AU2018318347B2

AU2018318347B2 - An oil-based concentrate, a preparation method therefor and the use thereof

Info

Publication number: AU2018318347B2
Application number: AU2018318347A
Authority: AU
Inventors: Yifan Wu
Original assignee: Jiangsu Rotam Chemical Co Ltd
Current assignee: Jiangsu Rotam Chemical Co Ltd
Priority date: 2017-08-14
Filing date: 2018-07-27
Publication date: 2023-05-18
Anticipated expiration: 2038-07-27
Also published as: AU2018318347A1; AR112396A1; CO2020002965A2; BR112020002933A2; CN107439569A; WO2019033918A1; MX2020001773A; TW201909743A

Abstract

Disclosed are an oil-based concentrate, a preparation method therefor and the use thereof, the oil-based concentrate comprises the following components: Component a: at least one spirotetramat active substance which is solid at room temperature; Component b: at least one pyriproxyfen active substance which is solid at room temperature; Component c: at least one fatty acid ester of general formula R

Description

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DESCRIPTION AN OIL-BASED CONCENTRATE, A PREPARATION METHOD THEREFOR AND THE USE THEREOF

Technical Field The present invention belongs to the field of pesticides, and relates to an oil-based concentrate, a preparation method therefor and the use thereof.

Background Art Spirotetramat is a tetronic acid-based compound developed by Bayer Corporation and is one of the modern insecticides with two-way systemic transport properties to date. The compound can move upwards and downwards throughout the plant in vivo and reach the foliage and bark so as to control, for example, pests on the inner leaves of lettuce and cabbage and the barks of fruit trees. This unique systemic property can protect new stems, leaves and roots, and prevent pest eggs and larvae from growing. Another characteristic thereof is that it has a long effect lasting period and can provide an effective control for up to 8 weeks. Pyriproxyfen is a phenylate-based insect growth regulator that disturbs the growth of insects, is a novel insecticide that is ajuvenile hormone analogue, and has the characteristics of having a systemic transport activity, a low toxicity and a long lasting period, being safe to crops and low in toxicity to fishes, and having a small impact on the ecological environment. It has a good control effect on Pear psylla, Bemisia tabaci Gennadius, scale insects, diamondback moth, Spodopteraexigua Hiibner, Spodopteraritura, Psylla pyricola, and thrips, etc.; in addition, this product has a very good control effect on sanitary insect pests such as flies and mosquitoes. It has the effects of inhibiting mosquito and fly larvae from pupation and eclosion. Mosquito and fly larvae, which have been exposed to the drug, basically all die in the pupal period and cannot undergo eclosion. The effect lasting period of the pesticide is as long as about 1 month, and the pesticide is easy to use, odourless, and is a better pesticide for mosquito and fly eradication.

I

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At present, patents regarding formulations by compounding spirotetramat and pyriproxyfen have also been reported; CN 103283787 A discloses a compounded combination of spirotetramat and pyriproxyfen; in addition, it is also mentioned that the prepared compounded formulations include a wettable powder, water dispersible granules, a suspension, a suspoemulsion, an emulsion in water, a microemulsion, and a microcapsule suspension. In the actual preparation process, there are more or less difficulties for any of the above formulations. For example, since the pyriproxyfen technical material has a melting point of 45-47°C, the pyriproxyfen technical material is unsuitable or impossible to process for the preparation of a wettable powder, water dispersible granules or a suspension due to the excessively low melting point; in addition, the products prepared from the above formulation can all fail due to melting of the technical material during storage at 54°C, which is theoretically not feasible. It is theoretically feasible to prepare as a microcapsule suspension or a microcapsule suspension-suspension; however, since microencapsulation is technically complicated, has high requirements on processing equipment and high costs, it is not used by the researchers. Although preparing as an emulsion in water or a microemulsion is relatively simple and mature in technique and low in cost, the method is limited by the solubleness and solubility of spirotetramat and pyriproxyfen, and it is very difficult to prepare a compounded formulation with high contents, especially a compounded formulation with the sum of the contents thereof being greater than 30%; furthermore, the method more or less relates to the use of an environmentally unfriendly solvent and is so eliminated by the market. Therefore, there is an urgent need in the market to develop an excellent formulation that is environmentally friendly, stable in particle size and dosage form, simple in processing process, and low in preparation costs.

