% acaricide, 8.0% comb-grafted acrylic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0165] Example 54:

[0166] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 10.0% comb-grafted acrylic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0167] Example 55:

[0168] The aqueous suspension was prepared by grinding the following components: 30% acaricide, 8.0% comb-grafted acrylic acid copolymer, 3% sorbitol-fatty acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0169] Example 56:

[0170] The aqueous suspension was prepared by grinding the following components: 30% acaricide, 8.0% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0171] Example 57:

[0172] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 10.0% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 1.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0173] Example 58:

[0174] The aqueous suspension is prepared by grinding the following components: 40% miticide quinone, 7% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water.

[0175] Example 59:

[0176] The aqueous suspension was prepared by grinding the following components: 40% acaricide, 7.5% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0177] Example 60:

[0178] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 8.5% comb-grafted acrylic acid copolymer, 3% maleic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0179] Example 61:

[0180] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 9.0% comb-grafted acrylic acid copolymer, 0.5% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0181] Example 62:

[0182] The aqueous suspension was prepared by grinding the following components: 40% acaricide, 10.0% comb-grafted acrylic acid copolymer, 5% maleic acid copolymer, 2.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0183] Example 63:

[0184] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 10.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0185] Example 64:

[0186] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 10.5% comb-grafted acrylic acid copolymer, 1.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0187] Example 65:

[0188] The aqueous suspension was prepared by grinding the following components: 40% acaricide, 9.0% comb-grafted acrylic acid copolymer, 1.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0189] Example 66:

[0190] The aqueous suspension was prepared by grinding the following components: 40% acaricide, 16% comb-grafted acrylic acid copolymer, 1.0% ethylenediamine-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0191] Example 67:

[0192] The aqueous suspension was prepared by grinding the following components: 5% miticide quinone, 5% spirodiclofen, 9.0% comb-grafted acrylic acid copolymer, 1.0% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0193] Example 68:

[0194] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 5% spirodiclofen, 10.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0195] Example 69:

[0196] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 5% spirodiclofen, 16.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0197] Example 70:

[0198] The aqueous suspension was prepared by grinding the following components: 5% miticide quinone, 10% spirodiclofen, 7.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0199] Example 71:

[0200] The aqueous suspension was prepared by grinding the following components: 10% miticide quinone, 30% spirodiclofen, 10.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0201] Example 72:

[0202] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 20% spirodiclofen, 25.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0203] Example 73:

[0204] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 30% spirodiclofen, 25.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0205] Example 74:

[0206] The aqueous suspension was prepared by grinding the following components: 5% miticide quinone, 5% spirodiclofen, 12.0% comb-grafted acrylic acid copolymer, 0.5% hydroxystearic acid-initiated ethylene oxide-propylene oxide block copolymer (EO-PO block polyether), 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0207] Example 75:

[0208] The acaricide is prepared by grinding 10% miticide quinone, 12.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water in a sand mill.

[0209] Example 76:

[0210] The acaricide is prepared by grinding 20% ​​acaricide, 15.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder is water in a sand mill.

[0211] Example 77:

[0212] The aqueous suspension was prepared by grinding the following components: 30% miticide quinone, 19.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0213] Example 78:

[0214] The aqueous suspension was prepared by grinding the following components: 40% miticide quinone, 23.0% comb-grafted acrylic acid copolymer, 0.3% xanthan gum, 0.5% magnesium aluminum silicate, 0.5% isothiazolinone, 5% ethylene glycol, 0.5% defoamer, and the remainder being water.

[0215] The defoamer in the above embodiments is dimethyl silicone oil.

[0216] In the above embodiments, the comb-shaped grafted acrylic copolymer is Atlox 4917 (CRODA), but other comb-shaped grafted acrylic copolymers can also be used, such as, but not limited to, Atlox 4917 (CRODA), Atlox 4916 (CRODA), T2612 (Indorama), Plexsurf 8000 (Solvay), Atlox 4913 (CRODA), GEROPON T / 36 (Solvay), and Agrilan 755 (nouryon). One or more of 2500 (HUNTSMAN), D205 (Dow Chemical), and TRN (Lamberti) can meet the requirements of this invention. These can be purchased from, but are not limited to, Croda, BASF, Solvay, Clariant, and Dow.

