TW200838420A - Liquid pesticide concentrate formulation comprising phenylsemicarbazone compounds - Google Patents

Abstract

The present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate, comprising (a) a phenylsemicarbazone compound of the formula A wherein R1 and R2 are each independently hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy and R3 is C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, or an agriculturally acceptable salt thereof; (b) one or more amides of the formula (bl) as defined in the description, and (c) one or more surfactants. The inventive concentrates are effective against a broad spectrum of insect pests and allow for high concentrations of the active ingredient, while still exhibiting excellent storage stability and producing highly stable compositions upon dilution with water.

Description

200838420 IX. OBJECTS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to liquid pesticide concentrate formulations comprising at least one phenyl half carbachol of formula A as defined below and relating to the control of organisms harmful to crops the use of. [Prior Art] Agricultural active compounds can be applied in the form of aqueous emulsions, solutions or suspensions. Typically, the active ingredient is diluted after being shipped as a liquid concentrate formulation. For example, an emulsifiable concentrate (EC) typically comprises an active ingredient, an intervening agent, and an organic solvent, and is used after dilution with water to form a creamy oil-in-water emulsion containing the active ingredient dissolved in small droplets of the solvent. Microemulsion concentrates (MC or MEC) have also been described and are understood to mean compositions which form a microemulsion after dilution with water. A microemulsion is understood to be an emulsion that is thermodynamically stable and has a droplet size typically in the submicron order (typically 2 〇〇 nnl or below 200 nm) emulsification phase. One of the problems with such liquid concentrates is that agriculturally active ingredients are generally shown to be extremely insoluble in water. When attempting to provide a liquid concentrate, difficulties associated with providing a high concentration of active ingredient are encountered. However, it is highly desirable to be able to transport the active ingredient at the highest possible concentration to minimize shipping costs. For the application of pesticides to crop fields, it is also important to form a stable emulsion after dilution with water, and the emulsion does not separate after standing. In addition, there should be no crystallization of the active ingredient from the emulsion after dilution with water. In addition, the concentrate itself must have a physical stability of 128803.doc 200838420 during extended storage periods and at widely varying storage temperatures. Phenyl semicarbazone compound of formula A:

Wherein R and R are each independently hydrogen, halogen, cyano, C]_c4, or a CrC4 alkoxy group, a CrC# haloalkyl group or a Ci-c4 haloalkoxy group, and are a C alkoxy group, C. -C4 haloalkyl 4Cl-C4 haloalkoxy, and agriculturally acceptable salts thereof are known from EP 0 462 456 A1. The compound of formula A has a broad spectrum of insecticidal activity against arthropod pests and nematodes, especially against harmful insects. Similar to most active ingredients used as pesticides, the formula is only slightly soluble or even insoluble in hydrophilic media such as water. By way of example, it typically has a water solubility of no more than 2 g/i and usually two at 2 rC/1013 mbar. Some attempts have been made to provide a pesticide formulation of Phenyl Semicarbazone of Formula A. W〇 2006/002984 A1 discloses a liquid pesticide formulation wherein at least one organic pesticide compound is dissolved in a water-miscible solvent 盥 at least one nonionic block copolymer mixture. The pesticidal compound may especially be a phenylhalocarbazone compound of the formula A. The solvent used is capable of dissolving the active ingredient and may contain water, with the proviso that the weight ratio of water to solvent does not exceed 128,803.doc 200838420 WO 2006/133928 A2 discloses phenyl half carbachol of formula a or an agriculturally acceptable salt thereof The use of seed treatment and seed treatment to control the corresponding methods of arthropod pests. Seed treatment formulations comprising phenylhalocarbazone are also disclosed. WO 2006/127399 A2 discloses a highly loaded concentrated composition comprising a metaflumizone, an optional bridging agent, a surfactant, and a suitable carrier solvent. The compositions can be administered topically to the animal and are suitable for prolonged prevention or treatment of parasite infestation in warm-blooded animals. WO 2007/017501 A2 discloses an emulsifiable concentrate formulation comprising (&) a succinyl semicarbazone compound of formula A, (b) comprising gamma-butyrolactone, one or more aliphatic and/or aromatic ketones and A solvent system of one or more aromatic hydrocarbons, (C) one or more emulsifiers and (d) other formulation additives as appropriate. JP 2006131515 A discloses a pest controlling agent composition containing a guanamine compound and at least one compound selected from the group consisting of a suicide compound, an acaricidal compound and a nematicidal compound as an effective component. WO 2007/077246 A2 discloses liquid concentration formulations which can be diluted with water, comprising (a) at least one organic pesticide compound having a water solubility of not more than 5 g/1 at 25 ° C / 1013 mbar, (b) comprising i) at least one C2_C4 alkanediol and ii) a solvent mixture of at least one CrC4 alkylene dicarbonate and (c) at least one surfactant. The pesticide compound may especially be a phenylhalofcarbazide compound of the formula A. WO 2007/1103 55 A discloses agrochemical formulations comprising phantom 01-50% comprising (especially) cyanofluorfen and arsonin, or cyanofluorfen and teflubenzuron or cyanofluorfen and At least two pesticides of flufensulfone 128803.doc 200838420 (flufen〇xuron), b) 30-99.8 wt% of at least two polar organic solvents, c) 0.1-50 wt% comprising nonionic distyrylcycloalkoxy a mixture of a complex and an ionic diphenylethylphenol alkoxylate, d) 0-50 wt% of a nonionic surfactant and e) 0-20 wt% of other formulation auxiliaries. PCT/EP2007/060449 discloses a liquid pesticidal composition comprising (4) a base semicarbazone compound of formula A; (b) a solvent selected from the group consisting of water and a polybasic c2_c4 alcohol and mixtures thereof at 25 ° C / 1013 mbar. The pesticide compound of A may be dissolved in the solvent in an amount of not more than 2 g/Ι; and (c)- or a plurality of surfactants, wherein the compound of the formula A is not more than 丨·5 μπι (as determined by dynamic light scattering) The volume median diameter of the particle form exists. There is still a need to provide a liquid concentrate formulation of this drug containing a relatively high concentration of a phenylhalocarbazone compound of the formula, which is particularly attractive from an economic standpoint. Despite the high pesticide loading, there is a further need for liquid concentrates that exhibit good stability characteristics. After dilution with water, the formulation should form a stable aqueous composition of the active ingredient and the formation of the coarse component should be avoided. In addition, precipitation of the active ingredient should be prevented when stored for extended storage or storage at elevated temperatures. It is also an object of the present invention to provide liquid pesticide formulations with good to excellent control over a wide range of harmful insects. SUMMARY OF THE INVENTION Surprisingly, it has now been found that these and other objects are attained by a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate. The condensate formulation comprises: a) a phenyl half carbachol compound of the formula A: 128803.doc -10 - 200838420 Η Η

(8), Cl_C4 alkoxy, CVC4 haloalkyl or C1-C4 haloalkoxy and R3 is

Cl_C4 alkoxy, Ci-C4 haloalkyl or anthracene-fluorenyl alkoxy, or an agriculturally acceptable salt thereof; b) as one of an organic solvent or a plurality of guanamines of the formula bl:

R4—co_nT

R, R6 (b1) wherein R, C6_C20 alkyl, hydrazine. A dilute group or a radical, and R and R6 are each independently hydrogen or an alkyl group, and e) or a plurality of surfactants. This liquid-based pesticide concentrate formulation is effective against a wide range of harmful insects. The formulation of the present invention contains a relatively high concentration of the pesticide compound, but it exhibits good stability at high temperatures for a long storage period without significant phase separation or significant agglomeration of the active ingredient. The high loading of the ingredients and the enhanced biological effects provide extreme value to the end user with, for example, better handling, lower cost and % environmental protection through low application rates, and low exposure to human M and better safety. Several advantages. In standard water and in hard water, the formulations of the present invention show good dilution and emulsification characteristics of SBOS.doc 200838420. The formulations of the present invention also have excellent wetting and leaf absorbing properties. The term "C1-C4 alkyl" as used herein (as used herein and as used in related terms such as C!-C4 alkoxy, c^c:4 haloalkyl 4Ci_c4 haloalkoxy) has 1 a linear or branched aliphatic alkyl group of up to 4 carbon atoms, such as an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

The term "self" as used herein is used in the context of a term such as halo, a, moth and desert, preferably selected from the group consisting of II and chlorine. More preferably, it is fluorine. The term "Cl_c4 alkoxy group, as used herein, refers to a c丨·C4 alkyl group as defined above via an oxygen atom, such as methoxy, ethoxy, propoxy, isopropoxy, positive Butoxy, second butoxy and third butoxy. The term "Cl_C4M group" as used herein refers to another one or more (e.g., 2, 3, 4, 5 or 6) as defined above (d). a Ci-C4 alkyl group as defined above, for example, a monofluoromethyl group, a difluoromethyl group and a trifluoromethyl group, a monochloroindenyl group, a dichloromethyl group and a trichlorof group, i•fluoroethyl group, 4, Ethylene, 2-fluoroethyl '2-chloroethyl, i-difluoroethyl, u-dichloroethyl, n-difluoroethyl ' 1,2-dichloroethyl ' 2,2_ two Fluoroethyl, 2,2-dichloroethyl, 2,2,2-difluoroethyl and 2,2,2·trichloroethyl. The term "Cl-C4_alkoxy" as used herein, refers to a CVC4 alkane as defined above, which additionally contains one or more (eg, 2, 3, 4, 5 or 6) of the aze atom as defined above. Alkyl groups such as monofluoromethoxy, dimethoxymethoxy, monooxymethoxy, dichloromethoxy and trichloromethoxy: core 128803.doc -12- 200838420 ethoxy, 1-chloro^ gas Ethoxy A diethoxy ethoxy, 2-chloroethoxy, U-dihydrocarbyl, 1 dichloroethoxy, i 2 an oxy, 2,2-difluoroethoxy, 2 , 2_dichloro: ethyl lactyl, 1,2-diethylene ethyl and 2,2,2-trichloroethoxy.,-,I-based, 2,2,2-trifluoroethoxy in the present invention In another embodiment, the formulas are independent of each other, and are particularly suitable for substituents R, R and R (