Summary of the Invention In view of the deficiencies of the prior art, an object of the present invention is to provide an oil-based concentrate, a preparation method therefor and the use thereof

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In order to achieve this object, the following technical solution is used in the present invention: in one aspect, the present invention provides an oil-based concentrate comprising the following components: Component a: at least one spirotetramat active substance which is solid at room temperature; Component b: at least one pyriproxyfen active substance which is solid at room temperature; Component c: at least one fatty acid ester with general formula R1 -COO-R2 and/or R1 -COO-R 2-OOC-R ,1 wherein R 1is an alkyl and/or alkenyl group having 10-25 carbon atoms, and R 2 is an alkyl group having 1-10 carbon atoms; Component d: at least one non-ionic surfactant and/or at least one anionic surfactant; and optionally Component e: one or at least two additives selected from an emulsifier, a defoaming agent, a preservative, an antioxidant, a colourant or an inert filling material; wherein the pyriproxyfen is dissolved in a molecular state in Component c, and the spirotetramat is suspended in a particle state in Component c. In the present invention, the specific selection and combination of components for the oil-based concentrate, particularly the use of the fatty acid ester component, makes the oil-based concentrate capable of effectively resolving the problem of particle size increase of spirotetramat during storage, greatly inhibiting the particle size of suspended spirotetramat particles from increasing, and improving the stability of the formulation and the effect of spirotetramat; in addition, pyriproxyfen is stably present in a molecular state in the concentrate without crystal precipitation, these two active substances are not affected by each other, and remain as their respective states in the concentrate, enhancing the compounding effect. In the present invention, the oil-based concentrate compounded from spirotetramat and pyriproxyfen does not contain any thickening agent (such as a vegetable oil or a mineral oil) but can exhibit an excellent stability, improving the stability of a formulation containing spirotetramat and pyriproxyfen active

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substances. In the present invention, the content of each component in said oil-based concentrate can be within a wider range. Preferably, said oil-based concentrate comprises the following components in weight percentage: 0.1-30% of Component a, 0.1-30% of Component b, 20-90% of Component c, 1- 3 0% of Component d, and 0- 4 0% of Component e; In the present invention, by the mutual cooperation of these components in specific amounts, the components of the oil-based concentrate achieve a better cooperation condition, effectively resolving the problem of particle size increase of spirotetramat during storage, inhibiting the particle size of suspended spirotetramat particles from increasing and improving the stability of the formulation. Preferably, the weight ratio of said spirotetramat to said pyriproxyfen is 1 10-10 : 1, e.g., 1: 1, 1 : 2, 1 : 3, 1 : 4, 1 :5, 1 : 6, 1 : 7, 1 : 8, 1 : 9, 1 : 10, 2 : 1, 3 : 1, 4 : 1, 5 : 1, 6 : 1, 7 : 1, 8 : 1, 9 :1 or 10:1, preferably 1 : 5 to 5 : 1. In the present invention, where the weight ratio of said spirotetramat to said pyriproxyfen is 1 : 10 to 10 : 1, these two can be respectively maintained to have more excellent activity and present in their respective states in the concentrate, which can produce a good compounding effect. In the present invention, said oil-based concentrate can completely dissolve the pyriproxyfen, such that the pyriproxyfen is present in a molecular state, and can suspend the spirotetramat particles. The Component c is preferably a fatty acid ester of general formula R1 -COO-R 2 and/or R 1 -COO-R 2-OOC-R .1 In the formula, R 1 is a linear or branched alkyl group and/or alkenyl group having 10-25 carbon atoms, and R 2 is a linear or branched alkyl group having 1-10 carbon atoms. A fatty acid ester complying with the above-mentioned structure is usually a C1 0 -C 2 5 fatty acid ester formed from a C1 -C 1 0 alkyl monohydric alcohol or dihydric alcohol and a fatty acid. Said C 1 -C 1 0 alkyl monohydric alcohol or dihydric alcohol may be ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, etc. Said fatty acid is preferably a fatty acid having an even number of carbon atoms, and may be, for example, decanoic acid, erucic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic

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acid, linolenic acid, arachidic acid, etc. Preferably, in Component c, R 1 is an alkyl group and/or alkenyl group having 12-20 carbon atoms, e.g., 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, and is further preferably an alkyl group and/or alkenyl group having 12-18 carbon atoms; and R 2 is an alkyl group having 2-8 carbon atoms, e.g., 2, 3, 4, 5, 6, 7 or 8 carbon atoms, and is further preferably an alkyl group having 2-6 carbon atoms. Preferably, said alkyl group is a linear or branched alkyl group. Preferably, said Component c is any one of or a combination of at least two of ethyl oleate, butyl oleate, hexyl laurate, ethylene palmitate or pentylene linoleate. In the present invention, the above-mentioned fatty acid esters or combinations thereof can regulate the stability of the oil-based concentrate, and can effectively inhibit particle size increase of spirotetramat during storage. Preferably, said non-ionic surfactant is selected from any one of or a combination of at least two of a copolymer of methacrylic acid and a methacrylate, a polymer of a fatty alcohol and ethylene oxide and/or propylene oxide, an ethylene oxide-propylene oxide block copolymer, a fatty alcohol polyoxyethylene ether, an alkyl glycoside, a polyvinyl alcohol, polyvinyl pyrrolidone, an alkyl ethoxylate, an alkyl aryl ethoxylate or Tween. In the present invention, said non-ionic surfactant has the effects of dispersing, emulsification, solubilizing, etc. Preferably, said anionic surfactant is selected from any one of or a combination of at least two of a lignosulphonate (Borresperse NA), a succinate sulphonate, a naphthalene sulphonate formaldehyde condensate, a sulphate of tristyryl ethoxylate, and a phosphate or polycarboxylate of tristyryl ethoxylate. In the present invention, said anionic surfactant has the effects of clarification and purification. In the present invention, the weight percentage of Component a in said oil-based concentrate is 0.1- 3 0%, for example, 0.1%, 0.8%, 2%, 5%, 6 .9 %, 8 .4 %,

