Pyrethroid tank-mix adjuvant suspension concentrates

Abstract

ZC formulations consisting of finely ground pyrethroids and encapsulating adjuvants, which have enhanced insecticidal efficacy of pyrethroid suspension concentrates against insects without increasing the mammalian toxicity of the formulations.

Description

[0001] The bioavailability of pyrethroids can be finely tuned by selecting appropriate formulations. For example, in controlling related pests, the bioavailability of pyrethroid suspension concentrates (SCs), in which the active ingredient is suspended in water in colloidal form, is often lower than that of formulations in which the pyrethroid is dissolved in a non-water-soluble organic solvent—such as emulsifiable concentrates (ECs).

[0002] The mammalian toxicological properties (and their insecticidal properties) of pyrethroids can also be modulated by the type of formulation. Therefore, formulations in which pyrethroids are soluble (e.g., emulsifiable concentrates, EC) have higher acute oral toxicity than those in which the active ingredient is in the form of a finely ground colloidal dispersion (e.g., suspension concentrates, SC) (Toxicology and Mode of Action of Pyrethroid Insecticides - Chapter 77; Hayes' Handbook of Pesticide Toxicology; 2010 Elsevier).

[0003] The inevitable consequence of the above statements is that, compared with pyrethroid EC formulations, pyrethroid SC formulations have improved safety, but their biological efficacy is more limited. Pyrethroid EC formulations show higher oral acute toxicity, but also have broader and higher biological efficacy.

[0004] Therefore, it is desirable to combine the high insecticidal efficacy of pyrethroid EC formulations with the lower mammalian toxicological properties of pyrethroid SC formulations.

[0005] One approach is to mix SC pyrethroid formulations with adjuvants that enhance the insecticidal efficacy of ground pyrethroids. By adding selected chemical adjuvants—for example, polymers (WO2012 / 055810), carboxylic acid esters (WO 97 / 12515), or oils (Progress in Plant Protection, Vol. 36, Issue 2, pp. 105-107 (1996))—SC pyrethroid formulations can be made more bioactive. Ideally, these adjuvants are formulated directly with the pyrethroid, eliminating the need for additional steps before use. In other words, it is desirable to provide users with ready-to-use (RTU) formulations, also known as in-can adjuvanted formulations, which eliminate the need for additional adjuvants to achieve the full biological potential of the pyrethroid. However, because these adjuvants tend to exhibit the potential to dissolve the active ingredient, suspension concentrates stored in the presence of polymers, carboxylic esters, or phosphates become unstable for crystal growth due to Ostwald ripening (Colloidal Dispersions. Suspensions, Emulsions and Foams; Ian-D. Morrison, Sydney Ross; Wiley-Interscience, 2002. The Colloidal Domain: Where Physics, Chemistry, Biology, and Technology Meet; D. Fennell Evans, Wiley-VCH; 1999. Die vermeintliche Isomerie des roten und gelben Quecksilberoxyds unddie fester ", W. Ostwald; Zeitschrift für Physikalische Chemie-Leipzig, 1900, 34, pp. 495-503).

[0006] It is known that the instability of finely ground dispersions to crystal growth in the presence of adjuvants capable of dissolving the ground active ingredient can be addressed by encapsulating adjuvants. Certain oils known as pyrethroid adjuvants are known to be encapsulated within polyurea membranes (WO 03 / 099005, EP1531667). Mixtures of encapsulated oils and suspension concentrates are also known to resist crystal growth, and therefore such encapsulated oils can be used in canned adjuvant suspension concentrates without affecting the long-term stability or biological efficacy of the suspension concentrate. This is indeed the case, although the polyurea membrane physically separates the dispersed active ingredient from the adjuvant (WO 03 / 099005). Therefore, since mixtures of SC formulations and encapsulating adjuvants (also known as ZC formulations) exhibit insecticidal properties comparable to those of formulations in which pyrethroids are dissolved, it is expected that the mammalian toxicological properties of such ZC formulations will be similar to those of EC formulations.

[0007] We have now unexpectedly discovered that the ZC formulation, composed of finely ground pyrethroids and encapsulated adjuvants, can surprisingly selectively enhance the insecticidal efficacy of pyrethroid suspension concentrates against insects without increasing the mammalian toxicity of the formulation. In other words, according to the present invention, the pyrethroid ZC formulation performs similarly against agriculturally relevant pests to the pyrethroid EC formulation, while exhibiting significantly improved mammalian toxicity compared to the corresponding EC formulation. Detailed Implementation

[0008] definition

[0009] a. Pyrethroids

[0010] As used in this article, the term "pyrethroid" refers to substances belonging to IRAC mode of action group 3A (sodium channel modulators).

[0011] Examples of pyrethroids include Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioallethrin s-cyclopentenyl isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, β-cyhalothrin, and Trifluralin. Cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, Cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, Cyphenothrin [(1R)-trans-isomer], Deltamethrin, Empenthrin [(EZ)-(1R)-isomer], Esfenvalerate, Etof The following are listed: enprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, kadethrin, pyrethrins (Pyrethrum), Halfenprox, Phenothrin [(1R)-trans-isomer], Prallethrin, Resmethrin, Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R)-isomer], Tralomethrin, Transfluthrin, Permethrin. In a preferred embodiment, the pyrethroid is deltamethrin.

[0012] B. Adjuvants / Adjuvant mixtures

[0013] As used herein, the term "adjuvant / adjuvant mixture" refers to

[0014] a) The “trialkyl phosphate” substance exemplified by Formula 1, wherein R1, R2, and R3 may be the same or different. R1, R2, and R3 may be any C1-C10 alkyl segment, preferably a C5-C10 alkyl segment, more preferably a C6-C8 alkyl segment, and most preferably a C8 alkyl segment.

[0015]

[0016] or

[0017] b) A mixture of the "trialkyl phosphate" substance and the "alkyl ester of vegetable oil" in a weight percentage (% w / w) ratio of 0.1:99.9 to 99.9:0.1, preferably 0.5:99.5 to 99.5:0.5, and most preferably 1:99 to 99:1. As used herein, the term "alkyl ester of vegetable oil" refers to a substance that is commonly used as a penetration enhancer in agricultural chemical formulations.

[0018] In an alternative embodiment, b) refers to a mixture of the "trialkyl phosphate" substance and the "alkyl vegetable oil ester" in a weight percentage of 0.1:99.9 to 99.9:0.1, 1:99 to 90:10, more preferably 5:95 to 80:20, even more preferably 7.5:92.5 to 70:30, and most preferably 10:90 to 50:50. As used herein, the term "alkyl vegetable oil ester" refers to a substance that is commonly used as a penetration enhancer in agricultural chemical formulations.

[0019] Examples of "trialkyl phosphates" are trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tri(2-ethylhexyl) phosphate, trinonyl phosphate, and tridecyl phosphate, with tri(2-ethylhexyl) phosphate being the most preferred.

[0020] Examples of “vegetable oil alkyl esters” are:

[0021] a. Straight-chain and / or branched alkyl esters of C10-C24 saturated fatty acids from plant or mineral sources: for example, methyl, ethyl, propyl, butyl, pentanoic acid, palmitic acid, alginic acid, stearic acid, nonadecanoic acid, arachidic acid, dodecanoic acid, tridecanoic acid, and tetradecanoic acid in the form of methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, and 2-ethylhexyl esters.

[0022] b. Straight-chain and / or branched alkyl esters of C10-C24 unsaturated fatty acids from plant or mineral sources: for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, and 2-ethylhexyl esters of α-linolenic acid, linoleic acid, trans-linolenic acid, palmitoleic acid, oleic acid, and erucic acid.

[0023] c. Alkyl esters of vegetable oils, such as sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, and olive oil. Examples of these are...

[0024] i. Methyl esters from rapeseed oil, soybean oil, sunflower oil, castor oil, corn oil, or substances classified under CAS number 67762-38-3 (fatty acids, C16-18 and C18-unsaturated fatty acids, methyl esters).

[0025] ii. Ethyl rapeseed oil, ethyl soybean oil, ethyl sunflower oil, ethyl castor oil, and ethyl corn oil.

[0026] d. A mixture of two or more of the above.

[0027] The most preferred vegetable oil alkyl ester is rapeseed oil methyl ester, and the most preferred mixture of trialkyl phosphate and vegetable oil alkyl ester is tri(2-ethylhexyl) phosphate and rapeseed oil methyl ester.