[0217] Different starting EO-PO block polyethers were purchased from, but not limited to, Croda, BASF, Nouryon, Lamberti, and HUNTSMAN.

[0218] According to relevant regulations on pesticide registration management, pesticide formulations must undergo accelerated storage testing at 54℃ for 14 days to ensure the quality of the product during transportation and storage before use.

[0219] After being stored at 54℃ for 14 days, the above-mentioned aqueous suspension formulations underwent a 54℃ heat storage test (GB / T 19136-2003 Method for Determination of Heat Storage Stability of Pesticides). The various indicators and performance of the acaricide quinone aqueous suspension formulation are shown in Table 1 below.

[0220] Table 1 Performance of Aqueous Suspension after 14 Days of Heat Storage at 54 Degrees Celsius

[0221] Note 1: In the appearance indicators column, the part before the slash corresponds to "normal temperature state", and the part after the slash corresponds to "cooled for 2 hours after heat storage".

[0222] Note 2: The lower the particle size growth rate after heat storage, the lower the viscosity, the higher the suspension rate, and the better the product quality stability.

[0223] As shown in Table 1, Examples 1 to 4, which did not use the technical solution described in this invention, showed severe agglomeration after 14 days of heat storage at 54°C, resulting in poor product quality and unusable products. Examples 5 to 8, which used succinic anhydride, tristyrene phenol polyether phosphate, or polyphenol sulfonate other than those described in this invention, combined with the comb-like grafted acrylic copolymer of this invention, showed fluidity after 14 days of heat storage at 54°C, without complete paste formation or solidification, but still with some original drug particles precipitating out. This indicates that the comb-like grafted acrylic copolymer of this invention has a significant improvement effect on heat storage. Examples 9 to 11, which used the adjuvant combination scheme described in this invention, showed no agglomeration after 2 hours of cooling after 14 days of heat storage at 54°C, and only slight agglomeration after 7 days of further cooling. The appearance and flowability were also significantly improved compared to other adjuvant schemes. However, the increase in particle size was still as high as 3-5 times, and the suspension rate was significantly lower than that of the room temperature sample. This shows that the adjuvant did improve thermal stability to some extent, but it was still insufficient to significantly improve the overall quality after heat storage. Examples 12-13, using the comb-like grafted acrylic copolymers described in this invention with increased quantities, improved the paste-like formation problem during the transition from heat storage to room temperature, significantly enhancing fluidity. Only a small amount of paste-like active ingredient remained on the surface, leading to a decrease in overall suspension rate, but this still demonstrates that these polymers improve thermal stability. Examples 14-15, using various types and combinations of the comb-like grafted acrylic copolymers described in this invention, combined with ethylenediamine-initiated EO-PO block polyethers, showed no clumping even after 14 days of heat storage at 54°C and 7 days of cooling. Appearance and fluidity remained good, viscosity did not increase significantly, and particle size growth was reduced to 1-2 times. Only the suspension rate was still somewhat low, around 80%-90%.Examples 16-28 use the adjuvants of the present invention, but without the correct combination or a certain quantity. However, the fluidity after heat storage is still guaranteed. Immediate use does not affect its effectiveness; only prolonged storage after heat storage will have an impact. However, compared to before using the adjuvants of the present invention, the improvement is already significant. Therefore, the adjuvants of the present invention can effectively solve the problem of paste formation during heat storage. Examples 29-34 use the adjuvants and combination schemes of the present invention. After heat storage, the fluidity is good, and there is no paste formation or clumping. Even at room temperature, there is no paste formation or clumping. The suspension rate does not decrease significantly compared to before heat storage. It fully meets the quality standards for pesticide formulations after heat storage and the requirements for actual use under different regional climatic conditions, achieving a significant improvement in thermal stability. Examples 35-41 illustrate the adjuvants and their combination schemes of the present invention, which are still applicable even with a high content of 20% active ingredient. Examples 42-46 do not use comb-grafted acrylic acid copolymers, and after heat storage... The paste-like consistency and lack of fluidity severely fail to meet the quality standards for pesticide formulations after heat storage. Examples 47 and 48, while using the adjuvant combination described in this invention, did not employ appropriate dosages. Although compliant with standards, these dosages would affect practical application. Examples 49-66 demonstrate that with an effective content of 30-40%, the adjuvants and combinations described in this invention can produce perfect formulations that meet the quality standards for pesticide formulations after heat storage and the actual application requirements under different regional climatic conditions. Examples 67-72 illustrate that the adjuvants and combinations of this invention can also satisfy the requirements of compound formulations containing 5%-30% miticide quinone + 5%-20% spirodiclofen. Examples 73-78 demonstrate that even without using EO-PO block polyether, simply increasing the amount of comb-grafted acrylic copolymer to 12% or more, combined with other adjuvants, can also produce perfect formulations that meet the quality standards for pesticide formulations after heat storage and the actual application requirements under different regional climatic conditions.