9 .6 %, 11%, 1 2 .9 %, 15%, 17%, 18%, 1 9 .5 %, 2 1. 2 %, 2 5 %, 2 7 .5 % or 30%, preferably 5-20%. In the present invention, the weight percentage of Component b in said

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oil-based concentrate is 0.1- 3 0%, for example, 0.1%, 0.8%, 2%, 5%, 6 .9 %, 8 .4 %,

9 .6 %, 11%, 1 2 .9 %, 15%, 17%, 18%, 1 9 .5 %, 2 1. 2 %, 2 5 %, 2 7 .5 % or 30%, preferably 5-20%. In the present invention, the weight percentage of Component c in said oil-based concentrate is 20- 9 0%, for example, 20%, 21%, 2 5 %, 3 2 %, 40%, 50%, 55%, 60%, 68%, 72%, 80%, 85% or 90%, preferably 30-80%; and In the present invention, by using any one of, or, a combination of at least two of, the esters of said Component c, the addition of traditional vegetable oils can be avoided. Where the content of said Component c is preferably in the range of 30-80%, the component can not only completely dissolve the pyriproxyfen but also can suspend spirotetramat particles, more effectively avoiding the risk of particle size increase and overcoming the problems encountered during storage. In the present invention, the weight percentage of Component d in said oil-based concentrate is 1- 3 0%, for example, 1%, 2%, 5%, 7%, 8 .7 %, 10. 5 %, 12%, 14%,15%,16.4%,17.5%,19%,21%,23.2%,25%,28% or 30%, preferably 5-25%. In the present invention, the weight percentage of Component e in said oil-based concentrate is 0- 4 0%, for example, 0%, 2%, 5%, 7%, 9 .2 %, 11%, 15%, 17%, 19%, 20%, 2 3 %, 2 5 %, 2 7 %, 30%, 34%, 37% or 40%, preferably 0- 3 0 %. Preferably, said emulsifier is any one of or a combination of at least two of a reaction product of an alkyl phenol with ethylene oxide and/or propylene oxide, an ethoxylated nonyl phenol, a castor oil ethoxylate, a mixture of polyalkoxylated alcohols, an alkyl calcium salt, a calcium alkylbenzene sulphonate salt, a sorbitan derivative or a polyethylene oxide-sorbitan fatty acid ester. In the present invention, suitable defoaming agents include all substances commonly used for this purpose in agrochemical compositions. Preferably, said defoaming agent is a silicone defoaming agent, preferably a siloxane defoaming agent. In the present invention, suitable preservatives include all substances commonly used for this purpose in agrochemical compositions. Preferably, said preservative is selected from Proxel series and/or Nipacide series preservatives. In the present invention, suitable antioxidants include all substances commonly

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used for this purpose in agrochemical compositions. Preferably, said antioxidant is 2,6-di-tert-butyl-4-methylphenol (BHT). In the present invention, suitable colourants include all substances commonly used for this purpose in agrochemical compositions. Preferably, said colourant is any one of or a combination of at least two of titanium dioxide, pearl powder, zinc oxide, a blue pigment, or Pigment Red BBN (i.e., Light Fast Scarlet BBN). In the present invention, suitable inert materials include all substances commonly used for this purpose but not as thickening agents in agrochemical compositions. Preferably, said inert filling material is any one of or a combination of at least two of urea, a silicate, a sulphate or an oxide. Preferably, said oxide is a metal oxide and/or a non-metal oxide. In another aspect, the present invention further provides a method for preparing said oil-based concentrate, said preparation method involving: stirring, mixing and grinding Component a, Component b, Component c, Component d and optionally Component e to obtain said oil-based concentrate. In the present invention, said oil-based concentrate is obtained by completely dissolving Component b in Component c by stirring, then adding Component a, Component d and Component e in any order to the above-mentioned mixed liquid to obtain a suspension, and further fully grinding same. Preferably, said grinding is carried out at 10-50°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, preferably 15-45°C. Preferably, said grinding is carried out such that the solid particles in said oil-based concentrate are ground into a particle size D90 < 10 pm, e.g., 0.4 ptm, 0.8

ptm, 1 m, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm or 10 pm, preferably D90 < 5 pm. In the present invention, the average size of the solid particles in said oil-based concentrate are less than 10 pm, and under normal temperature storage and/or hot storage conditions, the particle size changes little, increases relatively slow, and remains stable for a relatively long time. In the present invention, compared with the existing preparation method for microcapsule suspension or microcapsule suspension-suspension, said preparation