[0028] c. Dispersant

[0029] As used herein, the term "dispersant" refers to a substance that stabilizes a solid colloid of an active ingredient, as known in the art. In the context of this invention, "dispersant" refers to a surfactant used in the preparation of pyrethroid suspension concentrate formulations. When used as an emulsifier for liquid organic compounds in the context of this invention for the preparation of capsule suspension formulations, some dispersants and chemically similar compounds described below may also be used as emulsifiers. Surfactants of the same chemical class can be used to prepare dispersions or emulsions, depending on the solvent and / or compound to be stabilized, as known in the art (Chemistry and Technology of Surfactants, Ed. Richard J. Farn; 2006, Blackwell). Suitable dispersants in the context of this invention are selected from:

[0030] c1) Polycarboxylate dispersants, such as those of hydrophobically modified comb polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (e.g., isobutylene or diisobutylene), copolymers of acrylic acid with itaconic acid, copolymers of methacrylic acid with itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of maleic acid or maleic anhydride with sulfonated styrene, copolymers of acrylic acid with methacrylic acid, copolymers of acrylic acid and methacrylates, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, copolymers of sulfonated styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, modified copolymers of sulfonated styrene and methacrylic acid, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acid (e.g., C8-C18)-sarcosine salts, carboxylic acids such as resin acids or fatty acids (e.g., C8-C18) or salts of such carboxylic acids. The copolymers described above can also be in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium, or various amines. Examples of these include Geropen T / 36, Geropen TA / 72, Tersperse 2700, Atlox Metasperse 550S, Geropen Ultrasperse, Narlex D-72, Versa TL3, Agrilan 789Dry, Alcoguard 7100 / Agrilan 777, and Alcosperse 747. Furthermore, the copolymers described above can also be ethoxylated. Examples of these materials are Atlox 4913, Geropen DA, Step Flow 4000, and Tersperse 2500.

[0031] c2) Dispersants selected from sulfates of condensation products of formaldehyde and alkyl aromatic compounds, such as MORWET D-425 (from Akzo Nobel); OPARYL DT 120, OPARYL DT 201, OPARYL DT 530 (from Bozzetto); TERSPERSE 2020 (from Huntsman) and sulfates of condensation products of formaldehyde and xylene ether (e.g., BAYKANOL SL, from Levaco) and sulfates of condensation products of formaldehyde and cyclohexanone (e.g., LUCRAMUL DAC 210, from Levaco), and

[0032] c3) Dispersant, selected from lignin sulfonates and their salts, specifically Borregaard's Borresperse NA, Borresperse 3A, Ultrazine NA, Ufoxane 3A, Vanisperse CB, Marasperse AG, MARASPERSEN 22, MARASPERSEN C 21, MARASPERSEN CBOS-4, WAFEX CA122, and Borresperse CA; Ingevity's KRAFTSPERSE EDF-350, KRAFTSPERSE 25M, KRAFTSPERSE EDF-450, REAX 100M, REAX 83A, REAX 85A, REAX 88A, REAX 88B, REAX 907, REAX 910, POLYFON H, POLYFON O, and POLYFON T; Tembec's AGRINOL DN 19 and Agrinol C12, and...

[0033] c4) Dispersants selected from alkyl aryl sulfonates and their salts, such as AEROSOL OS (from Solvay); AGNIQUE ANS 3DNP-U, AGNIQUE ANS 4DNP, AGNIQUE NSC 2NP-U, NEKAL BX DRY (from BASF); MORWET B, MORWETDB, MORWET EFW, MORWET IP (from Akzo Nobel); OPARYL MT 704, OPARYL MT 800, OPARYL MT 804 (from Bozzetto); RHODACAL BX 78, SUPRAGIL WP, RHODACAL 60BE, RHODACAL 70 / B (from Solvay); SURFOM HRB (from Oxiteno), NANSA EVM 40 / 2NDL, ANSA EVM50 / DBC, NANSA EVM 50 / BB (from Innospec); NINATE 100L, NINATE 50H (from Stepan); ATLOX3467 (from Croda), and

[0034] c7) Dispersants selected from the sulfated products of alkylphenols reacted with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide; sulfated products of arylalkylphenols reacted with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide, and their salts, such as SOPROPHOR 4D384, STEOL TSP 16, LUCRAMULSPS16, SURFOM SC 8384, TERSPERSE 2218; and alkyl alcohol ethoxylated sulfates and their salts, such as GENAPOLLRO, AGNIQUE SLES grade, ALKOPON CN, ENVIOMET WT 4062, RHODAPEX ESB 70, and

[0035] c8) Dispersants derived from alkyl sulfonates and their salts, such as Aerosol OT (pure or at different concentrations in different solvents), Enviomet EM5665, Geropon DOS (pure or at different concentrations in different solvents), Synergen W10, Triton GR 7ME, or Agnique SLS (pure or at different concentrations in different solvents), Genapol LSS, Stepanol WA-100, or Witconate NAS-8 / AOS-10, WITCONATE AO5-12 (α-olefin sulfonate), and

[0036] c9) Dispersants selected from phosphorylated products of alkylphenols reacting with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide; or phosphorylated products of arylalkylphenols reacting with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide, and their salts, such as DISPERSOGEN LFH, DISPERSOGEN TP 160 (from Clariant); LUCRAMUL PPS16, LUCRAMUL PPS K 16 (from Levaco); PHOSPHOLAN PHB 14 (from Akzo Nobel); SOPROPHOR 3D 33, SOPROPHOR TS20-F, SOPROPHOR FL, SOPROPHOR FLK (from Solvay); STEPFAC TSP-PE, STEPFAC TSP PE-K (from Stepan); SURFOM 1323SC, SURFOM1325SC (from Oxiteno); TERSPERSE 2222 (from Huntsman); and alkyl alcohol ethoxylated phosphates, such as EMPIPHOS 03D (from Akzo Nobel); MULTITROP 1214, Crodafos series, Atphos 3226 (from Croda); PHOSPHOLAN PE 169 (from Akzo Nobel); RHODAFAC RS-410, RHODAFAC RS-710, RHODAFAC TD 20F (from Solvay); SERVOXYL VPDZ 20 / 100 (from Elementis); STEPFAC 8180, STEPFAC 8181 (from Stepan); CRAFOL AP261 (from BASF); GERONOL CF / AR (from Clariant).

[0037] c10) Dispersants selected from products of the reaction of alkylphenols with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide; products of the reaction of arylalkylphenols with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide / propylene oxide, such as LUCRAMUL EP 12-015, LUCRAMUL PS series (from Levaco); EMULSOGENTS series (from Clariant), Soprophor CY / 8, SOPROPHOR TS series, SOPROPHOR 796 / P (from Solvay), MAKON TSP series (from Stepan), and

[0038] c11) Dispersants derived from the reaction products of alkyl alcohols with ethylene oxide, propylene oxide, or mixtures of ethylene oxide and propylene oxide, such as LUTENSOL XP series, LUTENSOL XL series, LUTENSOL ON series, LUTENSOL AO series, LUTENSOL TO series, AGNIQUE TDA series, AGNIQUE KE 3551, AGNIQUE KE3552 (from BASF); GENAPOL EP series, GENAPOL ID series, GENAPOL XS series, GENAPOL UD series, GENAPOL LA series, GENAPOL C series, GENAPOL OX series, GENAPOL X series, EMULSOGEN EPN series, EMULSOGEN 3510, EMULSOGEN EP 4901, Synergen 848 (from Clariant); ATLAS G 5000, ATLAS G 5002L, ATLOX 4912, ATLOX AL3382, ATLOX 4894, ATLOX 4991, SYNPERONIC 13 / 6, SYNPERONIC 13 / 10, SYNPERONIC A series (from Croda); ECOSURF EH series (from Dow); Rhodasurf 840, Rhodasurf 870, Rhodasurf BC-610, Rhodasurf BC-720, Rhodasurf CC-10, Rhodasurf DA-630, Antarax B / 848 (from Solvay); Series, MAKON DA series, MAKON TD series, TOXIMUL 8315, TOXIMUL 8320, TOXIMUL 8325, TOXIMUL 8350 (from Stepan); BREAK-THRU VIBRANT, SURFYNOL 420, SURFYNOL 440, SURFYNOL 465 (from Evonik), Lucraum HOT, Lucraumul L 06, Lucraumul AG 412 (from Levaco); Series, and

[0039] c12) Dispersants derived from fatty acid ethoxylate / propoxylate derivatives, such as Agnique CSO series, Agnique RSO 60 (from BASF); Alkamuls A, Alkamuls 696, Alkamuls BR, ALKAMULS EL-620, Alkamuls EL-719, ALKAMULS OR / 36, ALKAMULS OR / 40, ALKAMULS R-81, ALKAMULS RG-20 (from Solvay); EMULSOGEN EL 300, EMULSOGEN EL 360, EMULSOGEN EL 400, EMULSOGENVO 13 (from Clariant), Etocas 10, Crovol CR70 (from Croda); LUCRAMUL CO 11, LUCRAMULCO 30, LUCRAMUL CO 40, LUCRAMUL SO 21 (from Levaco), TOXIMUL 8240, TOXIMUL 8242 (from Stepan), and

[0040] c13) Dispersant, derived from di- and triblock copolymers of epoxy alkyl groups, with a molecular weight of 200-10000 Daltons, for example... PE series (from Croda), Pluronic PE, Pluronic RPE series (from BASF), Genapol PF series (from Clariant), and

[0041] c14) Dispersants derived from betaine, such as Adinol CT95SD, Hostapon TPHC; Geropon T-77; Hostapon OSB; Witconate AOS; Agrho FKC 1000; Mackam CAB 818, and

[0042] c15) Dispersants derived from alkyl polyglucosides, such as TRITON CG-50 / 110, TRITON CG-600, TRITON 425-650 (from Dow), AGNIQUE PG 8105, AGNIQUE PG 8107 (from BASF), and

[0043] c16) Dispersant, derived from partially hydrolyzed polymers of vinyl alcohol / pyrrolidone, for example K series, Sokalan VA 64 (from BASF); Agrimer series (from Ashland)

[0044] Preferably, the suitable dispersant is selected from dispersants c1), c2), c3), c7), c8), c9), c13), and c16.