Rl is (the (10) form thereof) has the meanings given below: R is a cvc4i group', especially a trifluoromethyl group; R2 is a cyano group;

R3 is eve" methoxy, especially trifluoromethoxy. The preferred compound of formula 8 is that R1 is ringing (that is, 3 is placed in the meta position), R is 4-CN (that is, (3) is placed in the para position), and & 3 is 4-〇 (^3). The compound of CF3), which is cyanofluorfen. The cyanofluorfen is 2-[2_(aminophenyl)-1-[3-(di-methyl)phenyl]ethylene ]_Ν·[4·(Tri-methoxy)phenyl]decylamine (IUPAC nomenclature*: (called 2, _[2·(4·N-phenylphenyl)-1-(α,α,α a common name for -difluorom-tolyl)ethylidene]_4_(trifluoromethoxy)anilinocarbazide having the following formula VIII!:

(Α1) The compound Α1 is present in the form of two geometric isomers for the CN double bond 'i.e., 4-{(2Ε)-2-({[4-(trifluoromethoxy)anilinyl)carbonyl})肼)) 2-[3·(trifluoromethyl)-phenyl]ethyl}benzonitrile and 4-{(2Ζ)-2-({[4-(trifluoro-128803.doc -13- 200838420)曱oxy)anilino] benzylidene)·2·[3-(trifluoromethyl)phenyl]ethyl) styrene. It is to be understood that the cyanofluorfen oxime comprises the oxime-isomer and the oxime-isomer of the compound as defined above and any mixture thereof in any ratio. Compounds and oximes, isomers and oxime-isomers and their interconversions are generally described in WO05/047235, which is incorporated herein by reference. For details, refer to the above geometric isomers of cyanofluorfen (WO05/047235 refers to it as 1-E&1-Z (or description, synthesis and conversion# (W〇〇5/〇47235) Examples 1 to 3) and mixtures of the E-isomer and the Z-isomer, especially having a high E/Z ratio, because the insecticidal activity of the E-isomer is generally higher than that of the Z-isomer The activity is high, so it may be preferred to have a cyanofluorfen which is higher than the E/Z ratio. • In the formulation of the present invention, the compound A is present in the form of the pure compound A. The purity of the compound A is usually at least 90. % by weight, preferably at least 95% by weight. Compound 8 may be present in a neutral form or in the form of a salt obtained by treating Compound A with a suitable base. In one embodiment, the salt of Compound A contains A cation of a base equilibrium ion, such as sodium or potassium, an ion. Typically, compound A will be present in a neutral form. The amount of compound A can generally be from 65 wt% to % by weight based on the total weight of the formulation. 15 to 50% by weight and more preferably 17·5 to 48% by weight, particularly preferably 2 to 40% by weight In the above formula (b1), the following terms have the following meanings: - "CVC^alkyl" means a straight or branched aliphatic leuko having 6 to 2 carbon atoms, such as hexyl, heptyl, Octyl, sulfhydryl, fluorenyl, eleventh decyl, fourteen, fifteen, sixteen, seventeen, 128,803.doc •14·200838420 Α 十九 nineteen bases and ten bases and similar bases a group, and a naphthenic earth such as a cyclohexyl group and the like. _ = 语 "cvc2. County" means a branched or unbranched chain residue and a hydrocarbon group having 6 to 2 () carbon atoms, Any position containing at least one double bond, such as hexyl, heptenyl, octenyl, nonenyl, decyl, eleven, twelve, thirteen, tetradecenyl, ten Pentavalent, hexadecenyl, heptadecenyl, ten-membered, nine-alkenyl, penta-alkenyl and the like. The term cvc^oalkynyl means having 6 to 20 carbon atoms a branched or unbranched chain unsaturated hydrocarbon group having at least one reference bond at any position, such as hexynyl, heptyl, octynyl, anthracenyl, decynyl, undecynyl, eleven Alkynyl, tridecynyl, tetradecynyl, pentadecynyl, heptadedecyl, octadecynyl, ninthyl alkynyl, octadecyl and the like. In another embodiment, The substituents R4, V5 and Han6 (independently, but especially in combination) of the guanamine of formula (bl) have the meanings given below: R is a c6-c2 alkyl group, especially a c6_c12 alkyl group; R is a C1-C4 alkyl group, especially a methyl group; R6 is a fluorenyl-fluorenyl group, especially a methyl group. In another embodiment, R4 is CVC>2 alkyl, and R5 and R6 are both Ci_c4 alkyl. In another embodiment, R4 is CVCu alkyl, and both 5 and 6 are methyl. In another embodiment, R4 is selected from the group consisting of ketone, octyl, decyl and dodecyl and R5 and R6 are both fluorenyl. 128803.doc -15- 200838420 In another yoke, the amide of formula (bl) is selected from the group consisting of N,N-dimethylhexylamine, N,N-dimethyloctylamine, N,N Dimethyl decylamine and N,N•didecyldodecylamine. In another embodiment, the guanamine of formula (bi) is a mixture comprising N,N-dimercaptooctylamine and N,N-dimethylguanamine. In another embodiment, the indoleamine of formula (M) comprises N,N-dimethylhexylamine, hydrazine, hydrazine-methyl octylamine, N,N-:methyl decylamine, and N, A mixture of N-dimethyldodecanoate. In another embodiment, the indoleamine of formula (bi) is comprised of from 5 to 65 weight percent. N,N-dimethyloctylamine, 37 to 50% by weight of n,N-dimethyldecylamine, hydrazine to 5 wt% of N,N-dimethylhexylamine and hydrazine to 2 parts by weight of 0/〇 of a mixture of 1 dimethyl dodecylamine. a mixture of the above carboxylic acids of N,N-dimethylguanamine can be, for example,

Hallcomid® M-8-10 (from C.P. Hall Co.) and Agnique® KE 3658 (from Cognis) are commercially available.

The carboxylic acid ruthenium, ruthenium decyl decylamine has been described as a > granule or tooth penetration enhancer in agrochemical formulations, see, for example, us 3,342,673, US

5,206,225, US 5,283,229, WO 2006/029736 A1 and WO 2005/104844 A1. The amount of one or more indoleamines (bi) may generally range from 15 to 80% by weight, especially from 20 to 70% by weight, more preferably from 3 to 65, by weight based on the total weight of the formulation. /. Within the scope. The formulations of the present invention may additionally comprise one or more other organic solvents (b2) such as non-polar solvents, polar protic solvents or polar aprotic solvents 128803.doc -16-200838420 and mixtures thereof. For the purposes of the present invention, examples of other organic solvents (b2) are ') quaternary hydrocarbons such as pentane, hexane, octane, cyclohexane and aliphatic and isoparaffin mineral oils;

2) aromatic hydrocarbons, such as derivatives of benzene, such as alkylbenzenes, such as toluene, dimethyl methacrylate and monoisopropylbenzene; derivatives of naphthalene, such as alkyl naphthalene, such as 1-nonylnaphthalene or 2- Mercaptophthalene; and mixtures thereof, such as those obtained from Exx〇nM〇bil, such as s〇1vm(10)8 100, SolVess_ 15〇 (boiling point 187_2〇rc)&s〇lvess_ 2〇〇iS〇lvesso® series and Aromatic 100 , Aromatic 150 and Ar0matie "o fluid product; b2.3) halogenated aliphatic hydrocarbons such as dichloromethane; b2, 4) halogenated aromatic hydrocarbons such as chlorobenzene or dichlorobenzene; b2.5) lactones such as gamma - butyrolactone; and b2.6) ketones, especially aliphatic and / or aromatic ketones, such as c] _Cm aliphatic ketone, Ci-C2 oxime ring ketone and aromatic ketone, such as 2-g- Propylene ketone, cyclohexanone, isophorone and acetophenone. The amount of solvent b2 can generally be from 2 to 20% by weight, especially from 5 to 20% by weight, more preferably from 5 to 17% by weight based on the total weight of the formulation. In another embodiment of the present invention, the organic solvent b2 is selected from the group consisting of b2 2 and b2.6. In another embodiment, the organic solvent b2 is selected from the group b2.2. Especially Fang a hydrocarbon, preferably Solvesso 200 and Aromatic 200. The amount of aromatic hydrocarbon is from 8% to 8% by weight based on the total weight of the formulation, especially from 1 to 7% by weight, more preferably from 2 to 128,803.doc -17 - 200838420 5 In another embodiment, the organic solvent b2 #冯白h ^ / 蜊 is suitable from the b2.6 group, especially the Cr 〇2 〇 aliphatic ketone 'better C3_Cs aliphatic _ and more wei Further 1 soil 2_heptanone. C--C2 () The amount of aliphatic ketone is 〇 to 25% by weight, especially 3 to 2% by weight, more preferably 4 to 15% by weight, based on the total weight of the formulation. Inside.