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method has low formulation costs, a simple process, low equipment requirements and a high processing efficiency. In another aspect, the present invention provides a liquid spray comprising the oil-based concentrate as described above. In the present invention, by diluting with water, the oil-based concentrate of the present invention can be converted into a homogeneous liquid spray. Said liquid spray is applied by a conventional method, for example, by spraying, injection, dropping or pouring. In the present invention, where said oil-based concentrate is diluted with water, there is neither obvious emulsion layering nor any destructive flocculation effect, and also no phenomenon of pyriproxyfen crystallisation, having very good physical and chemical properties. In another aspect, the present invention provides the use of said oil-based concentrate as described above for application to a plant and/or the growing environment thereof When applied to a plant, the oil-based concentrate of the present invention can be absorbed by the plant, the penetration of the oil-based concentrate at the application site of the plant is enhanced, the application efficiency is improved, the bioavailability of the compounded spirotetramat and pyriproxyfen active substances is enhanced, and the utilisation amount thereof is reduced. In another aspect, the present invention provides the use of the oil-based concentrate as described above for the control of insects. The oil-based concentrate of the present invention has a high stability, can improve the compounding activity of the main active ingredients, spirotetramat and pyriproxyfen, and improves the control effect on insects. Preferably, said insects to be controlled are any one of or at least two of lepidoptera pests, diptera pests, hemiptera pests and homoptera pests. Lepidoptera pests are, for example, Earias insulana, Pieris rapae Linnaeus, Herpetogramma licarsisalisWalker Spodopterafugiperda, Spodopterafrugiperda, Rachiplusia nu, Pseudoplusia includens, Sesamia inferens, Cnaphalocrocis medinalis Guenee, Maruca testulalis, Cirphisunipuncta,Tuta absoluta, Trichoplusia

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ni, Sesamianonagrioides, Trichoplusia ni, Anticarsia gemmatalis, Grapholitha molesta, Phthorimaea operculella, Sitotroga cerealella, Earias vittella Fabricius, Adoxophyes orana, Pectinophoragossypiella Saunders, Heliothis armigera, Alabama argi llacea, Lymantria monacha, Cydia pomonella, Pandemis heparana, Lobesia botrana, Sparganothispilleriana,Endopiza vriteana Clemens, Scirpophaga incertulas, SpodopteraexiguaHiibner Spodopteraritura,Ephestia elutella, Heliothis virescens, Epinotia aporema, Tineola bisselliella, Plodiainterpunctella and OstrinianubilalisHiibner. Diptera pests are, for example, Aedes aegypti, Liriomyza brassicae, Sarcophaga haemorrhoidalis, Glossina morsi tans, Phorbia antiqua, Ceratitis capitata, Delia radicum, Dacuscucurbi tae, Tabanus lineola, Calliphora vricina, Psila rosae, Bactrocera dorsalis, Culicoides furens, Aedes vexans, Rhagoletis mendax, Chrysomya spp., Chrysops discalis, Phorbia brassicae, Si todiplosis mosellana, Liriomyza trifolii, Rhagoletis pomonella, Hippelates, Bactrocerasonata, Pegomya hysocyami, Pegomya betae, Lucilia cuprinaand Culexquinquefasciatus. Hemiptera and homoptera pests are, for example, SogatellafurciferaHorvrath, Trialeurodesvaporariorum, IeryapurchasiMaskell, Iceryapurchasi,Aphis glycines, Nilaparvata lugens, Nilaparvrata lugens, Brevicoryne brassicae, Bemisia tabaci, Diaphorina citri, Nephotettix nigropictus, Ceroplastesrubens, Aonidiella aurantii, Laodelphax striatellus, Aphis craccivroraKoch, Macrosiphum avenae, Aphis pomi, Psylla mali, Brachycaudus persicae, Myzuspersicae Sulzer; Acyrthisiphon pisum Harris, Trialeurodes vaporariorum, Bemisia tabaci Gennadius, Empoasca spp., Peregrinus maidis, Peregrinus maidis Ashmead, Rhopalosiphum maidis and Sogatodes orizicola Muir. The oil-based concentrate of the present invention is particularly suitable for the control of Bemisia tabaci Gennadius, Delphacidae, aphids, scale insects, thrips, Cnaphalocrocis medinalis Guenee, Scirpophaga incertulas, red spiders, Spodopteraritura, cabbage caterpillar, diamondback moth, Spodopteraexigua Hiibner, Phyllotreta vittata or Empoasca pirisuga Matumura. It is further particularly suitable for the control of Bemisia tabaci Gennadius and/or plant hoppers. Compared with the prior art, the present invention has the following beneficial