[0045] More preferably, the suitable dispersant is selected from dispersants c1), c2), c3), c7), c8), and c13).

[0046] Most preferably, the suitable dispersant is selected from dispersants c1), c2), c3), c7), and c8).

[0047] The above dispersants can be used alone or in combination, and preferably a combination of dispersants selected from dispersants c1), c2), c7), c8), c9), c13), and c16).

[0048] The above dispersants can be used alone or in combination, and combinations of dispersants selected from dispersants c1), c2), c3), c7), c8) and c13) are more preferred.

[0049] The above dispersants can be used alone or in combination, and even more preferably in combination of dispersants selected from dispersants c1), c2), c3), c7) and c8).

[0050] The above dispersants can be used alone or in combination, with the most preferred option being a combination of dispersants c1) and c2).

[0051] d) Wetting agents

[0052] As used herein, the term "wetting agent" refers to substances known in the art to enhance the wetting of plant leaf surfaces. These materials are particularly capable of dynamically reducing the surface tension of water, thus reducing the surface tension to <50 mN / m after 100 ms.

[0053] Suitable wetting agents are all substances commonly used for this purpose in agricultural chemical compositions. Alkylsiloxanes are preferred, especially alkoxylated alkylsiloxane derivatives, and more preferably ethoxylated / propoxylated alkylsiloxane derivatives. Examples of the above compounds are Momentive's Silwet series products and Evonik's... This product series is particularly recommended, especially the Silwet HS 312 and Silwet HS 604. S200 S240 S279, S301, SD260.

[0054] e) Rheology modifiers

[0055] As used herein, the term "rheology modifier" refers to a substance known in the art to stabilize a dispersion of an active ingredient by influencing the rheological properties of the dispersion.

[0056] The rheology modifier (e1) is preferably selected from modified cellulose ethers, more preferably from methylcellulose, and most preferably from hydroxypropyl methylcellulose (HPMC), such as Vivapur K15M from JRS Pharma.

[0057] The rheology modifier (e2) is preferably selected from hydrophilic synthetic amorphous silica, hydrophobic synthetic amorphous silica, and pyrolytic and precipitated silica, such as those from Evonik. Or any product in the Sipernat product line.

[0058] The preferred rheology modifier (e2) is from Evonik. 200 or Sipernat 22.

[0059] The rheology modifier (e3) is preferably selected from all modified polysaccharides and polysaccharide gums (other than e1) (e.g., gellan gum, jelutong gum, xanthan gum, guar gum, gum arabic, gum tragacanth, black locust gum, tara gum, locust gum, agar, carrageenan, alginic acid, alginate (e.g., sodium, potassium, ammonium or calcium alginate)), starch and its derivatives.

[0060] The preferred rheology modifier (e3) is a polysaccharide gum. The rheology modifier is particularly xanthan gum, such as that from Solvay. G, 23 or from Cargill CX911.

[0061] Any mixture of the aforementioned rheology modifiers e1)-e3) is also suitable, a mixture of rheology modifiers e2) and e3) is further preferred, and rheology modifier e3) is most preferred.

[0062] According to the present invention, clay is excluded as a rheology modifier, including montmorillonite, bentonite, smectite, sepiolite, palygorskite, synthetic lithium saponite, and lithium montmorillonite. Examples are... R; Van B; CT, HC, EW; M100, M200, M300, S, M, W; 50; RD; VAN

[0063] f) Isocyanates

[0064] As used herein, the term "isocyanate" refers to a substance commonly used in the preparation of capsules via interfacial polymerization. In the context of this invention, suitable isocyanates are selected from:

[0065] f1) Alkylphenyl isocyanates, particularly methylphenyl (toluyl) isocyanates. Examples include 1,4-phenylene diisocyanate; 1,5-naphthylene diisocyanate; 2,4- and / or 2,6-toluene diisocyanate (TDI); 1,3- and / or 1,4-bis-(2-isocyanate-propyl-2-yl)benzene (TMXDI); and 1,3-bis(methyl isocyanate)benzene (XDI). Commercial products of this type include, for example, those from Covestro. E, T, L, IL series products.

[0066] f2) Methylene diphenyl isocyanates. For example, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI). Such commercial products are, for example, from Covestro. 44M 44MC 44V40L 44V70L LS2424 2460M CD-S, Baymidur K88 VK series VL series.

[0067] f3) Linear alkyl isocyanates, particularly hexamethylene isocyanates. Examples include 1,4-butyl diisocyanate; 1,6-hexamethylene diisocyanate (HDI); 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate; alkyl-2,6-diisocyanate hexanoate (lysine diisocyanate), linear / branched alkyl groups having 1 to 8 carbon atoms; and 4-methyl-1,8-octyl diisocyanate (nonanetriisocyanate). Commercial products of this type include, for example, those from Covestro. N series XP 2675 XP 2840 Products for XP 2675.

[0068] f4) Cycloalkyl isocyanates, particularly isophorone isocyanates. Examples include isophorone diisocyanate (IPDI); bis-(4,4'-isocyanocyclohexyl)methane (H12-MDI); and 1,4-cyclohexyl diisocyanate. Commercial products of this type include, for example, those from Covestro. Z series XP 2565 XP 2489 XP 2838 XP 2763 product.

[0069] Isocyanates f1-f4 include mixtures of monoisocyanates, diisocyanates, and / or polyisocyanates, or reaction products of mixtures of isocyanates.

[0070] Furthermore, modifiers containing structures of urethane, urea diketone, carbamate, isocyanurate, biuret, iminooxadiazine diketone, or oxadiazine triketone are suitable components for constructing f1-f4 diisocyanates. Multifunctionalized substances such as polymeric MDI (pMDI, e.g., PAPI-27 from Dow or from Covestro) are also suitable. 44V20 type) is a suitable component for constructing f1-f4 diisocyanates.

[0071] Modifiers with an isocyanate functionality (NCO) of 2.0 to 6.0 are preferred.

[0072] More preferably, a modifier having an isocyanate functionality (NCO) of 2.0 to 4.5.

[0073] Modifiers with an isocyanate functionality (NCO) of 2.3 to 4.2 are particularly preferred.

[0074] Modifiers with an isocyanate functionality (NCO) of 2.3 to 3.8 are preferred.

[0075] Modifiers with an isocyanate functionality (NCO) of 2.4 to 3.0 are most preferred.

[0076] The preferred isocyanate / polyisocyanate functional group content is 3 to 50% w / w, more preferably 10 to 40% w / w, particularly preferably 15% to 35% w / w, and most particularly preferably 20 to 35% w / w.

[0077] Any mixture of the above isocyanates f1)-f4) is also suitable.

[0078] The most preferred is a mixture of isocyanates f1)-f2).

[0079] g) Crosslinking agent

[0080] As used herein, the term "crosslinking agent" refers to a substance known in the art that is used as a crosslinking agent during the polyurea interfacial polymerization of isocyanates.

[0081] Examples of such substances include aliphatic diamines, aliphatic triamines, aryl diamines, and aryl triamines. The amine can be a primary or secondary amine.

[0082] Examples include ethylenediamine (EDA), diethylenetriamine (DETA), monoisopropylamine, 4-aminopyridine (4-AP), n-propylamine, polyaziridine based on ethylene or propyleneimine, triethylenetetramine (TETA), tetraethylenepentamine, 2,4,4'-triaminodiphenyl ether, bis(hexamethylene)-triamine, trimethylenedipiperidine (TMDP), guanidine carbonate (GUCA), phenylenediamine, toluenediamine, pentamethylenehexamine, 2,4-diamino-6-methyl-1,3,5-triazine, 1,2-diaminocyclohexane, 4,4'-diaminodiphenylmethane, and 1,5-diaminonaphthylisophorone diamine (1 (5-Diaminonaphthalenisophorondiamine), diaminopropane, diaminobutane, piperazine, aminoethylene piperazine (AEP), poly(propylene glycol)-bis(2-aminopropyl ether) or o,o'-bis(2-aminopropyl)polypropylene glycol-polyethylene glycol-polypropylene glycol, hexamethylenediamine, bis-(3-aminopropyl)amine, bis-(2-methylaminoethyl)methylamine, 1,4-diaminocyclohexane, 3-amino-1-methyl-aminopropane, N-methyl-bis-(3-aminopropyl)amine, 1,4-diaminon-butane and 1,6-diaminon-hexane.