According to the invention, the formulation comprises (c) one or more surfactants. As used herein, the term "surfactant" is used broadly to include any organic material that can reduce the surface tension of the phase boundary between the organic phase and the aqueous phase and can be referred to as an emulsifier, detergent, dispersant, and wetting agent. Surfactant ((the nature of hydrazine is not particularly critical, for example it may be nonionic, anionic, cationic or amphoteric. Surfactants suitable for the purposes of the present invention and methods for their preparation are those skilled in the art) Well known. Such surfactants are, for example, "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, NJ, USA 1981; H Stache, ''Tensid-Taschenbuch", Second Edition, c. Hanser ,

Munich ^ Vienna ^ 1981 ; M.^J. Ash > ^Encyclopedia of

Surfactants,,, Volume I-III, Chemical Publishing Co., New

Revised in York, NY, USA 1980-1981. In each case, suitable surfactants are also commercially available, for example, under the trade names mentioned below. In general, the liquid pesticide concentration formulation of the present invention contains at least 0. 1 to 30% by weight, preferably 3 to 20% by weight and especially 5 to 15% by weight, based on the total weight of the formulation. A surfactant (c). In one embodiment, the formulation of the present invention comprises at least one nonionic surfactant. The nonionic surfactant is generally calculated from the total weight of the formulation 128803.doc -18 - 200838420, from 1 to 30 weight. /. In particular, it is present in an amount of from 5 to 15% by weight, more preferably from 5 to 1% by weight and even more preferably from 2.5% to 7.5 % by weight. In another embodiment, the formulation of the present invention comprises at least one anionic i interface and at least one nonionic surfactant. If such a combination of an anion-ionic surfactant and a nonionic surfactant is used, the amount of the anionic surfactant is 〇·5 to 2% by weight, especially i to 丨$% by weight and more preferably 2 Up to 7.5 wt%, and the amount of the nonionic surfactant is φ 〇·5 to 20% by weight, especially 1 to 15% by weight. And more preferably 2 to 7.5 weight. /❻, in each case based on the total weight of the formulation. Exemplary nonionic surfactants suitable for use in the present invention include: el) polyethylene glycol oxime 22 alkyl ethers, polyethylene glycol/polypropylene glycol 'alkyl ethers, especially linear or branched alkanols Ethoxylation and hydrazine - ethoxylate _ co-propoxylate, more preferably polyethoxylated C8_C22 fatty alcohol and polyethoxylated Cs_C22 oxyl alcohol, such as polyethoxylated lauryl alcohol, Polyethoxylated isotridecyl alcohol, polyethoxylated cetyl alcohol, polyethoxylated stearyl alcohol, lauryl alcohol poly-ethoxylate-co-propoxylate, cetyl alcohol Poly-ethoxylate-co-propoxylate, isotridecyl alcohol poly-ethoxylate 7 co-propoxylate, octadecyl poly-ethoxylate _ co-propoxylation '物' and its esters, such as acetate; c · 2) ethylene glycol aryl ether and polyethylene glycol / polypropylene glycol aryl ether, especially single Ci-C! 6 alkyl phenol or dialkyl phenol Polyethoxylates and poly-ethoxylate-co-propoxylates such as nonylphenol, nonylphenol, isodecylphenol, dodecylphenol or isotridecyl 128803.doc •19· 200838420 Phenol aggregation Oxide and polyethoxylate-co-propoxylate, polyethoxylate of monostyrylphenol, distyrylphenol and tristyrylphenol and poly-ethoxylates - propoxylate; and its esters, such as acetate; c.3) C6-C22 alkyl glycoside and C6-C22 alkyl polyglycosides; c. 4) partial esters of polyhydric alcohols with C^C22 succinic acid In particular, mono-, di- and tri-esters of glycerol and sorbitan and sorbitan, such as glyceryl monostearate, sorbitan monooleate, sorbitan tristearate Acid ester; c.5) C6-C22 alkyl glycoside polyethoxylate and 〇6_(:22 alkylpolyglycoside polyethoxylate; 'c.6) C^C22 fatty amine polyethoxylate Polycarboxylates and poly-ethoxylates _, propoxylates; c, 7) polyethoxylates of C6-C22 fatty acids and poly-ethoxylates - _ = oxylates and hydroxy C6_C22 fatty acids Polyethoxylate and Φ poly-ethoxylate-co-propoxylate; c.8) ethoxylate of decyl alcohol and C6_C22 succinic acid, especially glycerol: Diacetate polyethoxylate Polyethoxylates of monoesters, diesters and triesters of sorbitan, such as polyethoxylates of glyceryl monostearate, sorbitan monooleate, polyethoxylates Polysorbate of sorbitan monostearate: a complex and a ethoxylate of sorbitan tristearic acid; C.9) a polyethoxylate of vegetable oil or animal fat, such as corn Oil B 128803.doc -20- 200838420 oxylate, castor oil ethoxylate, tallow ethoxylate; C, 1 0) fatty amide, fatty decylamine or fatty acid diethanolamine polyethoxylate ; c.ll) polyethoxylates of monostyrylphenol, distyrylphenol and tristyrylphenol, and poly-ethoxylate-co-propoxylates, and S thereof Vinegar·, c. 12) a nonionic block comprising at least one poly(ethylene oxide) moiety pE〇 and at least one polyether moiety PAO derived from C3_C1G alkylene oxide and/or styrene oxide a copolymer, especially a polyoxyethylene-polyoxypropylene-block copolymer; c. 13) containing a graft a nonionic graft copolymer of a polyethylene oxide partial group PEO on a nonionic hydrophilic polymeric backbone; and c.14) an organopolyfluorene surfactant such as a polyoxylized polyalkylene oxide Copolymer. The terms polyethylene glycol, polyethoxylate and polyethoxylate refer to polyether groups derived from ethylene oxide. Similarly, the term poly-ethoxylate-co-propoxylate refers to a polyether group derived from a mixture of ethylene oxide and propylene oxide. Thus, the polyethoxylate has a repeating unit of the formula [Ch2CH2〇], and the poly-ethoxylate-co-propoxylate has repeating units of the formula [CH2CH2〇] and [CH(CH3)CH2〇]. In another embodiment, the nonionic surfactant is selected from the group consisting of ^6, c.7, c.i2, c.i4, and mixtures thereof. Particularly preferred nonionic surfactants are those selected from the group consisting of c. 12 and c. 14 . 128803.doc -21- 200838420 c- 12 Group of nonionic block copolymers of surfactants comprising at least one poly(ethylene oxide) moiety group PEO and at least one hydrophobic polyether moiety group PAO. The PAO moiety usually comprises at least 3, preferably at least 5, especially 10 to 100 repeating units (average number) derived from a C3-C1G alkylene oxide, the C3-C1G alkylene oxide being Such as propylene oxide, 1,2-butylene oxide, cis or trans-2,3-butylene oxide or oxidized isobutylene, 1,2-pentylene oxide, 1,2-oxyhexene, 1,2-decene oxide And styrene oxide, of which a C3-C4 alkylene oxide is preferred. Preferably, the PAO moiety comprises from 10 to 60% by weight of repeating units derived from propylene oxide. The PEO moiety usually contains 2 to 6, preferably 3 to 5, and more preferably 3 or 4 repeating units derived from ethylene oxide (average number). Surfactant c·12 having an average number average molecular weight Mn ranging from 600 to 8,000 Daltons, preferably from 1000 to 6000 Daltons, and especially from 1500 to 5000 Daltons, is preferred. The non-ionic block copolymer surfactants of group c. 12 described herein are commercially available, for example, under the following trade names: Pluronic®, such as Pluronic® P 65, P 84, P 103, P 105, P 123 And Pluronic® L 31, L 43, L 62, L 62 LF, L 64, L 81, L 92 and L 121 ; Pluraflo® such as Pluraflo® L 860, L 1030 and L 1060 ; Tetronic® such as Tetronic® 704 , 709, 1104, 1304, 702, 1102, 1302, 701, 901, 1101, 1301 (BASF Aktiengesellschaft); Agrilan® ABC 167 and Agrilan® AEC 178 (Akcros Chemicals); Antarox® B/848 (Rhodia); Berol® 370 and Berol® 374 (Akzo Nobel Surface Chemistry); Dowfax® 50 C15, 63 N10, 63 N30, 64 N40 and 81 N10 (Dow Europe); Genapol® 128803.doc -22- 200838420 PF (Clariaiit) ; Monolan positive, Such as Monolan 正 PB, Monolan® PC, Monolan® PK (Akcros Chemicals); Panox® PE (Pan Asian Chemical Corporation), Symperonic®, such as Symperonic® PE/L, Symperonic8 PE/F, Symperonic® PE/P, Symperonic ® PE/T (ICI Surfactants) ; Tergitol® XD ; Tergitol® XH and Terg Titol® XJ (Union Carbide); Triton® CF-32 (Union Carbide); Teric PE Series (Huntsman); Toximul® 8320 (Stepan Co.) and Witconol®, such as Witconol® ® APEB, Witconol® NS 500 K and Similar product name. In another embodiment, the group 12. nonionic surfactant is an ethylene oxide-propylene oxide block copolymer comprising an alkyl or alkylphenol ether matrix, such as butyl ether, methyl ether, propyl ether, Ether or a mixture thereof. As examples of such surfactants, mention may be made of the commercially available product Toximul® 8320 (Stepan Co.), i.e., a butyl ether derivative of an ethylene oxide-propylene oxide block copolymer. The amount of the above block copolymer may generally be from 2 to 20% by weight, especially from 5 to 17% by weight and more preferably from 5 to 12% by weight, based on the total weight of the formulation. In another embodiment, the c. 14 group of nonionic surfactants are polyfluorene-based oxide-modified dimercapto-polyoxalates, such as the Silwet® trademark, especially Silwet 8L-77 (GE). Silicones) Commercially available organic polysulfate interface. Active agent. Such surfactants are disclosed in U.S. Patent 2,970,150. The amount of the organic polyoxo surfactant is usually from 0 to 6% by weight, especially from 5 to 5% by weight and more preferably from 1 to 4% by weight, based on the total weight of the formulation. Anionic surfactants suitable for the purposes of the present invention include the sodium, potassium, calcium or ammonium salts of the following materials: 128803.doc -23- 200838420 c.15) G-C22 alkyl sulfonates, such as Lauryl sulfonate, isotridecyl sulfonate; i, 16)