[0224] In summary, after using the technical solution described in this invention, the heat resistance of the acaricide suspension has been significantly improved. The prepared suspension can maintain a uniform appearance and good fluidity after high-temperature storage, and its various performance indicators are almost unchanged compared with those of the room temperature sample. It fully meets the quality standard requirements of pesticide formulations after heat storage and the requirements for actual use under different regional climatic conditions, and has achieved a significant effect in improving thermal stability.

[0225] 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. Industrial applicability

[0226] This application discloses an aqueous suspension containing acaricide quinone, its preparation method, and its application. The aqueous suspension comprises the following raw materials in weight fractions: acaricide quinone 1-50%, a high molecular weight carboxylic acid copolymer 0.5-25%, EO-PO block polyether 0-1.0%, water, and dosage form excipients. The dosage form excipients are selected from one or more of antifreeze, thickeners, defoamers, and preservatives. This invention, through the use of a functional dispersant (high molecular weight carboxylic acid copolymer or high molecular weight carboxylic acid copolymer and EO-PO block polyether), ensures that the formulation, after storage at 54°C for 14 days, exhibits uniform and stable appearance, without clumping, paste formation, or precipitation. All quality indicators meet national standards and the requirements for actual transportation, storage, and use.

Claims

1. An aqueous suspension containing acaricide quinone, characterized in that, Raw materials include the following weight fractions: The formulation consists of 1-50% acaricide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, 0-1.0% EO-PO block polyether, water, and formulation excipients; among which, The dosage form excipients are selected from one or more of antifreeze, thickener, defoamer, and preservative.

2. The aqueous suspension agent according to claim 1, characterized in that, The EO-PO block polyether is selected from one or more of the following: ethylene oxide-propylene oxide block copolymers initiated by ethylenediamine, ethylene oxide-propylene oxide block copolymers initiated by hydroxystearic acid, ethylene oxide-propylene oxide block copolymers initiated by propylene glycol, and ethylene oxide-propylene oxide block copolymers initiated by butanol; optionally, the average molecular weight of the EO-PO block polyether is ≥4000, and optionally 4000 to 20000.

3. The aqueous suspension agent according to claim 1, characterized in that, The high molecular weight carboxylic acid copolymer includes one or more of comb-grafted acrylic acid copolymer, maleic acid copolymer, and sorbitol-fatty acid copolymer; Optionally, the functional monomers of the comb-grafted acrylic acid copolymer include carboxyl monomers, and optionally also include one or more of alkyl monomers, ether monomers, and sulfonic acid monomers; optionally, the average molecular weight of the high molecular weight carboxylic acid copolymer is ≥4000, and optionally is 4000-25000. Optionally, the high molecular weight carboxylic acid copolymer includes comb-grafted acrylic acid copolymer, and further includes one, two, or some of maleic acid copolymer and sorbitol-fatty acid copolymer; optionally, it is Atlox 4917, Atlox 4916, T2612, D305, Agrilan 788, Plexsurf 8000, etc. 2700、Atlox 4913、GEROPON T / 36、Agrilan 755(nouryon)、 One or more of 2500 (HUNTSMAN), D205 (Dow Chemical), and TRN (Lamberti); Optionally, when the content of acaricide quinone is ≥20%, the content of the high molecular weight carboxylic acid copolymer is ≥6%; Optionally, when the content of acaricide quinone is ≥30%, the content of the high molecular weight carboxylic acid copolymer is ≥7%.