[0083] Aliphatic primary diamines and aliphatic primary triamines are preferred.

[0084] Ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, diethylenetriamine, bis(2-aminoethyl)amine, bis(3-aminopropyl)amine, bis(4-aminobutyl)amine, bis(5-aminopentyl)amine, and bis(6-aminohexyl)amine are particularly preferred.

[0085] Further preferred are hexamethylenediamine, diethylenetriamine, and bis(6-aminohexyl)amine.

[0086] Examples of crosslinking agents include primary and secondary glycols, as well as aromatic glycols and polyols. Examples include ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butylene glycol (1,4), pentanediol (1,5), hexanediol (1,6), glycerol, and 1,2-propanediol.

[0087] Examples of crosslinking agents also include amino alcohols. Examples include triethanolamine, monoethanolamine, triisopropanolamine, diisopropylamine, N-methylethanolamine, and N-methyl-diethanolamine.

[0088] Another example is the use of water as a reagent to release the crosslinking agent. This occurs when isocyanates react with water, thereby releasing amines.

[0089] The amounts of crosslinking agent g) and isocyanate f) are kept in a certain ratio, and the weight of crosslinking agent g) is usually 0-0.4 times the weight of isocyanate f).

[0090] The preferred weight ratio of crosslinking agent g) to isocyanate f) is 0 to 0.3.

[0091] The optimal weight ratio of crosslinking agent g) to isocyanate f) is 0 to 0.2.

[0092] h) Emulsifiers

[0093] As used herein, the term "emulsifier" refers to a substance known in the art as a stabilizer for emulsions. In the context of this invention, "emulsifier" refers to a surfactant used in the manufacture of adjuvant capsule suspension formulations. Some emulsifiers described below may also be used as dispersants in the context of this invention for preparing suspension concentrate formulations. Surfactants of the same chemical class may be used to prepare dispersions or emulsions depending on the system / formulation and the compound used, as is known in the art (Chemistry and Technology of Surfactants, Ed. Richard J. Farn; 2006, Blackwell). Suitable emulsifiers in the context of this invention are selected from:

[0094] h1) Emulsifiers for di- and triblock copolymers of epoxy alkyl groups, with a molecular weight of 200-10000 Daltons, for example... PE series (from Croda); Pluronic PE, Pluronic RPE series (from BASF); Genapor PF series (from Clariant), and h2) are emulsifiers derived from the following: hydrophilic synthetic amorphous silica, hydrophobic synthetic amorphous silica, and emulsifiers for fumed silica and precipitated silica, such as those from Evonik. Or any product in the Sipernat product line, and

[0095] h3) Emulsifiers for partially hydrolyzed polymers of vinyl alcohol / pyrrolidone, such as K series, Sokalan VA 64 (from BASF); Agrimer series (from Ashland), Poval series (from Kuraray), and

[0096] h4) Emulsifiers for the reaction products of alkylphenols with ethylene oxide, or with propylene oxide, or with mixtures of ethylene oxide / propylene oxide; emulsifiers for the reaction products of arylalkylphenols with ethylene oxide, or with propylene oxide, or with mixtures of ethylene oxide / propylene oxide, such as LUCRAMUL EP 12-015, LUCRAMUL PS series (from Levaco); EMULSOGEN TS series (from Clariant); Soprophor CY / 8, SOPROPHOR TS series, SOPROPHOR 796 / P (from Solvay); MAKON TSP series (from Stepan), and

[0097] h5) Emulsifiers for the sulfated products of alkylphenols reacted with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide and propylene oxide; emulsifiers for the sulfated products of arylalkylphenols reacted with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide and propylene oxide, such as SOPROPHOR 4D384, STEOL TSP 16, LUCRAMULSPS16, SURFOM SC 8384, TERSPERSE 2218, and

[0098] h6) Emulsifiers for phosphorylated products of alkylphenols reacting with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide and propylene oxide; emulsifiers for phosphorylated products of arylalkylphenols reacting with ethylene oxide, or with propylene oxide, or with a mixture of ethylene oxide and propylene oxide, such as DISPERSOGEN LFH, DISPERSOGEN TP 160 (from Clariant); LUCRAMUL PPS16, LUCRAMUL PPS K 16 (from Levaco); PHOSPHOLAN PHB 14 (from Akzo Nobel); SOPROPHOR 3D 33, SOPROPHOR TS20-F, SOPROPHOR FL, SOPROPHOR FLK (from Solvay); STEPFAC TSP-PE, STEPFAC TSP PE-K (from Stepan); SURFOM 1323SC, SURFOM1325SC (from Oxiteno); TERSPERSE 2222 (from Huntsman).

[0099] h7) Emulsifiers of lignin sulfonates and their salts, comprising the following substances: Borresperse NA, Borresperse 3A, Ultrazine NA, Ufoxane 3A, Vanisperse CB, Marasperse AG, MARASPERSE N 22, MARASPERSE C 21, MARASPERSE CBOS-4, WAFEX CA122 and Borresperse CA from Borregaard; KRAFTSPERSE EDF-350, KRAFTSPERSE 25M, KRAFTSPERSE EDF-450, REAX100M, REAX 83A, REAX 85A, REAX 88A, REAX 88B, REAX 907, REAX 910, POLYFON H, POLYFONO and POLYFON T from Tembec; AGRINOL DN 19 and Agrinol from Tembec. C12, and

[0100] Emulsifiers preferably selected from the group consisting of h1), h2), h3), and h7).

[0101] Emulsifiers selected from the group consisting of h1), h3), and h7) are particularly preferred. Emulsifiers selected from the group consisting of h3) and h7) are most preferred.

[0102] The most particularly preferred emulsifiers are those selected from the group containing h3).

[0103] A mixture of the above emulsifiers h1)-h7) is also suitable.

[0104] The most preferred emulsion mixture contains the group consisting of h3) and h7).

[0105] i) pH buffer

[0106] As used herein, the term "pH buffer" refers to a substance known in the art to maintain a specified pH value in an aqueous solution. Examples of such buffers are listed in the CRC Handbook of Chemistry and Physics (ISBN: 1-4987-5428-7).

[0107] Preferred ingredients include acetic acid, citric acid, formic acid, phosphoric acid, and sulfuric acid.

[0108] Acetic acid and citric acid are further preferred.

[0109] Citric acid is the best choice.

[0110] j) Defoamer

[0111] As used herein, the term "defoamer" refers to a substance known in the art that can prevent excessive foaming in formulations during customer preparation and / or application. Appropriate defoaming properties should ensure that agrochemical formulations maintain the FAO foam persistence limits specified in CIPAC Method 47.3 throughout their service life.

[0112] Suitable defoamers are all substances commonly used for this purpose in agricultural chemical compositions.

[0113] Silicone oil and magnesium stearate are preferred.

[0114] k) Biocides

[0115] As used herein, the term "biocide" refers to a substance known in the art as capable of preventing the growth of microorganisms / fungi in water-based formulations.

[0116] Suitable preservatives are generally all substances used for this purpose in such agrochemical compositions. Examples that can be mentioned include... (From Lanxess and Proxel)

[0117] l) Antifreeze

[0118] As used herein, the term "antifreeze" refers to a substance known in the art that can prevent agricultural chemicals from freezing. Suitable antifreeze substances commonly used for this purpose in agricultural chemical compositions include propylene glycol, glycerin, and urea.

[0119] m) Antioxidants

[0120] As used herein, the term "antioxidant" refers to a substance known in the art that can prevent the oxidation of agricultural chemicals. Suitable antioxidants commonly used for this purpose in agricultural chemical compositions are butylated hydroxytoluene (BHT) and suitable derivatives thereof.

[0121] The canned adjuvant ZC pyrethroid formulation composition of the present invention

[0122] Examples of canned pyrethroid ZC formulations with adjuvants are as follows:

[0123] One embodiment of the present invention comprises a pyrethroid concentrate formulated as a suspension concentrate in the concentration range of 0.5-20% w / w.

[0124] The preferred concentration range is 1-15%.

[0125] The optimal concentration range is 2-10% w / w.

[0126] An alternative embodiment of the invention comprises a pyrethroid concentrate formulated as a suspension concentrate in the concentration range of 0.5-20% w / w.

[0127] The preferred concentration range is 0.75-15%.

[0128] The optimal concentration range is 1-10% w / w.

[0129] One embodiment of the present invention comprises an encapsulating adjuvant / adjuvant mixture in a concentration range of 1-60% w / w.

[0130] The preferred concentration range is 2-50% w / w.