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effects: (1) compared with the other existing formulations, the oil-based concentrate of the present invention can effectively control the increase of the particle size of spirotetramat during storage, solving the problem of the increase of the particle size of suspended spirotetramat particles; in addition, pyriproxyfen is stably present in a molecular state in the concentrate without crystal precipitation, the two active substances are not affected by each other, and remain as their respective states in the concentrate, maintaining and exerting the biological activities of the two to a greater extent. (2) The oil-based concentrate of the present invention overcomes the constraints of conventional conditions, does not contain any vegetable oil or mineral oil thickening agent, has an excellent stability, and is particularly suitable for the enhancement of the stability of the formulation compounded from the spirotetramat active substance and pyriproxyfen. (3) The oil-based concentrate of the present invention has good physical and chemical properties. Where the oil-based concentrate of the present invention is diluted with water, there is neither obvious emulsion layering nor destructive flocculation effect; furthermore, the phenomenon of pyriproxyfen crystallisation is avoided. (4) The oil-based concentrate of the present invention improves the biological activities of spirotetramat and pyriproxyfen, reduces the use amounts of these two, increases the bioavailability, finally reduces costs, and has a good control effect on Bemisia tabaci Gennadius; after 25 days of high concentration administration, the control effect on adult Bemisia tabaci Gennadius can reach 95% or more, and the control effect on Bemisia tabaci Gennadius nymphs can reach 85% or more. (5) The method for preparing the oil-based concentrate of the present invention has a simple process, low equipment requirements and a high processing efficiency, is advantageous for industrial scale production, reducing production costs.

Detailed Description of Embodiments

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The technical solution of the present invention is further described below by way of specific examples. It will be clear to a person skilled in the art that said examples merely aid in the understanding of the present invention and should not be taken as a particular limitation on the present invention. The substances used in the following examples would be obtained by a person skilled in the art via conventional channels. Example 1 In this example, the oil-based concentrate comprised the following components: Spirotetramat 10% Pyriproxyfen 10% Polyoxyethylene-sorbitol oleate 15% Mixture of polyalkoxylated alcohols 7%

Lignosulphonate 3%

Polydimethylsiloxane 1%

2,6-di-tert-butyl-4-methylphenol 0.5%

Ethyl oleate 53.5% The preparation method was as follows: pyridoxine was added to ethyl oleate and thoroughly stirred such that the pyriproxyfen was completely dissolved in the ethyl oleate. The other materials were added to the above-mentioned mixed liquid in any order, and uniformly stirred to obtain a suspension. The suspension was subjected to primary coarse grinding and secondary fine grinding in a sand mill at 45°C or less to obtain an oil-based concentrate with suspended particles of D90 of less than 5 pm. Comparative Example 1 In this comparative example, the oil-based concentrate comprised the followingcomponents: Spirotetramat 10%

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Pyriproxyfen 10%

Polyoxyethylene-sorbitol oleate 15%

Mixture of polyalkoxylated alcohols 7%

Lignosulphonate 3%

Polydimethylsiloxane 1%

2,6-di-tert-butyl-4-methylphenol 0.5%

Vegetable oil (soybean oil) 53.5%

The preparation method was as follows: The raw materials were added to the soybean oil in any order, and uniformly stirred to obtain a suspension. The suspension was subjected to primary coarse grinding and secondary fine grinding in a sand mill at 45°C or less to obtain an oil-based suspension with suspended particles of D90 of less than 5pm. Example 2-7 and Comparative Example 2-7 were prepared according to the above method with the same settings, and the components thereof and the amounts thereof were as shown in Table 1. Table 1 Comp Comp Comp Comp Comp Comp Exa arativ Exa arativ Exa arativ Exa arativ Exa arativ Exa arativ Component mpl e mpl e mpl e mpl e mpl e mpl e e 2 examp e 3 Exam e 4 Exam e 5 Exam e 6 Exam e 7 Exam le 2 ple 3 ple 4 ple 5 ple 6 ple 7 Spirotetramat 30%30% 5% 5% 15%15% 20%20% 5% 5% 30%30%

Pyriproxyfen 5% 5% 130%30% 1 15%15% 110%10% 5% 5% 120%20%

Tween80 10%10% - - - - - - - - -

Calcium dodecylbenzene5% 5% - - 15%15% 15%15% - - -

sulphonate Nonylphenol 5% 5% - - - - - - - - - ethoxylate Castor oil polyoxyethylene- - 15%15% - - - - - - -

ether

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Alkyl naphthalene sulphonate - - 5% 5% - - 5% 5% - - -

formaldehyde condensate Alkyl glycoside - - 5% 5% - - - - - - -

Succinate - - - - 5% 5% - - - - - sulphonate Ethylene oxide and propylene- - - - 10%10% - oxide tert-butyl ether Fumed white- - - - 3% 3% - - - - - carbon black Fatty acid polyoxyethylene- - - - - - 5% 5% - - - ether Lignosulphonat - - - 10%10% 10%10% e eolyoxyethylen- - - - - - - - 10%10% 20%20% e-sorbitol oleate Polydimethylsil 1% 1% 1% 1% 1% 1% 1% 1% - - - oxane 2,6-di-tert-butyl 0.50 0.50% 0.50 0.50% 50 0.50% 0.50 0.50% -4-methylphenol% % % 1 % I I Pearlescent 1%1% - - - - - - - - - powder