4. The aqueous suspension agent according to any one of claims 1 to 3, characterized in that, The weight ratio of acaricide to the high molecular weight carboxylic acid copolymer is (0.1–5):1, optionally (0.1–4.5):1, optionally (0.5–4.4):1; And / or, the weight ratio of the high molecular weight carboxylic acid copolymer to the EO-PO block polyether is (6.5-200):(0-1), optionally (6.5-200):1, optionally (7.5-200):1, optionally (7.5-60):

1.

5. The aqueous suspension agent according to any one of claims 1 to 4, characterized in that, The raw materials include the following weight fractions: 1-50% acaricide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, 0-1.0% EO-PO block polyether, water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 6-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 12-25% high molecular weight carboxylic acid copolymer, water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 1-50% miticide quinone, 0.5-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether, water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 5-50% miticide quinone, 4-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 5-40% miticide quinone, 5-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 10-20% miticide quinone, 6-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 10-20% miticide quinone, 6-10% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 20-40% miticide quinone, 6-25% (optionally 7-25%) high molecular weight carboxylic acid copolymer, 0.1-1.0% (optionally 0.5-1.0%) EO-PO block polyether, water, and formulation excipients; Optionally, the raw materials include the following by weight fractions: 20-40% miticide quinone, 8-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients; Optionally, the raw materials include the following weight fractions: 30-40% miticide quinone, 8-25% high molecular weight carboxylic acid copolymer, 0.1-1.0% EO-PO block polyether (optionally 0.5-1.0%), water, and formulation excipients.

6. The aqueous suspension agent according to any one of claims 1 to 5, characterized in that, The aqueous suspension contains the following dosage form excipients by weight: 0-10% antifreeze, 0-2% thickener, 0-4% defoamer, and 0-5% preservative; Optionally, the aqueous suspension contains the following dosage form excipients by weight: 3-10% antifreeze, 0.3-2% thickener, 0.3-4% defoamer, and 0.5-5% preservative; Optionally, the aqueous suspension contains the following dosage form excipients by weight: 5-10% antifreeze, 0.8-2% thickener, 0.5-4% defoamer, and 0.5-5% preservative; Optionally, the aqueous suspension contains the following dosage form excipients by weight: xanthan gum 0-0.5%, magnesium aluminum silicate 0.5-2.0%, silica 0-10%, isothiazolinone 0-10%, antifreeze 0-10%, and defoamer 0-10%. Optionally, the aqueous suspension contains the following dosage form excipients by weight: xanthan gum 0.3-0.5%, magnesium aluminum silicate 0.5-2.0%, isothiazolinone 0.5-10%, antifreeze 5-10%, and defoamer 0.5-10%. And / or, the antifreeze is selected from one or more of ethylene glycol, propylene glycol and urea; And / or, the defoamer is dimethyl silicone oil and / or polyether silicone; Optionally, the formulation may contain 0-2.0% of a dye, which may be an azo dye or a triphenylmethane dye.

7. The aqueous suspension agent according to any one of claims 1 to 6, characterized in that, It also includes other active pesticide ingredients, optionally including spirodiclofen; And / or, add water to bring the level up to 100%.

8. A method for preparing an aqueous suspension agent according to any one of claims 1 to 7, characterized in that, include: First, mix the acaricide technical, high molecular weight carboxylic acid copolymer, EO-PO block polyether, water, and formulation excipients in a certain proportion, then cut and mill them to obtain a water-dispersible aqueous suspension; optionally, mill them to a particle size of less than 5 micrometers.

9. The application of an aqueous suspension agent according to any one of claims 1 to 7 or an aqueous suspension agent prepared by the preparation method according to claim 8 in the control of plant pests.

10. The application according to claim 9, characterized in that, The plant pests mentioned are mites, aphids, or nematodes. Optionally, the mites are selected from one or more of spider mites and rust mites. Optionally, the spider mites include one or more of the following: carmine spider mite, hawthorn spider mite, oval short-haired mite, and citrus spider mite. Optionally, the rust mites include one or more of the following: citrus leaf gall mite, rust mite, and rust spider mite.

Images