[0131] More preferably, the concentration range is 4-40% w / w.

[0132] The optimal concentration range is 5-30% w / w.

[0133] Even the optimal concentration range is 6-30% w / w.

[0134] Another embodiment of the invention comprises a dispersant in the concentration range of 1-30% w / w.

[0135] The preferred concentration range is 1.5-25%.

[0136] The optimal concentration range is 2-20% w / w.

[0137] An alternative embodiment of the invention comprises a dispersant in the concentration range of 0.5-10% w / w.

[0138] The preferred concentration range is 1-7.5%.

[0139] The optimal concentration range is 1.3-6% w / w.

[0140] Another embodiment of the invention optionally includes a wetting agent in the concentration range of 0-10% w / w.

[0141] The preferred concentration range is 0-7.5% w / w.

[0142] The optimal concentration range is 0-5% w / w.

[0143] Another embodiment of the invention must contain a wetting agent with a concentration range of 1-10% w / w.

[0144] The preferred concentration range is 1-7.5% w / w.

[0145] The optimal concentration range is 1-5% w / w.

[0146] Another embodiment of the invention comprises an isocyanate in a concentration range of 0.1-2.0% w / w.

[0147] The preferred concentration range is 0.2-1.5% w / w.

[0148] More preferably, within the concentration range of 0.2-1.25% w / w,

[0149] The optimal concentration range is 0.2-1.0% w / w.

[0150] An alternative embodiment of the invention comprises an isocyanate in a concentration range of 0.01-2.0% w / w.

[0151] The preferred concentration range is 0.01-1.5% w / w.

[0152] The optimal concentration range is 0.02-1.25% w / w.

[0153] The preferred concentration range is 0.04-1.0% w / w.

[0154] Another embodiment of the invention comprises a crosslinking agent in the concentration range of 0.05-2.0% w / w.

[0155] The preferred concentration range is 0.1-1.5% w / w.

[0156] More preferably, the concentration range is 0.15-1.0% w / w.

[0157] The optimal concentration range is 0.2-0.8% w / w.

[0158] An alternative embodiment of the present invention comprises a crosslinking agent in the concentration range of 0.005-2.0% w / w.

[0159] Preferably, the concentration range is 0.01-1.0% w / w.

[0160] More preferably, the concentration range is 0.02-0.5% w / w.

[0161] The optimal concentration range is 0.04-0.1% w / w.

[0162] Alternative embodiments of the present invention do not contain crosslinking agents.

[0163] Another embodiment of the invention comprises an emulsifier in the concentration range of 0.001-0.5% w / w.

[0164] The preferred concentration range is 0.005-0.45% w / w.

[0165] The optimal concentration range is 0.01-0.30% w / w.

[0166] The optimal concentration range is 0.02-0.3% w / w.

[0167] Even the optimal concentration range is 0.05-0.41% w / w.

[0168] Another embodiment of the invention comprises a rheology control agent in the concentration range of 0.01%-0.8% w / w, preferably 0.4%-0.7% w / w.

[0169] Another embodiment of the invention optionally includes a pH buffer in the concentration range of 0-1% w / w. Preferably, the pH buffer is mandatory and is present at 0.01-1% w / w.

[0170] Another embodiment of the present invention further includes a defoamer with a concentration range of 0.01-0.1% w / w.

[0171] Another embodiment of the invention further comprises a biocide in the concentration range of 0.01-0.2% w / w.

[0172] Another embodiment of the invention further includes an antifreeze agent in the concentration range of 1-10% w / w.

[0173] Another embodiment of the invention further includes an antioxidant in the concentration range of 0.01-0.1% w / w.

[0174] The compositions of the present invention contain water as a filler up to 100% w / w.

[0175] Preparation of canned adjuvant pyrethroid ZC formulation

[0176] One embodiment of the present invention is a method for preparing ZC agricultural chemical formulations. The pyrethroid adjuvant formulation is prepared by mixing the following formulations in a desired proportion:

[0177] • Pyrethroid suspension concentrate (SC)

[0178] • Adjuvant capsule suspension (CS)

[0179] The resulting preparation is called ZC preparation.

[0180] The pyrethroid SC formulations can be isolated and stored for further use, or prepared in situ immediately before being mixed with the corresponding adjuvant CS formulations to prepare the ZC formulations of the present invention (Table 8). In-situ preparation of the pyrethroid SC formulations means that the water content of the SC pyrethroid formulation is not filled to 100%, as described in Table 2, but rather reduced to suit the concentration of the SC formulation, which is then mixed with the CS formulation to prepare the ZC formulations of the present invention.

[0181] One embodiment of the present invention is a mixture of SC:CS in a ratio ranging from 99:1% w / w to 1:99% w / w.

[0182] A mixture with an SC:CS ratio ranging from 98:2% w / w to 2:98% w / w is preferred; a mixture with an SC:CS ratio ranging from 97:3% w / w to 3:97% w / w is particularly preferred.

[0183] A mixture of SC:CS in a ratio ranging from 96:4% w / w to 4:96% w / w is even more particularly preferred.

[0184] Even more preferably, a mixture in which the ratio of SC:CS ranges from 95:5% w / w to 30:70% w / w.

[0185] The most preferred SC:CS mixture is an SC:CS mixture with a ratio ranging from 90:10% w / w to 30:70% w / w.

[0186] Materials used in the examples

[0187] Adjuvant / Adjuvant mixture

[0188] Product Name CAS number Manufacturer / Supplier Chemical name Disflamol TOF 78-42-2 Lanxess Tris(2-ethylhexyl) phosphate Phytorob 926.65 85586-25-0 Oleon Fatty acids, rapeseed oil, methyl ester Ethyl oleate 111-62-6 Sigma-Aldrich Ethyl oleate

[0189] dispersant

[0190]

[0191]

[0192]

[0193] wetting agent

[0194] Product Name CAS number Manufacturer / Supplier Chemical name Silwet HS 312 - Momentive Polyalkyleneoxysilane Silwet 806 134180-76-0 Momentive Polyepoxide-modified heptamethyltrisiloxane

[0195] rheology modifier

[0196] Product Name CAS number Manufacturer / Supplier Chemical name Rhodopol 23 11138-66-2 Solvay Xanthan Gum Sipernat 22 112926-00-8 Evonik Hydrated silica Van Gel B 12199-37-0 Vanderbilt Montmorillonite minerals

[0197] Isocyanate / crosslinking agent

[0198]

[0199]

[0200] emulsifier

[0201]

[0202] pH buffers / defoamers / biocides / antifreeze agents / antioxidants

[0203]

[0204]

[0205] Tests and methods used in the embodiments

[0206] The evaluation of formulation characteristics is similar to that of DIN 10964 "Sensory analysis - Simple descriptive test". For this purpose, the shape, physical state, color, and other characteristics of the sample to be tested are examined visually and by shaking and tilting (if necessary), especially for example, clumps, agglomerates, sediment formation, subsequent thickening, marbled appearance of sediment, etc.

[0207] granularity Determined by laser diffraction (media: propylene glycol) according to the CIPAC MT 187 Malvern Mastersizer, or by optical microscopy (40x magnification). The intended stable and convenient formulation contains small particles to ensure good storage stability in the concentrate and good suspension stability in aqueous diluents.

[0208] Agglomeration The determination was performed using an optical microscope (40x magnification). The formulation is expected to be stable and convenient, free of agglomerates to ensure good storage stability of the concentrate and good suspension stability of the aqueous diluent.

[0209] Suspension stability Evaluation was performed according to a simplified method based on CIPAC MT 180, and measurements were taken in CIPAC C or CIPAC D water with a 2% aqueous dilution, followed by a 1-hour settling period. The stable and convenient formulation is expected to produce little or no sediment at the bottom of the test container to ensure uniform application of the spray solution.

[0210] Storage stability Tests were conducted for a given number of weeks (w) at different temperatures, such as 0°C, 20°C, 30°C, 40°C, and 54°C, or at thaw-freeze cycling (=TW; a constant temperature change from -15°C to +30°C and recovery within one week).

[0211] Directly after storage Phase separation Record this as the precipitate fraction, and calculate it based on the quotient of H1 [the height of the interface layer between the precipitate phase and the supernatant] divided by H0 [the total packing height of the sample].

[0212] Precipitate fraction = (H1 / H0) * 100 [%)

[0213] Alternatively, directly after storage. Phase separationRecorded as a separation percentage, and calculated by dividing H0-H1 [total packing height of the sample minus the height of the interface layer between the deposited phase and the supernatant] by H0 [total packing height of the sample].

[0214] Separation percentage = (H0-H1) / H0*100

[0215] Expectedly stable and convenient formulations show little or no phase separation when stored at elevated temperatures for extended periods and are easily rehomogenized. Significant phase separation after a short storage period indicates limited storage stability and a marked tendency to form, if any, difficult-to-disperse precipitates during storage.