CpC22 alkyl sulfate, such as lauryl sulfate, isotridecyl sulfate, hexadecasulfate, octadecyl sulfate; earth c.17) alkylarylsulfonate, such as Isopropyl benzene sulfonate, octyl benzene sulfonate, decyl benzene sulfonate and dodecyl benzene sulfonate, naphthyl sulfonate, mono C1_C16 alkylnaphthyl sulphate and di(^- (:^alkylnaphthylsulfonate, such as dibutylnaphthylsulfonate; "" c.18) Single Ci-C 6 alkyl diphenyl ether (di) sulfonate and two Ci_Ci6 Alkyl diphenyl ether (di) sulfonate, such as dodecyl diphenyl ether bis acid salt; c. 1 9) fatty acid and fatty acid ester sulfate and sulfonate; c. 20) polyoxygen CrC3 alkyl alkyl c ^ C22 alkyl ether sulfate, especially ethoxylated Q-C22 alkanol sulfate, such as ethoxylated lauryl sulfate;) κ oxygen C2 〇 3 stretch $ yuan base Ci- Ci6 alkyl phenyl ether sulfate, especially ethoxylated Ci-C! 6 alkyl phenol sulfate; c. 22) s butyl succinic acid C 4 - C18 alkyl ester (= C4-C18 dialkyl sulfonate Butadiene vinegar), such as dioctyl sulfosuccinate; ) g F, Ssl C^C〗 6 alkyl naphthalenesulfonic acid or a condensate of aged acid and formic acid (=(Cl_ci6 alkyl)naphthalenesulfonate-formaldehyde condensate and phenolsulfonate formaldehyde condensate); c.24) ♦oxycrC3 alkylene monostyryl, diphenyl Vinyl or triphenyl 280803.doc -24· 200838420 Vinyl phenyl ether sulfate, especially monostyryl, distyryl or tristyryl phenyl age polyethoxylate; c.25) single C8 -C22 alkyl and di-C8-C22 alkyl sulfate; c.26) polyoxy C2-C3 extended alkyl C8-C22 alkyl ether hydrochloride; c.27) polyoxy C2-C3 extended alkyl Ci- Ci6 phenyl phenyl sulphate; c. 28) polyoxy C ^ C: 3 alkyl monostyryl, distyryl or tristyrylphenyl ether phosphate; c. 29) polyethylene oxide a polycarboxylate, especially a homopolymer and a copolymer of a monoethylenically unsaturated mono or dicarboxylic acid having from 3 to 8 carbon atoms, the copolymer also having a polyoxyethylene side chain; c. 30) fatty acid Salts such as stearates; c. 31) polyphosphates such as hexametaphosphate and triphosphate (=tripolyphosphate); and c.32) poly (preferably 2 to 30) ethyl groups (preferably Cl to C22) fatty alcohol and amine phosphate Sulfate. In another embodiment, the anionic surfactant is selected from the group consisting of c26, c.28, c, 32, and mixtures thereof. In another embodiment, the formulation of the present invention comprises at least one non-ionic surfactant selected from the group consisting of c. 12 and c. 14 as described above and at least one selected from the group c.26 as described above. Anionic surfactants of groups c.28 and c.32. The components a), b) and c) (ie compound a, solvent and surfactant) generally comprise at least 60% by weight, preferably at least (10)% by weight, at least 95% by weight or even 100% by weight of the total weight of the formulation. %. 128803.doc -25 - 200838420 The formulations of the present invention may also comprise (d) other conventional additives such as antifoaming agents and preservatives. The amount of the additive (d) is generally not more than 5% by weight, particularly 4% by weight, based on the total weight of the formulation. Antifoaming agents suitable for use in the formulations of the present invention are, for example, long chain alcohols, fatty acids, organofluorine compounds, and mixtures thereof. Typical preservatives are, for example, vitamin E acetate, benzoic acid, sorbic acid, sodium benzoate and formaldehyde. Preferred is vitamin E acetate. The amount of preservative is generally from 〇 to 5% by weight, preferably from 1 to 3% by weight, based on the total weight of the formulation. The formulations of the present invention may also optionally contain pigments or dyes, especially when the formulation is intended for seed treatment purposes. Seed treatment formulations: Suitable pigments or dyes are Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow! , Pigment Yellow 13, Pigment Red ιΐ2, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green%, Pigment Green 7, Pigment White 6, Pigment Brown 25, Alkaline Violet 1 , Alkaline Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Alkaline Red (7) and Alkaline Red 1 〇 8. The formulations of the present invention may comprise one or more other active ingredients for crop protection selected from the group consisting of acaricides, algicides, antecedents, arricides, fungicides, and flooding agents. Avian, chemical sterilant, fertilizer, fungicide, herbicide, herbicide safener, insect attractant, insect repellent, insecticide, mammalian repellent, mating interference agent, molluscicide, nematicide , plant activator, plant growth regulation Qibo rodenticide 128803.doc -26· 200838420, synergist and viricide. Combinations with other active ingredients as described herein may be prepared as a final formulation or as a tank mix. The term "liquid pesticide concentrate formulation" as used herein means a pesticide concentrate formulation that is liquid at standard temperatures. According to the present invention, the liquid pesticide concentrate formulation is in the form of an emulsifiable concentrate (EC) or a microemulsion concentrate (Mc or MEC). The formulation of the present invention is preferably a water-free concentrated formulation which is liquid-diluted with water. In one embodiment, the formulation of the invention is an emulsifiable concentrate. In another embodiment, the formulation of the invention is a microemulsion concentrate. In a preferred embodiment, the present invention is directed to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) from 10 to 65 weight percent of compound eight based on the total weight of the formulation (especially a compound of formula A1) or an agriculturally acceptable salt thereof; b) from 15 to 80% by weight, based on the total weight of the formulation, of one or more of the guanamines of formula (bl); c) based on the total weight of the formulation 0.1 to 30% by weight of one or more surfactants; and d) from 0 to 1% by weight, based on the total weight of the formulation, of other conventional additives. In a more preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) from 10 to 65% by weight, based on the total weight of the formulation, of Compound A (especially a compound of formula A1) or an agriculturally acceptable salt thereof; b) one to 15 to 8% by weight, based on the total weight of the formulation, or a plurality of amines of formula (bl); 128803.doc -27- 200838420 C) one or more nonionic surfactants based on the total weight of the formulation (especially selected from the group consisting of C. 12 and e. 14 groups of surfactants as described herein) And; d) other conventional additives based on the total weight of the formulation to 1% by weight. In an even more preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) from 1% to 65% by weight based on the total weight of the formulation Compound A (particularly a compound of formula A1) or an agriculturally acceptable salt thereof; b) from 15 to 80% by weight, based on the total weight of the formulation, of one or more of the indoleamines of formula (b1); c) 0.1 to 30% by weight of the total weight of the oxyethylene oxypropylene propylene block copolymer comprising an alkyl or alkylphenol ether matrix; and d) other conventionally known to be 0 to 1% by weight based on the total weight of the formulation additive. In another preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) from 15 to 50% by weight, based on the total weight of the formulation, of a compound A (especially a compound of formula A1) or an agriculturally acceptable salt thereof; b) 30 to 65 parts by weight based on the total weight of the formulation. One or more of the indoleamines of formula (bl); c) from 1 to 30% by weight, based on the total weight of the formulation, of one or more surfactants; and d) from 10% by weight based on the total weight of the formulation % of other conventional additives. In a more preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: 128803.doc -28- 200838420 a) 20% by total weight of the formulation Up to 40% by weight of compound A (especially the compound of formula A1) or an agriculturally acceptable salt thereof; b) from 30 to 65% by weight, based on the total weight of the formulation, of one or more of the guanamines of formula (bi); 1 to 30% by weight, based on the total weight of the formulation, of one or more surfactants; and d) from 0 to 10% by weight, based on the total weight of the formulation, of other conventional additives. In an even more preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) from 10 to 65 weight percent based on the total weight of the formulation Compound A (particularly a compound of formula A1) or an agriculturally acceptable salt thereof; b 1) from 5 to 8 % by weight, based on the total weight of the formulation, of one or more formulas (as found) of decylamine; b2) One or more than 5 to 2% by weight, based on the total weight of the formulation, of one or more other organic solvents (b2) selected from the group consisting of b2.2 and b2.6 as described herein; c) based on the total weight of the formulation 1 to 30% by weight of one or more nonionic surfactants (especially selected from the group consisting of c l2 and 〇.14 as described herein); and d) based on the total weight of the formulation 〇 to 10% by weight of other conventional additives. In another even more preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: 15 to 50% by weight, based on the total weight of the compound Compound A (especially a compound of formula A1) or an agriculturally acceptable salt thereof; bl) from 3 to 65% by weight based on the total weight of the formulation - or a plurality of formulas of (IV) 128803.doc -29-200838420; B2) from 3 to 20% by weight, based on the total weight of the formulation, of one or more Cj-C^o aliphatic ketones (especially 2-heptanone) and one to 8 weights per gram based on the total weight of the formulation Or a plurality of aromatic hydrocarbons; c) from 0.5 to 15% by weight, based on the total weight of the formulation, of one or more nonionic surfactants (especially selected from the group consisting of c · 12 2 and c · 14 as described herein) They are surfactants; and d) from 0 to 1% by weight, based on the total weight of the formulation, of other conventional additives. In a preferred embodiment, the invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or microemulsion concentrate comprising: a) 15 to 50% by weight of Compound A based on the total weight of the formulation (especially a compound of formula A1) or an agriculturally acceptable salt thereof; bl) from 3 to 65 weight based on the total weight of the formulation. /g one or more of the indoleamines of formula (bi); b2) 3 to 2 Torr by weight based on the total weight of the formulation. One or more C _ CM aliphatic ketones (especially 2-heptanone) and 1 to 7 wt% based on the total weight of the formulation. One or more aromatic hydrocarbons; c) 0% by total weight of the formulation 5 to 15% by weight of one or more nonionic surfactants (especially selected from the group 2 and c·丨4 groups of surfactants as described herein); and d) total of the formulations Other conventional additives having a weight of 0 to 1% by weight. The formulations of the present invention can be prepared by conventional methods for preparing emulsifiable concentrates or microemulsion concentrates. For example, the formulation of the present invention can be mixed with each other by using G έ, A, 洛 (8), surfactant (4) and, as appropriate, other 128,803.doc -30-200838420 conventional additives (d), if appropriate , stirring and / or heating steps: method to prepare. More specifically, the formulation of the present invention can be prepared by dissolving the surfactant (c) and optionally other conventional additives (d) in the solvent (b). ,

σ Benming's liquid sorrow concentration formulation is suitable for combating valuable objects such as arthropod pests and line bombs. For this purpose, the formulation may be applied as such or preferably after dilution with water. Preferably, the so-called aqueous spray system is prepared by diluting the liquid concentrate formulation of the present invention with water (e.g., tap water) for various purposes for end user application. In general, the application rate of 'pure compound Α will be in the range of GG1SG 5 kg/ha, ruthenium.05 to 0.4 kg/ha and especially 〇·ι to 〇3 kg/ha of active compound a. For field application, t, the diluted composition (spray liquid) is primarily (for) plant or soil by spraying, especially foliar spray. Application can be carried out by using a spray technique using, for example, water as a carrier and a spray liquid rate of about (10) to 1 〇〇〇 l/ha (e.g., 3GGS 4GG ι/ha). In principle, the formulation of the invention can be used for plant and crop protection in all fields and for the protection of materials in the field to control harmful organisms or to promote the growth of plants. The formulations of the invention can be used to protect plants and protective materials against The attack of the animal pests m uses the plants and materials of the present invention and destroys or at least inhibits the growth of the harmful organisms so as not to cause damage. The formulations of the present invention are specifically adapted to the protection of materials in different fields to combat the attack of animal pests. The formulations of the present invention can be used, for example, to protect fiber-containing materials, such as wood, and skin, hides, Leather, textiles, non-wovens and the like are effective against animal pests. In general, the formulations of the invention may be applied to combat pests from the following insects: LepMopiera, such as the small tiger, the yellow tiger, the Mgro, the cotton leaf moth