Butyl oleate 42.5

Ethylene 38.5 palmitate 0% Pentylene 35.5 linoleate 0% 43.5 Hexyl laurate - - - - - - 0% Ethyl oleate - - - - - - - - 70%- 20%

Vegetable oil 38.50 (rapeseed oil) %

Vegetable oil 42.5%o- - - - - - - - - 20% (soybean oil) Vegetable oil 35.50 43.50 (maize oil) % %

Mineral oil 0 - (paraffin oil) Comparative Example 8

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In this comparative example, the water-based concentrate comprised the following components: Spirotetramat 10% Pyriproxyfen 10%

Aliphatic alcohol polyoxyethylene ether 5%

Methacrylate 5%

lignosulphonate 3%

Polydimethylsiloxane 1%

Xanthan gum 0.2%

Biological bactericide 0.2%

2,6-di-tert-butyl-4-methylphenol 0.5%

Water 6 5 .1%

The preparation method was as follows: Except the xanthan gum and the biological bactericide, the other raw materials were added to water in any order, and uniformly stirred to obtain a suspension. The suspension was subjected to primary coarse grinding and secondary fine grinding in a sand mill at 45°C or less to obtain a water-based concentrate with suspended particles of D90 of less than 5 pm. Furthermore, the xanthan gum and biological bactericide were added in proportion, and stirred until uniform, thus obtaining a water-based suspension. The samples prepared in Examples 1-7 and the samples of Comparative Examples 1-8 as mentioned above were stored for a long term for testing by comparing the samples in terms of fluidity and particle size increase. The test method was as follows: the above-mentioned seven samples were placed in an oven at 54°C for 14 days and 28 days, and then the fluidities of the samples were observed and the particle sizes thereof before and after storage were tested using a Malvern particle size analyser. The specific liquidity measurement results were as shown in Table 2, and the particle size measurement results were as shown in Table

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3: Table 2

Sample No. Fluidity before Fluidity after 14d at 54°C Fluidity after 28d at storage 54 0 C Example 1 Good fluidity Good fluidity Good fluidity

Example 2 Good fluidity Good fluidity Good fluidity

Example 3 Good fluidity Good fluidity Good fluidity

Example 4 Good fluidity Good fluidity Good fluidity

Example 5 Good fluidity Good fluidity Good fluidity

Example 6 Good fluidity Good fluidity Good fluidity

Example 7 Good fluidity Good fluidity Good fluidity

Comparative Good fluidity Poor fluidity, and having Creaming, and failure of Example 1 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 2 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 3 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 4 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 5 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 6 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having more Creaming, and failure of Example 7 agglomerates pouring out Comparative Good fluidity Poor fluidity, and having many Creaming, and failure of Example 8 agglomerates pouring out The experiments in Table 2 showed that the conventional water-based suspension and oil-based suspension, due to the lower melting point of pyriproxyfen, melt under 54 0C storage conditions, and the melted technical material oil droplets polymerized with each other, causing changes in the physical and chemical properties of the samples. In addition, by the oil-based concentrate of the present invention, i.e., the compounded formulation of spirotetramat and pyriproxyfen, this problem was solved. Table 3

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D90 before 14d D90 at Rate of 28d D90 at Rate of SampleNo. storage ([tm) 54°C ([tm) increase (%) 54°C ([tm) increase (%) Example 1 4.88 5.12 4.92% 7.12 45.9%

Example 2 4.61 5.24 13.67% 7.55 63.8%

Example 3 4.78 5.18 8.68% 7.01 46.7%

Example 4 4.95 5.50 11.11% 8.35 68.7%

Example 5 4.69 4.99 6.40% 8.26 76.1%

Example 6 4.81 5.26 9.36% 9.19 91.1%

Example 7 4.56 5.41 18.64% 7.88 72.8% Comparative 4.76 10.27 116% Creaming, Example 1 undetectable Comparative 4.69 13.84 195% Creaming, Example 2 undetectable Comparative 4.59 15.22 256% Creaming, Example 3 undetectable Comparative 4.72 14.25 202% Creaming, Example 4 undetectable Comparative 4.84 18.11 274% Creaming, Example 5 undetectable Comparative 4.96 14.59 294% Creaming, Example 6 undetectable Comparative 4.81 15.49 222% Creaming, Example 7 undetectable Comparative 4.35 25.28 481% Creaming, Example 8 undetectable The experimental data in Table 3 showed that the oil-based concentrate of the present invention, which was compounded from spirotetramat and pyriproxyfen, effectively controlled the rate of particle size increase of suspended particles after long-term storage and improved the stability of the oil-based concentrate. Application Example 1 In this application example, the samples prepared in Examples 1-7 above and Comparative Examples 1-8 above were subjected to a bioactivity test, and the method was as follows: Test object: Bemisia tabaci Gennadius on tomato