[0216] Example 1: Screening of dispersants for pyrethroid SC formulations

[0217] All formulation components as described in Table 1 were combined in 25 ml polyethylene screw-cap vials, with 10 g of glass beads (1-1.25 mm in size) added. The vials were capped, clamped in a stirrer (Retsch MM301), and treated at 30 Hz for 45 minutes; during this time, the samples were heated. After this time, the samples were cooled to room temperature, and the consistency of the formulation was assessed. The appearance was examined under a microscope (Zeiss transmission light microscope, 40x magnification), and the particle size was determined by laser dispersion. Very small particle sizes indicated good grindability, while the presence of agglomerates indicated poor dispersion characteristics.

[0218]

[0219]

[0220]

[0221]

[0222] Table 1 Experimental Evaluation

[0223] From the experiments in Table 1, we can select the most suitable dispersant for preparing pyrethroid SC formulations. Suitable dispersants are those combinations in which no aggregates are visible in the micrographs of the formulation, such as Examples 4, 10, 11, 12, 13, 14, 15, 29, 30, 31, 34, 47, 52, 53, 54, 55, 65, 66, 72, 73, 74, 75, and 79-84.

[0224] Example 2: Preparation of pyrethroid SC formulation

[0225] One embodiment of the present invention also relates to a method for preparing a suspension concentrate agricultural chemical formulation as described below. To test the compatibility of the pyrethroid SC formulation with the dispersant identified in Example 1, the pyrethroid SC formulation can be prepared by one of the methods mentioned below:

[0226] 1) Homogenize the pyrethroid a), dispersant c), defoamer j (if appropriate), and water using a colloidal mill, followed by grinding in a bead mill (Eiger mill, 80% 1-1.25 mm beads, 3500 rpm, circulating grinding). After the time required to achieve the desired particle size of the pyrethroid colloid has elapsed, cool the sample to room temperature. After grinding, mix the remaining components of the formulation (rheology modifier, pH buffer, defoamer, biocide, antifreeze, final water concentration, and optional wetting agent) with stirring.

[0227] 2) Mix the pyrethroid a), dispersant c), defoamer j (if appropriate), and water in a bottle, then cap the bottle, clamp it in a stirrer (Retsch MM301), and treat it at 30 Hz for 45 minutes; during this process, heat the sample. After the time has elapsed, cool the sample to room temperature. After grinding, mix the remaining components of the formulation (rheology modifier, pH buffer, defoamer, biocide, antifreeze, final water concentration, and optional wetting agent) with stirring.

[0228] Table 2 Examples of Pyrethroid SC Formulations

[0229]

[0230]

[0231]

[0232]

[0233] Example 3: Preparation of pyrethroid EC formulation

[0234] To test the reconstitutionability of pyrethroid EC formulations, all components specified in Table 3 were mixed together in a suitable container (e.g., glass beaker, steel reactor) and stirred at room temperature with a magnetic stirrer or overhead stirrer until a homogeneous solution was obtained.

[0235] Table 3 - Comparative Examples of Pyrethroid EC Formulations

[0236]

[0237] Example 4: Preparation and characterization of adjuvant CS formulation

[0238] One embodiment of the present invention is a method for preparing a capsule suspension of agricultural chemical concentrate. To test the reconstitutionability of the adjuvant CS formulation, the CS formulation is prepared according to the steps mentioned below:

[0239] I. Preparation of organic phase A)

[0240] II. Preparation of aqueous phase B)

[0241] III. Preparation of emulsion A in B).

[0242] IV. If necessary, add a crosslinking agent (g)

[0243] V. Heating

[0244] VI. Post-processing

[0245] In step (I), the adjuvant / adjuvant mixture b) and isocyanate f) and antioxidant m) (if suitable) are mixed together with stirring. Step (I) of the method of the present invention is generally carried out at a temperature of 10°C to 80°C, preferably 0°C to 50°C, particularly preferably 2°C to 40°C, and most particularly preferably 2°C and 30°C.

[0246] In step (II), the emulsifier or emulsifier mixture h) and, if appropriate, pH buffer i), defoamer j), biocide k), and antifreeze l) are dissolved in water with stirring. Step (II) of the method of the present invention is generally carried out at a temperature of 10°C to 80°C, preferably 0°C to 50°C, particularly preferably 2°C to 40°C, and most particularly preferably 2°C and 30°C.

[0247] In step (III), the organic phase A) is supplied to the aqueous phase B) to obtain an emulsion of A) in B). Typical emulsifier devices for this purpose, such as rotor-stator mixers or jet streams, can be used to prepare the emulsion. Step (III) of the method of the present invention is generally carried out at temperatures from 10°C to 80°C, preferably from 0°C to 50°C, particularly preferably from 2°C to 40°C, and most particularly preferably from 2°C to 30°C. The preparation of the emulsion can be carried out in batches or continuously.

[0248] In step (IV), the emulsion prepared in step (III) is optionally treated with a crosslinking agent (g).

[0249] In step (V), the mixture obtained in step (III) or optionally in step (IV) is stirred for a period of time to ensure complete reaction and efficient capsule formation. Typically, step (V) requires 0 to 24 hours, preferably 0.5 to 8 hours. Step (V) of the method of the present invention is generally carried out at a temperature of 5°C to 80°C, preferably 10°C to 75°C, and most preferably 20°C to 70°C.

[0250] In step (VI), after the capsule formation reaction is complete, the capsule suspension obtained in step (V) is cooled to room temperature and then treated with rheology modifier e). If step (II) has not yet been completed, pH buffer i), defoamer j), biocide k), and antifreeze L) are added to the obtained capsule suspension.

[0251] The method of the present invention is carried out under atmospheric pressure.

[0252] The thickness of the capsule wall can theoretically be calculated based on the amount of isocyanate f) and crosslinking agent g) forming the capsule wall and the particle size of the resulting capsule. The calculated wall thickness of the capsule suspension obtained by the present invention is 0.001 μm to 4 μm, preferably 0.01 μm to 2 μm, and most preferably 0.01 μm to 1 μm.

[0253] Examples of adjuvant / adjuvant mixture CS formulations are provided for preparing the ZC formulation of the present invention by mixing an adjuvant / adjuvant mixture CS formulation with a suitable amount of a pyrethroid SC formulation. Examples of adjuvant / adjuvant mixture CS formulations prepared according to the present invention are listed in Table 4.

[0254] Table 4 - Adjuvant / Adjuvant Mixture CS Formulations

[0255]

[0256]

[0257]

[0258] Technical characterization and storage stability of the adjuvant CS formulation showed stability over time, with no decrease in particle size or capsule instability (Table 5).

[0259] Table 5 - Storage stability of adjuvant CS formulations

[0260]

[0261] Alternatively, the adjuvant / adjuvant mixture (b) can be formulated into an emulsion (EW).

[0262] The adjuvant, emulsifier, water, and optionally polyvinylpyrrolidone are stirred together until a homogeneous white solution is obtained. Then, a stator-rotor emulsifier (e.g., [missing information]) is used. It was further homogenized at 10,000-25,000 rpm until a white homogeneous emulsion was obtained. The particle size of the resulting emulsion was d. 50 0.5-1μm, d 90 1-5μm (emulsifier = Pluronic PE10500) or d 50 5-9μm, d 9015-20 μm (emulsifier = Aerosil R816). The remaining ingredients are added to the emulsion (biocides, defoamers, antifreeze). Examples of adjuvant EW formulations are listed in Table 6.

[0263] Table 6 - Adjuvant EW formulations

[0264]

[0265]

[0266] The technical characteristics of EW formulations are shown in Table 7.

[0267] Table 7 - Technical Characteristics of Adjuvant EW Formulations

[0268]

[0269] Example 5: Preparation and characterization of canned adjuvant ZC pyrethroid formulation

[0270] To test the reconstitutionability of the pyrethroid adjuvant ZC formulation, the pyrethroid SC formulation was stirred together with the adjuvant CS formulation at room temperature until a homogeneous mixture was obtained. The pyrethroid SC formulation can be isolated and stored for further use or prepared in situ before being mixed with the corresponding adjuvant CS formulation to prepare the ZC formulation of the present invention (Table 8). In-situ preparation of the pyrethroid SC formulation means that the water content of the SC pyrethroid formulation is not filled to 100%, as described in Table 2, but rather the water content is reduced to suit the concentration of the SC formulation, which is then mixed with the CS formulation to prepare the ZC formulation of the present invention.

[0271] Alternatively, the pyrethroid SC formulation may be mixed with the adjuvant / adjuvant mixture CS formulation, and the resulting preliminary ZC formulation may be mixed with any other formulation component or water filler to 100% of the final composition, or the necessary volume.

[0272] Examples of the ZC formulation according to the present invention are described in Table 8.