, Lido genus, Argyresthia conjugella, Y (Autographa gamma), Pine stalks, ζ / / / / / 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The moth, the moth, the Choristoneura fumiferana, the 蔷K, the larvae, the American armyworm 6Cz>p/n\w?n>z^cia), the apple moth [C>(iz_(2;7〇mc^e//a), European pine hair A (Dendrolimus pinQ, Diaphania nitidalis, D/airaea grandiosella, Egyptian diamondworm) Earz.as insulana), small corn mold (five/like mopa/pws), grape moth (five European powder twigs • training β), grainy tiger wfeierrawea), large soil mold ((^β//πΖ) ·α mellonella), 孥+食心 A (Grapholitha funebrana, pear + food A^iGrapholithamolestal'^^^^lHeliothisarmigera), American tobacco leaf moth (price - \y like), American cotton bollworm (8) e / - zea) > Hellula undalis, Hibernia defoliaria, Hyphantria, Hyponomeuta malinellus, tomato moth (foot ez/erk 1 28803.doc -32- 200838420 lycopersicella) ^ ^^%{Lambna fiscellaria) ^ ^ ^ ^(Laphygma exigua) ^ Φ ^ ^ ^(Leucoptera coffeella) 'Zemcopiera, Spotted Leaf Moth ( Lithocolletis blancardel丨a), Lobesia botrana, W/criz'cah's, Gypsy moth {Lymantria, LymaWr/a monacha, narrow wings

Leaf miner (Ay (four) buckle clerkella), Tianmu hair [Malacosoma neustria) ^ ^ M ^ ^ {Mamestra brassicae ^ ^ Douglas sinensis moth {〇rgyia pseudotsugata), so sarcasm (Ostrinia nubilalis), winter night moth {Panolis Flamma), $cl 铃义 (Pectinophora, variegated tiger (Perz'droma, Phalera bucephalci), horse bell integrated 1 woven (Phthorimaea, tangerine moth ciire / / a), large cabbage butterfly (corpse) , cabbage butterfly (Ρζ·βΓΖ·5, green night moth {Plathypena scabra), square moth (P/wie//a maculipennis), λ (, Plutella xylostella, Pseudoplusia includens), Pine: Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, S. cerevisiae (S/mrga (4), Southern Spodoptera sinensis {Spodoptera eridania), grass viscous Insect {Spodoptera /irwg/per<ia), Spodoptera litura""ara/zi, Spodoptera litura, Thomatopoea pityocampa, Wr/(ia/ 7a), Spodoptera litura (TWc/20/7/wWa π/) and cloud Cedar leaf curler (Zeirap/zera, 128803.doc -33- 200838420

Beetles (Hymenoptera, such as pear long Jiding (dgn·/like feet αί(10)), striped armor // (10) as if), Agriotes obscurus, horse bells and pros. ^Amphimallus •SO /si/Wa/b), Despa, 棉, Anthonomus grandis, Anthonomus pomorum, dwarf beet beetle, Blastophagus piniperda, Blitophaga undata , 暮Sl l {Bruchus rufimanus), 窥 lt {Bruchus pisorum, 乌瓦象(Bruchus lentis), 卷叶象, (Byctiscus betulae), beet tortoiseshell (CasWc/a, Bean (Ceroioma trifurcata), Ganyanyan I "f (Ceuthorrhynchus assimilis), Gangai stem turtle elephant like /? /), beet stem flea ί / Μβ / b), tobacco golden worm ((7〇^2 6 > ^ factory 1 ^ "577 has been /«1^), Crioceris asparagi, Diabrotica longicornis, 12-star melon leafhopper, Diabrotica virgifera, Mexican bean ladybug ^ ( Epilachna varivestis), tobacco flea (Epitrix hirtipennis), merlot {Eutinobothrus brasiliensi s), Hylobius abietis, Egyptian elephant / (//xpera, 苜蓿叶甲甲 paWica), spruce 八 tooth small 蠹 (/??*?, striped negative mud (Lema bilineata), ticket, Lema melanopus, potato aphid (four), beet golden nymph (Limonius californicus), rice locust (Lissorhoptrus oryzop/zi/ws), golden worm (Me/awoii/s, rape noodles 128803.doc - 34- 200838420 尾f (Meligethes, Great Chestnut Tortoise (Me/o/oW/m hippocastani), Western M Golden Gas (Melolontha melolontha), Rice Mud A (Oulerna, Grape Black Ear Locust

(Ortiorrhynchus η/Μί(10)), strawberry root weevil (Oi/orr/zync/z(10) <9vaiw), horseradish beetle coc/z/eariae), Phyllantreta chrysocephala, Phyllophaga Sp·), Liangyuan Lijin turtle (corpse, Phyllotreta nemorum, Phyllotreta striolata, 曰本丽金龟, 婉豆叶甲甲 lineatus, 反数 l{Sitophilus granaria), double Wings (Diptera, eg Aedes aegypti (jeAs aegxpiz), Aedes νβΧα), Mexican orange fly, Anopheles sinensis, Mediterranean solid rope (Cerai/i/s cap/iaia), snoring Golden rope, American golden rope (CZ/rj^omya hominivorax), rice gold insects (C/zrjv^omya mace//aria), sorghum '鏖 mosquito (Coniarz'm'a sorg/n'co/a) , Shield wave rope {Cordylobia anthropophaga), Cu 匕 { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { { ?ra with icae), yellow-bellied reins (Fa (four) ζ · α cam'cw / ar / s), Malaysian stomach rope (Gasierop / n' / i ^, thorn worm iCCJ / owha mom 'iaw), blood transfusion / Rr/iaw), horse light edge [Haplodiplosis equestris), seed rope p/aiwra), leather rope (i/>77C^erma /Μαία), Liriomyza sativae ^ # /'j+| M ^(Liriomyza trifolii) ^ Mountain 128803 .doc -35- 200838420

Lepidopteran ephak), copper green rope czfpr/wa), mercerized green rope (Ζ^(:ζ7ζ·β ser/caia), black-chested mosquito (Lj/corz'a pecMra/k), Hessian wheat rope ( Majei/o/a desirwcic^), home rope (Mwca, Musca autumnalis, Muscina stabulans, sheep nose rope ov/s), Swedish straw rope (6^cMe//a / Wi), beet leaf line (jPegomya / zysocyam/), ancient grass rope (Ρ/ζοΑία antiqua), cabbage grass rope (P/zorWa Ζ^αυ/crae), narrow grass rope (P/2〇rZ ?/a ααπίαία), cherry fruit fly (ii/mgo/ei/s cerwz·), apple solid rope (and /mgo/eih pomone//a), cattle it Z>oWm^), gan bang: K Tipuia oleracea) Tipula paludosa, hummer (Hymenoptera, such as Tobacco's frankliniella fuse a), Frankliniella occidentals, Frankliniella ir/i/cr/ ), orange scorpion {Scirtothrips czVrz·), rice scorpion horse (TTzrz·/^ oryzae), southern scorpion horse {Thrips palmV) anti-subsequent horse {Thrips tabaci), pteridophyte (Hymenoptera (//yme(10)piera) ), for example, Xinjiang leaf bee (Α/ζα/ζ·α rosae) , tropical leaf-cutting ants (diia cep/m/oies), South American leaf-cutting ants (Αία Mxdew), Texas leaf-cutting ants (yliia, Hoplocampa minuta, iiop/ocawpa testudinea, Tickets, weaving (Lasius niger), window weaving (Monomorium pharaonis), fire soil {Solenopsis geminata) 3^ ^cl ^^ (Solenopsis invicta) ? Isoparms (Hymenoptera (//derapiera)), such as green 蝽 ( Dcroskr(10)m /n7are), hairy long scorpion (5/by *yw, tobacco black spot blind culture (Cyriope/i/s ποίαίι^), cotton red 蝽 (jDj/Siiercws c/wgw/aiws), medium 128803.doc -36 - 200838420 椿 (D;; We re like intermedius), JEurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, lineolaris, 苜蓿 blind 蝽Aygw, rice green 蝽WrzWa), beet 捡 net 蝽 (Pz'esma, purple skunk (5^/heart ea z'/uw/ar/s) and front elephant Thyanta perditor),

Homoptera (Hymenoptera (//^通, such as 驴豆虫{Acyrthosiphon onobrychis, Adelges laricis, A, D, Aphidula nasturtif, Aphis fabae), Strawberry Rootworm teeth «ρ/π, /br6wz·), apple insect teeth (dp/n, powz·), cotton insect teeth, goose worm teeth growzz/ar/ae), Shishicai, spirea fangs (^( household/2 /5 *s7?z>(2eco/a), Aphis sambucV, Acyrthosiphon pisum, Ma Lingji, Aulacorthum solani, Brachycaudus cardzn· , roundworm teeth/zenc/z^yh), Brachycaudus persicae, Brachycaudus prunicola, Brassica oleracea, Capitophorus /20ΓΝΖ, square wing net蝽(CerO^/f/za g〇WJ;/7Z·/), Chaetosiphon fragaefoliP, tea vine, fg tumor field [Cryptomyzus η·6ζ·$), silver worm (Drey/wWa) (4) /απαβ), spruce vertebrate tooth (Drey/z^z'a pkeae), rhizobial tooth rashan 'co/α), green potato tooth {Dysaulacorthum pseudosolani), rose Block apple money, pear leafhopper (DyMp/nj ργζ_), broad bean radish {Empoasca fabae), plum kt worm [Hyalopterus pruni), tea wins 128803.doc -37- 200838420 vegetable insect tooth lactucae), the governor's tube farm (Macrosiphum avenae), Macrosiphum euphorbiae, Macrow/p/zcm rosae, MegOwra Wcz'ae, Melanaphis pyrarius, Salvia Field (Metopolophium dirhodum), ^ if (Myzus persicae), winter onion worm (Myzws