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The examples of Examples 1-7 and Comparative Examples 1-8 as mentioned above were tested using a spray method in a tomato planting area, wherein the application was carried out at the peak of young insects, both sides were sprayed uniformly, and each was repeatedly treated 3 times. Adult investigation: eight tomato trees were labelled in each area, two large branches were labelled in each plant, and when the adults were not active in the early morning, the number of adults on the large branches were investigated. Nymph investigation: three leaves were collected from the top, middle and bottom of each of five unlabelled tomato trees, i.e., 15 leaves in total, and the numbers of nymphs on these 15 leaves were recorded respectively. The numbers of adults and nymphs on the plants after 7, 14 and 25 days after application were investigated. Efficacy calculation method: Insect population reduction rate = Population before application - Population after application X1000 Population before application

Control effect = Insect population reduction rate in treated area - Insect population reduction rate in blank control area x 100% 100 - Insect population reduction rate in blank control area

The results of the control effect on adult Bemisia tabaci Gennadius were as shown in Table 4: Table 4 Use amount7-day control14-day control25-day control Sample (g/mu) effect(%) effect(%) effect(%) CK (untreated) - - -

Example 1 2 25.42 70.45 92.53

Example 1 4 35.59 77.89 96.25

Example 2 2 24.55 68.54 93.23

Example 2 4 33.87 76.34 97.12

Example 3 2 26.78 67.82 91.67

Example 3 4 37.11 76.06 95.89

Example 4 2 24.09 67.33 92.56

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Example 4 4 33.95 78.22 97.20

Example 5 2 22.98 66.88 93.23

Example 5 4 36.26 75.26 96.71

Example 6 2 24.02 67.36 92.10

Example 6 4 35.68 76.22 96.12

Example 7 2 26.15 67.20 91.09

Example 7 4 34.37 77.26 95.34

Comparative 2 20.67 58.25 83.18 Example 1 Comparative 4 30.23 66.11 90.16 Example 1 Comparative 2 19.89 57.90 82.89 Example 2 Comparative 4 31.32 65.14 91.25 Example 2 Comparative 2 19.34 60.24 83.47 Example 3 Comparative 4 29.88 68.11 89.43 Example 3 Comparative 2 18.89 59.83 84.23 Example 4 Comparative 4 29.11 69.78 91.24 Example 4 Comparative 2 21.34 57.45 84.78 Example 5 Comparative 4 30.04 67.89 91.69 Example 5 Comparative 2 20.38 60.12 84.45 Example 6 Comparative 4 29.76 67.19 91.71 Example 6 Comparative 2 19.15 57.84 83.57 Example 7 Comparative 4 28.89 70.12 89.88 Example 7 Comparative 2 15.22 40.25 75.92 Example 8 Comparative 4 20.28 55.29 80.56 Example 8 The oil-based concentrate of the present invention, which was compounded

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from spirotetramat and pyriproxyfen, had an excellent control effect on adult Bemisia tabaci Gennadius, and the control effect on adult Bemisia tabaci Gennadius after 25 days of a high dose application can reach 95% or more. The control effect on Bemisia tabaci Gennadius nymph was as shown in Table s 5: Table 5 Use amount7-day control effect14-day control25-day control Sample (g/mu) (%) effect(%) effect(%) CK (untreated) - - -

Example 1 2 7.18 50.62 80.29

Example 1 4 15.59 70.81 87.95

Example 2 2 7.68 51.60 81.29

Example 2 4 16.51 69.11 88.25

Example 3 2 7.38 51.23 81.25

Example 3 4 16.29 72.00 86.92

Example 4 2 6.89 49.37 80.60

Example 4 4 14.19 69.98 86.15

Example 5 2 8.22 50.22 79.54

Example 5 4 15.79 68.99 88.15

Example 6 2 8.12 51.36 82.21

Example 6 4 16.50 68.88 85.92

Example 7 2 6.79 49.62 78.21

Example 7 4 16.79 72.84 88.95 Comparative 2 6.67 44.35 72.68 Example 1 Comparative 4 16.63 63.98 80.26 Example 1 Comparative 2 7.54 43.23 69.34 Example 2

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Comparative 4 15.76 55.37 78.25 Example 2 Comparative 2 6.88 43.45 68.23 Example 3 Comparative 4 13.34 56.48 79.76 Example 3 Comparative 2 6.68 42.41 69.65 Example 4 Comparative 4 15.87 57.32 79.49 Example 4 Comparative 2 5.89 43.22 70.85 Example 5 Comparative 4 15.34 55.44 81.35 Example 5 Comparative 2 5.23 41.56 71.75 Example 6 Comparative 4 14.23 54.63 80.38 Example 6 Comparative 2 4.78 43.56 69.83 Example 7 Comparative 4 13.56 57.54 79.31 Example 7 Comparative 2 2.20 25.79 59.42 Example 8 Comparative 4 5.33 46.22 70.26 Example 8 The oil-based concentrate of the present invention, which was compounded from spirotetramat and pyriproxyfen, had an excellent control effect on Bemisia tabaci Gennadius nymph, and the control effect thereof on Bemisia tabaci Gennadius nymph after 25 days of a high dose application can reach over 85%. The applicant states that the oil-based concentrate, the preparation method therefor and the use thereof of the present invention are illustrated by way of the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, i.e. not meaning that the present invention has to be implemented depending on the above-mentioned examples. It will be clear to a person skilled in the art that any improvements to the present invention, equivalent replacements of the raw materials of the product and the addition of auxiliary ingredients in the present invention, the selection of specific manners, etc., all fall within the scope of protection and the scope of disclosure of the present invention.