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282] Example 6: Preparation and characterization of canned adjuvant SE pyrethroid formulation

[0283] To test the reconstitutionability of the pyrethroid adjuvant SE formulation, the pyrethroid SC formulation (Table 2) was stirred together with the adjuvant / adjuvant mixture EW formulation (Table 6) at room temperature until a homogeneous mixture was obtained. Water was added to 100% if necessary. The SE pyrethroid formulation served as a comparative example to the ZC pyrethroid formulation because the adjuvant added to the pyrethroid SC formulation was not encapsulated and may contribute to crystal growth during storage.

[0284] Pyrethroid SC formulations can be isolated and stored for further use, or prepared in situ immediately before being mixed with the corresponding adjuvant EW formulation to prepare SE formulations (Table 9). In-situ preparation of pyrethroid SC formulations means that the water content of the SC pyrethroid formulation is not filled to 100%, as described in Table 2, but rather reduced to suit the concentration of the EW formulation, and the SC formulation is then mixed with the EW formulation to prepare the SE formulation.

[0285] Comparative examples of SE formulations are described in Table 9.

[0286]

[0287] Example 7: Technical characterization and storage stability of ZC and SE formulations

[0288] The ZC formulations of the present invention are generally stable during storage and only slightly lose some of their technical properties (Tables 10-12). On the other hand, the comparative SE formulations are unstable during storage and are prone to crystal growth or phase separation.

[0289] Table 10: Granularity assessment during storage

[0290]

[0291]

[0292] Comments on the results in Table 10

[0293] The formulations of the present invention do not exhibit particle size growth, or if any, it is very limited. This contrasts with the comparative SE formulations, in which the adjuvants are not encapsulated and therefore directly contact the pyrethroid active ingredient, thus always exhibiting particle size growth. Upon contact with the pyrethroid, the adjuvant can dissolve the pyrethroid and initiate the Oswald ripening process, leading to a final particle size increase of the pyrethroid and instability in the SE formulation, resulting in the potential sedimentation of the grown particles. This process is particularly evident in Comparative Examples 7-1 and 7-4, but less so in Comparative Example 7-3.

[0294] In contrast, most embodiments of the present invention do not exhibit crystal growth, and those that do show some growth are only to a very small extent. The improved stability of the ZC formulation in terms of crystal growth can be attributed to the fact that the adjuvant in the ZC formulation is coated with the polymer film of the capsule. This prevents direct physical contact between the adjuvant and the pyrethroid. This is impossible for the SE formulation because the adjuvant is emulsified, coated with surfactants, and these emulsifiers do not constitute a sufficiently strong barrier to the establishment of physical contact between the adjuvant and the pyrethroid.

[0295] Table 11: Separation Assessment During Storage

[0296]

[0297]

[0298] Table 12: Assessment of pyrethroid concentrations during storage

[0299]

[0300]

[0301] Comments on the results in Tables 11 and 12

[0302] Both the comparative formulation examples and the formulation examples of the present invention showed good to acceptable stability against separation during storage and maintained satisfactory homogeneity over time, as evidenced by the low to acceptable percentage of separation. Only after 2 weeks at 54°C did the comparative examples show unacceptable separation.

[0303] Furthermore, no significant changes in pyrethroid concentration were detected during storage in either the comparative formulation examples or the formulation examples of the present invention.

[0304] Example 8: Greenhouse bioactivity of the formulation of the present invention

[0305] Peach aphid (Myzus persicae) - Spray test

[0306] Pepper plants (Capsicum annuum) or cabbage plants (Brassica oleracea) severely infested with the peach aphid (Myzus persicae) can be treated by spraying with a formulation of the required concentration.

[0307] The mortality rate was determined as a percentage after 7 days. 100% indicates that all aphids have been killed; 0% indicates that no aphids have been killed.

[0308] Cotton aphid (Aphis gossypii) - Spray test

[0309] Cotton plants (Gossypium hirsutum) severely infested by cotton aphids were treated by spraying with a formulation diluted with water to the required concentration of active ingredients.

[0310] The mortality rate was determined as a percentage after 7 days. 100% indicates that all aphids have been killed; 0% indicates that no aphids have been killed.

[0311] Potato beetle (Leptinotarsa ​​decemlineata) - Spray test

[0312] Potato leaves (Solanum tuberosum) were treated with a formulation of the required concentration and then artificially infected with the Colorado potato beetle (Leptinotarsa ​​decemlineata).

[0313] After 2 and 6 days, the mortality rate was determined as a percentage. 100% indicates that all beetles have been killed, and 0% indicates that no beetles have been killed.

[0314] Tables 13-17 show that the ZC formulation of the present invention has significantly higher activity than the comparative SC formulation, even though both formulations are made from colloidal solid particles of pyrethroids.

[0315] Diamondback moth (Plutella xylostella) - Spray test

[0316] Cabbage leaves (Brassica oleracea) were treated with a formulation diluted with water to the desired concentration and then infected by the larvae of the diamondback moth (Plutella xylostella).

[0317] Two days later, the mortality rate was determined as a percentage. 100% meant that all caterpillars had been killed, and 0% meant that no caterpillars had been killed.

[0318] Table 13 - Biological efficacy of pyrethroid EC, SC, and ZC formulations against peach aphids

[0319]

[0320] Table 14 - Biological efficacy of pyrethroid EC, SC, and ZC formulations against peach aphids

[0321]

[0322] Table 15 - Biological efficacy of pyrethroid EC, SC, and ZC formulations against potato beetles

[0323]

[0324] Table 16 - Biological efficacy of pyrethroid EC, SC, and ZC formulations against peach aphid / cotton aphid / diamond moth

[0325]

[0326] Table 17 - Biological efficacy of pyrethroid EC, SC, and ZC formulations against peach aphids / cotton aphids

[0327]

[0328] Explanation of the results in Table 13-17

[0329] As previously mentioned, the bioactivity of pyrethroids is significantly affected by their formulation. Formulations containing dissolved pyrethroids are more bioactive than those where the active substance is in colloidal solid form. Therefore, the deltamethrin EC formulation examples (emulsifiable concentrate, pyrethroid dissolved) shown in Tables 13-17 consistently demonstrate higher bioefficacy (higher % mortality) than the comparative deltamethrin SC (suspension concentrate, pyrethroid suspended as a solid in water) formulation.

[0330] Surprisingly, the ZC formulation examples of this invention exhibit significantly higher activity than the comparative SC formulation, even though both formulations are made from colloidal solid particles of pyrethroids. The improved performance of the ZC formulation can be attributed to the presence of an encapsulating adjuvant in the formulation. When the formulation is sprayed onto the target plant / pest, the encapsulated adjuvant is released from the capsule. The released adjuvant then dissolves the solid pyrethroid particles, thereby transforming the solid, low-activity pyrethroid into a dissolved, high-activity pyrethroid. Crucially, this dissolution process occurs only when the formulation is applied to the biological system, not during formulation storage. Otherwise, significant crystal growth would be observed during formulation storage, but this is not the case in this application (Table 10).

[0331] Example 9: Field test bioactivity of the formulation of the present invention

[0332] The biological efficacy of the formulations of the present invention was evaluated under field testing conditions. In some cases, the formulations of the present invention showed higher efficacy than comparative example DLTEC100 (Formulation Examples 1-18, Table 18).

[0333]

[0334] Example 10 Toxicological characteristics of the formulation of the present invention

[0335] This application describes a detailed toxicity assessment of the formulation deltamethrin ZC 025 (formulation examples 6-7). As can be seen from Table 19, the toxicological properties of the ZC pyrethroid formulation of this invention are milder than those of the comparative EC / SC formulation. This is demonstrated by lower acute oral toxicity compared to the comparative EC 025 formulation (FL examples 1-17) in screening tests and the absence of eye / skin irritation compared to the EC / SC pyrethroid comparative formulation.

[0336] Screening tests were conducted using deltamethrin ZC 025 (Formulation Examples 6-7).

[0337] - Acute oral toxicity screening test used corn oil as a carrier in male and female mice (n=3 /

[0338] The drug was administered at a dose of 3 (sex). All animals were observed individually, first for 6 hours after administration, then once daily for 14 days or until death. Based on results from 6 treated animals, the acute oral median lethal dose (LD50) of SC was determined in Cr1:WIWistar rats.

[0339] Greater than 520 mg / kg bw. This is a non-GLP study, but follows OECD number 423.

[0340] - In vitro skin irritation screening assay using a reconstructed human epidermal EPISKIN model (non-GLP study, but following OECD number 439). Epidermal units treated with the test sample and those treated with negative controls (2 units / group) were exposed for 15 minutes. Cell proliferation and viability were measured after 42 hours. After exposure to deltamethrin ZC 025, the mean cell viability was 79.7% compared to the negative control. This is above the 50% threshold, therefore the test sample was considered non-irritating to the skin.