, Afyzws cerwz·, Mj/zws varkw, worm tooth (iVasonoWa rMfs-m'grz·), brown rice wind (Nilaparvata lugens), cystic snail (Pemphigus bursarius), Yan Feiqian (hu ah·like • yacc/zarkzWa), sisal fatigue/zwmw/z·), Pingmufeng*(/^3;//α ma/ί), pear wood wind Piri), Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi > II ^ Ιέ ^ ^ (Rhopalosiphum insertum) ' IB > C worm ma/a ), Marley's round-tailed money (iSappap/ni mfl/z·), Mai Erwen's worm {Schizaphis gram/m/m), cleavage leaf insect tooth (iS^/n'zoMwa lanuginosa) ^ 麦长管虫牙(ΑίοΜοπ avenae ^Greenhouse white powder wind {Trialeurodes vaporariorum), large locust tooth {Toxoptera aurantiiand) anti-vine root nodule worm (Viteus vitifolii), termites (Isoptera, such as yellow neck wood white sacrifice (Ca/oiermes /7av/co//b ), Lewcoiermes //ανφα, Reticulitermes lucifugus, Reticulitermes (10) End), Glaser black termite gr sW) and Natal termites, Orthoptera (Orthoptera (<9ri/^/7ier(2)), for example, total 蜱 ("c/zeia 128803.doc - 38- 200838420

, Oriental cockroach, German cockroach (Blattella germanica), Forficula auricularia, European 蝼蛄gryllotalpa) - arbo (Loc (10) ία, double 蚱 蚱 (Μβ/απορ/(10) WWiiaiws), red legs 蚱 fierce { Melanoplus A, Mexico's Kunxi mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, America: & 1 {Schistocerca americana) > ^ }% {Schistocerca peregrina) - ^ ^ ^ ^Lik{Stauronotus maroccanus) % 迷l{Tachycines asynamorus). Arachnoidea, such as the arachnid (Euphorbia, such as the soft-spotted family, the genus Lycidae, the χο山 Ww), and the Sarcopteridae, such as the American H 缉 (Amblyomma americanum), the decorative flower 蜱 varz 'egaiwm), Persian 蜱perdcws, Boophilus decoloratus, QBoophilus microplus, forest var. silvarum, long glazed eye (Hyalomma truncatum), hard Monument (Jx〇des ricinus, Ixodes rubicundus, Moba’s monument, 〇mithodorus moubata), ear wreckage, galloping gallinae, Psoroptes ovis, aconite l {Rhipicephalus appendiculatus), Rhipicephalus evertsi, Sarcopia • ycaWez· and Brassica species 128803.doc •39- 200838420

(Eriophyidae spp.), such as the thorn worm, the orange rust (household "ocopiraia o/e/vora) and the citrus sheldoni; the genus Tarsonemidae spp., such as cyclamen Worm (corpse / ^ sound (10) pan-like claw / 7 (2 / / / < ^ like) and side polyphagous nematode 茜 {Polyphagotarsonemus latus); pseudo genus (Tenuipalpidae spp.), such as purple pseudo-leaf Road (Brevipalpus; Tetranychidae spp.), such as Tetranychus cinnabarinus, Tetranychus, Pacific red worm (TWra^yc/zws pac//c), cotton Red leaf larvae and cotton leaf mites (reira^yc/z like wriz'cae), apple full-claw scorpion scorpion (corpse w/mz·), orange full claw cz7r/) and grass small claw worm (9); nematodes, special Plant parasitic nematodes, such as root-knot nematodes, northern root-knot nematodes, southern root-knot nematodes {Meloidogyne incognita), claws. Genus knotworm yava/7z_ca) and other Meloidogyne species; cyst nematodes, horse worms (G/ohdera rc^iac/z/ew/s) and other nematodes (Globodera) Species; cyst nematode (Tfeierodera yang (9) post), soybean cyst nematode g/yches, beet cyst nematode {Heterodera schachtii), clover cytoplasmic line (Heterodera ir (/b//z·) and Other species of Heterodera; seed nematodes, Anguina species; nematodes of stems and leaves; aphelenchoides; thorns nematodes, acupuncture Belonolaimus longicaudatus and other species of the genus Thornworm 128803.doc -40- 200838420 (Belonolaimus); pine nematode, pine wood nematode {Burs ap helenchus xy/op/n'/ws) and other species of Bursaphelenchus ; ringworm, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; stem and bulb nematodes, potato rot nematode

Sweet potato stem nematode (JD/i and other Ditylenchus species; cone nematodes, Dolichodorus species; spiral nematodes, Spirulina elegans {Helicotylenchus and other Helicotylchus) Species; outer sheath nematodes and sheath-strands, Hemicycliophora species and Hemicriconemoides species; Hirschmanniella species; crown nematodes, Hoplolaimus species; False root knot nematodes, Nacobbus species; needle nematodes, Echinococcus elegans ([OTzg/ciorws and other species of the genus Longidorus; rot nematodes, unselected short-body nematodes (10), puncture of nematodes) (corpse, curved root rot nematode cwrWiaiws), damaged root rot nematode (iVaiy/ewc/z like goode;;/) and other root rot (Pratylenchus) species; perforated nematodes, perforated nematodes (iiWop/zo/ws Wmi /z,) and other species of the genus Radopholus; nematode, Nematodes (and similar) and other Rotylenchus species; Scutellonema species; Residual nematode, Kebo 128803.doc -41 · 200838420 Residual nematode (TV/c/zoiiorz^ and other species of the genus Trichodorus, Quercus genus) Paratrichodorus) species; dwarf nematodes, Clayton dwarf nematode c/ayiom·), indefinite dwarf nematodes (Tylenchorhynchus dubius) and other species of the genus Tylenchorhynchus; citrus nematodes, Tylenchulus Species; Sphingidae, Xiphinema species: and other plant-parasitic nematode species.

The formulation of the present invention can also be used against rice pathogens, such as rice water weevil (Lissorhoptrus oryzaphilus), rice stem borer (C/n7o si/ppraa/), rice vertical leaf curling (rice leaf roller), rice leaf beetle, rice leaf miner (Agromyca or jyzae), leafhoppers (spp.), especially small brown leafhopper, rice black tail leaf Green rice leafhopper), planthopper (De/p/mcMae), especially white backed planthopper, brown rice planthopper, Jiuxiang Stinkbug o The formulations of the present invention are particularly useful for combating pests of the order Lepidoptera and Coleoptera. The liquid pesticide formulations of the present invention may also be applied as such or in the form of aqueous diluents or powder compositions as described above to combat non-crop pests. Accordingly, the present invention is also directed to a method of controlling a non-crop pest comprising contacting a pest or a source thereof, a habitat, a breeding plot or a locus thereof with a formulation of the present invention. The invention further relates to the use of the formulations of the present invention for protecting inanimate materials from the use of non-crop pests of 128803.doc-42-200838420. Non-crop pests are pests of the genus Pleurotus and the genus Heteroptera and Isoptera, Diptera, Odonata, Hymenoptera, Hemiptera, Hymenoptera, Orthoptera, Odonata, Iris, Hairy In addition to the pests of the genus, the parasitic genus (Parasitiforme) and the genus genus, such as the worms (lipods), such as the cocoon (co/eopiraia), • the millipede (the foot), E.g,

• Insects (arachnidae), such as the black-spotted worm (macia) and the brown-spotted worm (rec/wsa), • The worm (the genus): for example, the genus Sarcopia ν), • Ticks and parasitic mites (send the genus) · ticks (Scorpion), such as the scapular scapularis (Jxodes scapularis, the full ring 缉 {Ixodes holocyclus), the Pacific 蜱 ( /xodes, Rhiphicephalus sanguineus, Deermacentor andersoni, ^ si {Dermacentor vahaZH'/zi), American bud, spotted maculatum, and thorns Ornithodorus hennsi), Tukata soft palate, and parasitic mites (middle valve suborder), such as the avian worm (acoii) and chicken skin thorns {Dermanyssus gallinae) 5 • termites (Isoptera), such as yellow Cervical termites, yellow-legged termites, golden allogenic termite awrews, yellow-breasted termites //αν^α), southern termites (and eiz'ew/z'iermes virgkicws), southern European netted termites, Natal termites and Taiwan milk termite (Copioiermes 128803.doc -43- 200838420 formosanus), •蟑螂(Blattaria-Blattodea), such as German cockroach, Asian 蟑螂αα/π'παβ, American cockroach (10)βία americana), 曰本大蠊 (corpse, brown 蠊{Periplaneta brunnea) {Peroplaneta fuligghosa), Periplaneta australasiae, anti-I 蜚蠊, • ropes, mosquitoes (Diptera), such as Aedes aegypti, Aedes albopictus

"//叩化纟), 剌 伊 Aedes, Mexican orange rope, Anopheles sinensis, Anopheles sinensis (乂 (10) p / ze / es crwcians), Anopheles sinensis albimanus), Anopheles gambiae , Anopheles freeborni v (Anopheles leucosphyrus), micro, i, Anopheles minimus, IV, quadrimaculatus, Calliphora vz'c/na , sputum golden fly, American golden rope (C/zrysomjKa /zomk/vorax), rice golden rope, deer rope (C/zrysoj^ (i/sca/b), deer spot, Atlantic spot it W/(10)"cws) , spiral rope {Cochliomyia hominivorax), shield wave field, raging 蠓 / wre like), Culex pipiens, ringworm (Cw / ex nigripalpus) 'Cw / ex quinquefasciatus (Cw / ex quinquefasciatus), ^ Μ mosquito (Cw/ex, 粦ο粦αία), black-tailed mosquito {Culiseta melanura), Dermatobia hominis, pedicure reins, Malaysian stomach 43⁄4, tongue jar, tongue rope (G/owha) Pa/pa/b), black foot tongue, strong tongue rope 128803.doc -44· 200838420