Claims

WO 2019/033918C-en PCT/CN2018/097417 CLAIMS

1. An oil-based concentrate, characterized in that said oil-based concentrate comprises the following components: Component a: at least one spirotetramat active substance which is solid at room temperature;

Component b: at least one pyriproxyfen active substance which is solid at room temperature;

Component c: at least one fatty acid ester of general formula R 1 -COO-R 2

and/or R1 -COO-R 2 -OOC-R ,1 wherein R 1is an alkyl and/or alkenyl group having 10-25 carbon atoms, and R 2 is an alkyl group having 1-10 carbon atoms; Component d: at least one non-ionic surfactant and/or at least one anionic surfactant; and optionally Component e: one or at least two additives selected from an emulsifier, a defoaming agent, a preservative, an antioxidant, a colourant or an inert filling material; wherein the pyriproxyfen is dissolved in a molecular state in Component c, and the spirotetramat is suspended in a particle state in Component c.

2. The oil-based concentrate according to claim 1, characterized in that said oil-based concentrate comprises the following components in weight percentage: 0.1- 3 0% of Component a, 0.1- 3 0% of Component b, 20- 9 0% of Component c, 1- 3 0% of Component d, and 0-40% of Component e; preferably, the weight ratio of said spirotetramat to said pyriproxyfen is 1 : 10 to 10 : 1, preferably 1 : 5 to 5 : 1.

3. The oil-based concentrate according to claim 1 or 2, characterized in that in said Component c, R1 is an alkyl group and/or alkenyl group having 12-20 carbon atoms, preferably an alkyl group and/or alkenyl group having 12-18 carbon atoms; R 2 is an alkyl group having 2-8 carbon atoms, preferably an alkyl group having 2-6

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carbon atoms; and preferably, said alkyl group is a linear or branched alkyl group.

4. The oil-based concentrate according to any one of claims 1-3, characterized in that said Component c is any one of or a combination of at least two of ethyl oleate, butyl oleate, hexyl laurate, ethylene palmitate or pentylene linoleate.

5. The oil-based concentrate according to any one of claims 1-4, characterized in that said non-ionic surfactant is selected from any one of or a combination of at least two of a copolymer of methacrylic acid and a methacrylate, a polymer of a fatty alcohol and ethylene oxide and/or propylene oxide, an ethylene oxide-propylene oxide block copolymer, a fatty alcohol polyoxyethylene ether, a polyvinyl alcohol, an alkyl glycoside, polyvinyl pyrrolidone, an alkyl ethoxylate, an alkyl aryl ethoxylate or Tween; and preferably, said anionic surfactant is selected from any one of or a combination of at least two of a lignosulphonate, a succinate sulphonate, a naphthalene sulphonate formaldehyde condensate, a sulphate of tristyryl ethoxylate, and a phosphate or polycarboxylate of tristyryl ethoxylate.

6. The oil-based concentrate according to any one of claims 1-5, characterized in that the weight percentage of Component a in said oil-based concentrate is 5- 2 0 %; preferably, the weight percentage of Component b in said oil-based concentrate is 5-20%; preferably, the weight percentage of Component c in said oil-based concentrate is 30-80%; preferably, the weight percentage of Component d in said oil-based concentrate is 2-20%; and preferably, the weight percentage of Component e in said oil-based concentrate is 0-30%.

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7. A method for preparing the oil-based concentrate according to any one of claims 1-6, characterized in that said preparation method involves: stirring, mixing and grinding Component a, Component b, Component c, Component d and optionally Component e to obtain said oil-based concentrate; preferably, said grinding is carried out at 10-50°C, preferably 15-45°C; and preferably, said grinding is carried out such that the solid particles in said oil-based concentrate are ground to a particle size D90 < 10 pm, preferably D90 < 5 pm.

8. A liquid spray, characterized in that said liquid spray comprises the oil-based concentrate of any one of claims 1-6.

9. Use of the oil-based concentrate according to any one of claims 1-6 for application to a plant and/or the growing environment thereof

10. Use of the oil-based concentrate according to any one of claims 1-6 for the control of insects; wherein preferably, said insects to be controlled are any one of or at least two of lepidoptera pests, diptera pests, hemiptera pests or homoptera pests; and preferably, said insects to be controlled are Bemisia tabaci and/or plant hoppers.