[0341] - In vitro ocular stimulation screening test of isolated chicken eyes (non-GLP study). Stimulation was assessed according to OECD number 438, but with a reduced number of eyes (n=2 / group). Corneal thickness and corneal opacity were measured before treatment and approximately 30, 75, 120, 180, and 240 minutes after application of the test substance to the central cornea within 10 seconds and before PBS rinsing. Fluorescein retention was measured at baseline (t=0) and approximately 30 minutes after post-treatment rinsing. No significant corneal swelling, significant changes in corneal opacity (severity 0.5), and significant changes in fluorescein retention (0.5) were noted during the four-hour observation period following exposure to deltamethrin ZC 025. Based on this in vitro ocular stimulation test of isolated chicken eyes, the test substance was non-irritating to the eyes.

[0342] Table 19 - Toxicological endpoints

[0343]

[0344] Comments on the results in Table 19

[0345] As can be seen from Table 19, the toxicological properties of the ZC pyrethroid formulation of the present invention are milder than those of the comparative EC / SC formulation. This is demonstrated by lower acute oral toxicity compared to the comparative EC 025 formulation (comparative formulations 1-39) in screening tests and the absence of eye / skin irritation compared to the EC / SC pyrethroid comparative formulation.

[0346] Importantly, the improved toxicological characteristics of the ZC formulations of the present invention in Examples 6-7 did not come at the cost of lower technical stability, as can be seen from the absence of crystal growth during storage (Table 10).

[0347] Furthermore, the milder toxicological characteristics are not associated with lower biological efficacy (Tables 13-18): on the contrary, in Table 18, the formulation examples of the present invention generally have higher biological activity than the EC formulation comparison examples, which have higher acute toxicity than the ZC formulation examples of the present invention.

[0348] In summary, we have now surprisingly discovered that the ZC formulation, consisting of ground colloidal pyrethroids and encapsulated adjuvant / adjuvant mixtures, can selectively enhance the insecticidal efficacy of pyrethroid suspension concentrates against insects without increasing the mammalian toxicity of the formulation. That is, according to the invention, the pyrethroid ZC formulation performs similarly to the pyrethroid EC formulation against agriculturally relevant pests (results in Tables 13-18), but exhibits significant improvements in mammalian toxicology compared to the comparative pyrethroid EC formulation (results in Table 19).

[0349] Comparison of acute toxicity test results of DLT formulations

[0350]

[0351] Deltamethrin ZC 025, specification number 102000034755.

[0352] Table 20 shows the acute toxicity test results of deltamethrin ZC 025, specification number 102000034755-01.

[0353]

Claims

1. Capsule suspension concentrate, which contains A) Particulate dispersion phase, which includes a) Capsules obtained by reacting isocyanate with a crosslinking agent, optionally. b) The capsule contains an adjuvant or a mixture of adjuvants. B) An aqueous phase containing finely dispersed pyrethroids. The adjuvant or adjuvant mixture is selected from "trialkyl phosphate" of Formula 1, wherein R1, R2, and R3 are the same or different, and R1, R2, and R3 are any C6-C10 alkyl segments. Or a mixture of trialkyl phosphates of Formula 1 and alkyl esters of vegetable oils.

2. The capsule suspension concentrate according to claim 1, wherein the trialkyl phosphate is tri(2-ethylhexyl) phosphate.

3. The capsule suspension concentrate according to claim 1, wherein the mixture is a mixture of tris(2-ethylhexyl) phosphate and rapeseed oil methyl ester.

4. The capsule suspension concentrate according to any one of the preceding claims, wherein the pyrethroid is selected from: flufenacetate, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, biobenzylfuran, cypermethrin, deltamethrin, β-cypermethrin, deltamethrin, λ-cypermethrin, γ-cypermethrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, ... Cypermethrin [(1R)-trans-isomer], deltamethrin, dextromethorphan [(EZ)-(1R)-isomer], cis-cypermethrin, ethoxysulfuron, cypermethrin, fenvalerate, flufenoxuron, flufenoxuron, t-flumethinyl, thiamethoxam, pyrethrin (pyrethrum), fenvalerate, ethoxysulfuron [(1R)-trans-isomer], dextromethorphan, bensulfuron, flusilylpyrethrin, heptafluthrin, methoxysulfuron [(1R)-isomer], tetrabromopyrethrin, tetrafluoropyrethrin, bensulfuron-methyl.

5. The capsule suspension concentrate according to claim 1, further comprising, in the aqueous phase: c) One or more dispersants. d) Optionally, one or more wetting agents, e) One or more rheology modifiers, f) One or more isocyanates g) Optionally one or more crosslinking agents h) One or more emulsifiers.

6. The capsule suspension concentrate according to claim 1, further comprising, in the aqueous phase: c) One or more dispersants. d) Optionally, one or more wetting agents, e) One or more rheology modifiers, f) One or more isocyanates g) Optionally one or more crosslinking agents, h) one or more emulsifiers, and Optionally selected from i) pH buffers, j) defoamers, k) biocides, l) antifreeze additives, and l) antioxidants.

7. The capsule suspension concentrate according to claim 1, further comprising, in the aqueous phase: c) One or more dispersants. d) One or more wetting agents, e) One or more rheology modifiers, f) One or more isocyanates g) One or more crosslinking agents, h) one or more emulsifiers, and Other ingredients may be selected from i) pH buffers, j) defoamers, k) biocides and l) antifreeze additives.

8. The capsule suspension concentrate according to claim 1, wherein the dispersed pyrethroid is present in an amount of 0.5% w / w to 20% w / w based on the total weight of the formulation.

9. The capsule suspension concentrate according to claim 8, wherein the dispersed pyrethroid is present in an amount of 0.75-15% w / w based on the total weight of the formulation.

10. The capsule suspension concentrate according to claim 9, wherein the dispersed pyrethroid is present in an amount of 1-10% w / w based on the total weight of the formulation.

11. The capsule suspension concentrate according to claim 1, comprising the following components: Adjuvant / adjuvant mixtures with concentrations ranging from 1% to 60% w / w Dispersants with a concentration range of 0.5-10% w / w Wetting agents with a concentration range of 0-10% w / w Isocyanates with concentrations ranging from 0.01% to 2.0% w / w. Emulsifiers with a concentration range of 0.001-0.5% w / w. Rheology control agents with a concentration range of 0.01%-0.8% w / w. Mix with water up to 100% w / w.

12. The capsule suspension concentrate according to claim 11, wherein the concentration range of the wetting agent is 1-10% w / w.

13. The capsule suspension concentrate according to claim 1, comprising the following components: Adjuvant / adjuvant mixtures with concentrations ranging from 1% to 60% w / w Dispersants with a concentration range of 1-30% w / w Wetting agents with a concentration range of 0-10% w / w Isocyanates with concentrations ranging from 0.01% to 2.0% w / w. Emulsifiers with a concentration range of 0.001-0.5% w / w. Rheology control agents with a concentration range of 0.01%-0.8% w / w. Mix with water up to 100% w / w.

14. The capsule suspension concentrate according to claim 13, wherein the concentration range of the wetting agent is 1-10% w / w.

15. The capsule suspension concentrate according to claim 1, comprising the following components: Adjuvant / adjuvant mixtures with concentrations ranging from 1% to 60% w / w Dispersants with a concentration range of 1-30% w / w Wetting agents with a concentration range of 0-10% w / w Isocyanates with concentrations ranging from 0.1% to 2.0% w / w. Emulsifiers with a concentration range of 0.001-0.5% w / w. Rheology control agents with a concentration range of 0.01%-0.8% w / w. Mix with water up to 100% w / w.

16. The capsule suspension concentrate according to claim 15, wherein the concentration range of the wetting agent is 1-10% w / w.

17. The capsule suspension concentrate according to claim 1, comprising the following components: Adjuvant / adjuvant mixtures with concentrations ranging from 1% to 60% w / w Dispersants with a concentration range of 1-30% w / w Wetting agents with a concentration range of 0-10% w / w Isocyanates with concentrations ranging from 0.1% to 2.0% w / w. Emulsifiers with a concentration range of 0.001-0.5% w / w. Rheology control agents with a concentration range of 0.01%-0.8% w / w. pH buffers with a concentration range of 0-1% w / w Defoamers with a concentration range of 0.01-0.1% w / w. Biocides with a concentration range of 0.01-0.2% w / w. Antifreeze with a concentration range of 1-10% w / w Antioxidants with a concentration range of 0.01-0.1% w / w. And as filler water up to 100% w / w.

18. The capsule suspension concentrate according to claim 17, wherein the concentration range of the wetting agent is 1-10% w / w.

19. The capsule suspension concentrate according to any one of claims 11-18, further comprising a crosslinking agent in the concentration range of 0.05-2.0% w / w.

20. A method for preparing the capsule suspension concentrate according to any one of claims 1-7, characterized in that... Mix pyrethroid suspension concentrate SC with adjuvant capsule suspension concentrate CS.

21. A capsule suspension concentrate, obtained by the method according to claim 20, characterized in that... The SC:CS ratio ranged from 90:10% w / w to 30:70% w / w.

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