Iac/n·Feet Wes), stalking blood flies (7/heart plus 6^/(2/, factory ""like), saddle-shaped cockroach, genus (//ppe/aia fpp.), Leather rope, Torrance fine ior factory), goat green 43⁄4, copper green rope, mercerized green rope, black-chested mosquito, marsh mosquito sp;?), home rope, scorpion rope, sheep nose rope, P. arge Wipa), Psorophora columbiae, Psorophora, Pros/mw/iwm mz'xiwm, Sarcophaga haemorrhoidalis, 0i 43⁄4 (Sarcophaga sp., With 蚋 (57mw/iwm Wiiaiwm), reins (SVomoxjs), cow it, black horse it (Γα&β?2ζ^ airaiz/s), thin strip horse rainbow: (!Γα6 training w //πβο/β) and Like the same as Ma Hong: like 5 / / /), • 蠼螋 (Geoptera), such as European 螋, • 椿 (Hemiptera), such as temperate bed bugs (C7mex / eciw / ariws), tropical Bug (Cz'mex, old hunting scorpion, Triatoma spp., Rhodnius prolixus, back stalking ants) • Ants, bees, wasps, saw bees (Hymenoptera), for example: tail Ant (CremaiogMier Spp·), small horned bee, bud, ant, fire ant, red fire ant, black fire ant ric/zierz·), southern fire ant (Solenopsis xyloni), ^% (Pogonomyrmex barbatus), California harvest sacrifice Ex ca/i/orm'cws), Dasymutilla occidentalis, Bombus spp, Fapw/a, Common Wasp vulgaris, © (Paravespula pennsylvanica) ^ 128803.doc -45- 200838420 Parcivespula germanica, Dolichovespula maculata ^ {Vespa crabro) ^ M ^ {Polistes rubiginosa) - ^ % it ^ (Campodontus floridanus) Argentine ant / zwmz7e),

• cockroaches, locusts, cockroaches (Orthoptera), such as cockroaches, European cockroaches, cockroaches, cockroaches, red-legged pheasants, Mexican pelicans, migratory crickets, rocky mountains, red-winged hawksbills, American desert otters, African desert baboons Gregar/a), Moroccan cockroach (DOciwiflz/rw maroccfl (4)^), greenhouse cockroach, Senegal car worms), zebra worms (Zowozerws variegaiws), 蔑4J. (Hieroglyphus daganensis) ^ Indian yellow sandalwood angulifera), Italian worm emperor, Australian cockroach QChortoicetes terminifera) Anti-South African ridiculous (Locustana pardalina) 5 • Flea 蚤 (蚤目)' such as anchor 0 (0 / 7〇〇叩 / ^ / / / 1 ^/^/), canine (Cteno cep halides canis), Indian egg cheopis, JPulex irritans, Tunga penetrans: strip, egg {Nosopsyllus fasciatus) • Locust , the family fish (Iguana), such as the western squid (1 叩 saccharincT),], the clothes, [Thermobia domestica'), the wind (rat), such as the head cap / ^), human wind (corpse ecorpora) And infighting (corpse ί/ζζ>ζ^ pubis), cow wind {Haematopinus eurysternus), pig wind {Haematopinus suis) ^ 牛f member wind (LMog (four) Wiw//), cattle bird 128803.doc -46- 200838420 虱 (BoWco /α , chicken 虱 (Μβποροπ, 虱 虱 {Menacanthus stramineus) 反 Argon QSolenopotes capillatus) ° For example, the formulation of the present invention can be used to protect inanimate organic materials 'including but not limited to, daily commodities, Such as fats, oils, organic monosaccharides, organic sugar or organic polysaccharides, protein or fresh or rotten fruit; cellulose-containing materials such as wooden materials such as houses, trees, wooden barriers or sleepers, and paper; Materials, furniture, leather, animal, plant and synthetic fibers, vinyl articles, wires and cables, and styrene foam. In addition, the formulation of the present invention can be used to protect an inanimate organic material against resistance selected from the group consisting of the genus Diptera and Isoptera, Diptera, Acarina, Lepidoptera, Hemiptera, Hymenoptera, Orthoptera and Non-crop pests of the group consisting of the appendix. The present invention is also directed to a method of protecting an inanimate organic material against non-crop pests as described above, which comprises effectively rendering the pest or its food source, habitat, breeding area, its location or the inanimate organic material itself and insecticidal. The amount of the formulation of the invention is contacted. In addition, the formulations of the present invention can be used to protect cellulose-containing inanimate organic materials, such as protecting cellulose-containing inanimate organic materials from resistance to the order of the order Hymenoptera, Hymenoptera, Hymenoptera, and Orthoptera. Good from non-crop pests of Isoptera. The present invention also provides a method for protecting a cellulose-containing inanimate organic material from the non-crop pests preferably from Isoptera, Diptera, F. elegans, Hymenoptera, and Orthoptera, preferably from Isoptera. The method comprises contacting the pest or the source of the food, the habitat, the worm (four), the locus thereof, or the cellulose-containing inanimate material with the formulation of the present invention. In addition, the formulations of the present invention can be used to protect monosaccharides, sugar-supplying or polysaccharides and proteins. In addition, the formulation of the present invention can be used to protect monosaccharides, sugar-supplying or polysaccharides and proteins from resistance to selected from the order of the order of the order of the order Hymenoptera, Bactrian, Isoptera, Diptera, Odonata, Hymenoptera, Orthoptera. And the appendix, the best selected from non-crop pests such as Isoptera, Diptera, Acarina and Hymenoptera.

In addition, the formulations of the present invention can be treated in the body of water and/or in or around buildings (including but not limited to wall walls, dung heaps, turf grass, pastures, sewers, and the like by the formulations of the present invention. The pests used to construct the building materials and the mattresses and beddings are used to protect the animals against the genus Lipidae and the arachnids, the Hemiptera, the Diptera, the Eyes, the Eyes, the Eyes, and the Whitefly. Non-crop pests. Animals include warm-blooded animals 'including humans and fish. Because & the formulations of the present invention can be used to protect warm-blooded animals such as cattle, 4, pigs, camels, deer, horses, chickens, rabbits, goats, dogs and cats. The composition of the present invention can be used to protect wooden materials such as trees, wood slabs, pillows, etc., and buildings such as houses, outhouses, factories, and building materials, leather, fibers, women's articles, wires, and electricity. It is protected from ants and/or termites and is used to control code ants and white sacrifices: crops or humans (eg when pests invade houses and public settings). The formulation of the present invention can be applied not only to the surrounding soil surface or underground soil to protect the wooden material, but also to articles such as underground concrete, concave to column, girders 'plywood, furniture, etc., such as 128803.doc -48- 200838420 Wood products such as particle board, half board, etc., and vinyl articles such as coated wires, vinyl sheets, heat insulating materials such as styrene foam, and the like. The ant control formulation of the present invention is applied directly to the ant's lair or applied to it or contacted via a bait, in the event that it is applied to resist damage to the crop or human. Furthermore, the formulations of the present invention can be prophylactically applied to where pests are expected to occur. 7Γ

For example, the heart, the work, the lieutenant, for example, 'suitable seeds are various crop seeds, fruit types, vegetables, spices and ornamental plant seeds, such as corn (sweet corn and non-sweet stomach $, durum wheat, soybean, wheat, Fushuang, 夕大麦, hot wheat, rye, black wheat, banana, rice, cotton, sunflower, * by one, 'Ma Linglu, Muzhuo, Ziqi f, grass, Zhuopi,... rapeseed, alfalfa Moss, sugar beet 1 , stalk, stalk, pepper, cucumber, pumpkin, melon, beans, _, beans, leeks, garlic, onions, kale, carrots: phantom, tobacco , curry trees, turf and forages such as stalks, vines, peppers, beet, stalks, plants, gourd R clothes > from picking, pansy, stalks, petunias and geraniums. Or, preferably, it is within the scope of the invention or the invention. The combination of the following examples is intended to further read the present invention without the scope of the invention. The invention is limited in any way. 1. Preparation Example 128803.doc - 49. 200838420 Registered trademarks used herein and His name indicates the following ingredients: Table 1 Composition _---' Agent X 3050-69A (Stepan Co.) ^ Type / 3⁄43⁄4 Cleaner Change ^ '^' Agent X 3109-14 (Stepan Co.) Anionic / Non Ionic Cleaner Blend_____ Agnique KE 3658(Cognis) 50-65 wt% N,Ncmethyloctylamine 37·50 wt% N,N-Dimercaptoamine 0-5 wt% N, N-dimercaptohexylamine 0-2 wt% N,N-dimethyldodecanamine ___一 Aromatic 200 (ExxonMobil) aromatic hydrocarbon mixture __ Silwet L-77 (GE Silicones) Alkoxide-modified dioxopolyoxane Toxul 8320 (Stepan Co.) ethylene oxide/propylene oxide (EO/PO) block copolymer butyl ether Yanwa series of liquid concentration formulations (see Preparation Example 1) To 6, Table 2) Prepare by weighing the ingredients in the exact proportions and mixing them in a bottle until complete dissolution (if needed at the same time). First weigh the solvent. Compound A1 (ie (5) Z)-2,-[2-(4-cyanophenyl)-1-(α,α,α-trifluoro-m-tolyl)ethylidene]-4-(trifluoromethoxy)anilinyl Hyperthyroidism) completely dissolved in the solvent system, then added Surfactants and other additives. All of Preparation Examples 1 to 6 gave clear homogeneous liquids. In the following examples, unless otherwise specified, all amounts are by weight or by weight based on the total formulation. Table 2 Examples of ingredient preparation , edited? Tiger 1 2 3 4 5 ------__ ------ _6 Compound A1*(8) 18.00 18.03 21.30 21.30 21.30 ------ 17.50 Agnique KE 3658(bl) 56.00 56.00 58.00 58.00 63.70 ---------- _5100 2·heptanone (b2) 11.65 11.97 5.25 5.10 4.00 — Aromatic 200(b2) 2.50 2.40 4.75 2.85 3.00 Agent X3050-69A(c) 9.00 9.50 1.55 - ----- --- — ----- Agent X 3109-14(c) - - - - 7.00 】28803.doc -50- 200838420

Toximul 8320(c) • - 6.30 7.80 Silwet L-77(c) - 2.10 - 2.10 Vitamin E Acetate (d) 2.85 - 2.85 2.85 1.00 3 〇〇 Total 100.00 100.00 100.00 100.00 100.00 1 100.00 * Contains 96.1% Compound A1 Industrial Grade Active Ingredients 2. Stabilizing Properties 2.1 Emulsion Stability The liquid concentrate formulations of Examples i to 6 were prepared by diluting with a 1:100 and 2:100 formulation/water weight ratio. Use different water hardness conditions (342 melon, 500 ppm and 1000 ppm WHO hard water). All formulations of the present invention exhibited good water dilution and emulsification characteristics over a range of different water hardnesses. No crystals were observed after dilution with water. 2. 2 freeze-thaw stability and chemical stability Test preparation examples 丨 to 5 at -15. (: freeze-thaw stability between temperatures up to 40 t. One cycle consists of a total of 24 hours, wherein the sample is exposed to _15 for 10 hours and exposed at 40 ° C for 1 hour, where 2 hours to another temperature. All samples showed excellent stability after 5 cycles, showing no crystal formation or no change in emulsifying properties or physical appearance after dilution of the concentrate. It was also found to have chemistry after freeze-thaw cycles. Stability. The condensation stability of Example 5 was prepared in Table 3 below (5 cycles, see above) and the chemical stability test (at different storage times and temperatures). 128803.doc •51 - 200838420 Table 3 Compound A1 w/w% Recovery % Initial 20.1 101.0% 5 freeze-thaw cycles 20.3 101.5% at 0 °C for 12 weeks 20.4 98.5% at 0 °C for 26 weeks 19.8 99.5% at 25 °C for 12 weeks 20.0 98.5% at 25°C for 26 weeks 19.8 98.0% at 40°C for 12 weeks 19.7 98.0% at 40°C for 26 weeks 19.2 95.5% at 54°C for 2 weeks 19.4 96.5%* * at 54°C A recovery of 95% or higher after 2 weeks indicates good chemical stability. 3. Bioactivity 3.1 resistance to Gan The stock composition of the formulation of Example 4 was diluted to a container of water at the activity of the third-instar butterfly (Pier rapae) on the dish at 0.3, 1, 3, 5, 10 and 30 and 100 ppm. Test Preparation Example 4. Cabbage leaves were immersed in the thus prepared diluent and allowed to air dry. The single-processed leaf discs were placed on the filter paper moistened with water in a plurality of plastic cultures, respectively, in a leaf-facing manner. Ten larvae (third age) were placed on each leaf, and each test dish was then sealed with a petri dish lid. Each treatment was repeated 4 times using 10 insects (1 repetition = 1 culture fox) The larval complete mortality was assessed 72 hours after infection. Table 4 lists the LC50 and LC90 data obtained for various concentrations of ai (active ingredient) applied after 72 hours of exposure. The probability unit analysis of the observed mortality was used to calculate LC50 and LC90. Based on the LC50/LC90 values (2.413 and 4.7 ppm), Preparation Example 4 provided excellent performance against 128803.doc -52-200838420 against the larvae of the white butterfly. Preparation Example 4 Also mention Based on ingestion hazard ratio (313%) Protective effect good blade at the 1 ppm Table 4: blade dipping study made by each ^ Preparation shell Example 4 Resistance brother efficacy 3rd instar groove Baidie of (LC50 / LC90) ^

3 · 2 resistance to Lima Beans: r age 4 + younger one-year-old southern Spodoptera litura (Somhern Armyworm, do (7) · (1) · α) activity

The stock composition of each of the formulations of Preparation Example (1) was diluted into water. The Lima bean leaves were sprayed with a nebulizer-prepared dilution and allowed to air dry. The nebulizer was calibrated to apply _L/ha and all dilutions were calculated as g 11/11 & Place the individual treated leaf discs on top of each other in a plurality of plastic petri dishes with water-wet filter paper: Seven larvae were placed on each leaf, and each site was then sealed with a petri dish lid. Each treatment was repeated 4 times with 7 insects (1 repetition = 1 petri dish field). After treatment application, the infested plants were kept in the laboratory under fluorescent lighting and at a constant temperature of 26 °C. The feeding hazard rate (0-100%, visual assessment) was recorded after administration (DAT) 4, 7 and day. The results are summarized in Table 5 below. See all 4 Examples 1 to 5 not only provide good initial activity against the larvae of Spodoptera frugiperda, and provide excellent performance. 128803.doc -53- 200838420 Table 5: Preparation examples under artificial exposure in UV chambers 丨 to 5 resistance to southern Spodoptera litura effect product application rate (gai/ha) HH i food hazard rate %~' __4DAT 100 7 DAT ϊόο 11 DAT ioo Untreated control B^0 ^ Example 1 25 15.8 56.3 51) 14.0 11.5 563 75 10.0 15.0 26 3 Example 2 25 ---~ __18·8 16.5 100 50 16.3 14.5 76.3 75 _15.8 13.8 35 〇Example 3 25 _ 19,5 22.5 47.5 50 15.0 15.0 60.0 75 12.0 10.0 32 S Example 4 25 17.8 28.8 100 50 17.5 20.0 68.8 75 12.0 17.5 61 3 Example 5 25 16.3 18.8 87.5 50 14.3 113 ~ 52.5 75 11.0 7.8 18.0 3 • 3 resistant Colorado potato aphids in the potato (c〇iorad〇pQtat() beetle, Leptinotarsa decemlineata)^ The test was placed in a random complete block and repeated three times. The block is 1 〇 m long and 1 column wide. The application was carried out at a pressure of 3 bar and 300 1/ha using a machine-mounted sprayer with a three-nozzle planting sprayer transfer surface and an overhead cover. The number of larvae per plant (Ll/2) (L3/4) was recorded 3, 7, 14 and 21 days after application (DAT) and the feeding hazard rate was assessed 21 days after application (see Tables, 7 and 8 for springs). ). No crop damage was observed 3-14 days after application of the formulations tested. It can be seen that all Preparation Examples 1 to 5 provide excellent control of Colorado potato aphid larvae. 128803.doc -54- 200838420 Table 6 - Preparation of Examples 1 to 5 to control the effectiveness of Colorado potato beetles in potatoes, larval stage: 1st and 2nd instar moths treated untreated control tSi Z.. 25 ^^ -丨· 3 DAT lL3a Ob Ob ^ the average number (5 8 DAT 37.3a 0b n repetitions | _ ijgg^^ ^3bc^^^ ----- Example 2 - Example 4 Example 5 with the same Fengmu 25^ -- ^25 ^ Ob Ob Ob Ob 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 Control of Colorado potato beetle 1 in potato, larval stage: 3rd and 4th instar. Insect 4a ~ application rate - average number of bacterial insects (3 replicates) ^ η untreated control g ai/ha 3 DAT 32a 8 DAT 87a 14 DAT 144.7a~ 64?7i Example 1 25 0c 0.7b 2.3 b ~79JT~ 50 0c 0b 0.7b 30a Example 2 25 0c 0.3b 15b 78?7i 50 0c 0b 0b 71,3a Example 3 25 0c 0b 2.7b 48.3 a 50 0c 0.3b 0.3b 57.3a Example 4 25 1.3b 0b 5.7b 84.7a 50 0.3c 0b 0.3b 48a Example 5 25 0c 0.3b 7b 48a 50 0c 0b 14b 42.3a with the same letter average The difference is not significant (P> 〇.〇5) SNK 〇 raw data was transformed from l〇g(x+l) 128803.doc -55- 200838420 Table 8: Preparation of Examples 1 to 5 to control the effect of Colorado potato beetle in potato. Larval stage: 1 2nd, 3rd and 4th instar. Treatment rate g ai/ha 21 DAT feeding hazard rate % (0-100% measure) Untreated control 0 70a Example 1 25 22b 50 10b Example 2 25 28b ' 50 17b Example 3 25 13b ... 50 20b Example 4 25 32b 50 19b Example 5 25 30b 50 22b The average of the same letter is not significant (P > 〇. 〇 5) SNK. The original data is converted from the square root arc sine 3.4 resistance Diamondback moth (Diamond backmoth, P/uieZ/a)

And the activity of the Common Cutworm. Test Preparation Example 4 was resistant to two species of the cabbage moth and the Spodoptera litura on the cabbage at an application rate of 160, 200 and 250 ppm. The products of different application rates were diluted in water and sprayed in the field at a spray rate of 2000 Ι/ha. Prior to spraying, the newly developed leaves of the cabbage plants planted in the field were marked. The leaves of the labeled leaves or the labeled leaves were collected for laboratory bioassays, respectively, at 1, 3, 7, and 14 days after application (DAT). Self-collecting leaves Five leaf discs (2.5 cm in diameter) were removed and placed in a Petri dish. Approximately 10 third instar larvae/culture dishes were released thereon and maintained in an insect breeding room at 24t, 16 hours light/8 hours dark. The second and third days after insect release were evaluated according to SCHNEIDER-ORELLI. Preparation Example 4 provides excellent aftereffect control for both species (see Tables 9 and 10) 〇128803.doc -56- 200838420 Table 9: Preparation of Example 4 Resistance Compounds of Resistance to Brassica campestris in Cabbage Application rate (ppm) % control (Plutella xylostella) - third age 3 DAT 7 DAT 14 DAT untreated control 0 27.3 19.7 0.0 Example 4 160 96 97 59 + 200 96 90 64 Adjuvant * 250 96 97 76 * 0.02% adjuvant (Kumiten 8)

Table 10 · Preparation in the field bioassay test Example 4 Effect of application of compound compound against Spodoptera litura on cabbage (ppm) % Control (S. cerevisiae) - 3rd instar 3 DAT 7 DAT 14 DAT Untreated Control 0 19.3 0.0 0.0 Example 4 160 100 100 96 + 200 100 100 90 Adjuvant* 250 100 100 100 * 0.02% adjuvant (Kumiten®) 4. Penetration into cotton leaves Preparation Example 6 was evaluated according to the following procedure Penetration into cotton leaves: • C-14 labeled Compound A_1 was incorporated into the formulation of Preparation Example 6. The treatment solution was prepared at a concentration of 240 g/ha and diluted with water to 200 Ι/ha. The treatment solution was applied to the surface of the cotton leaf in the form of microliters of small droplets using a microliter syringe. The treated leaves can be dried in a furnace enclosure and the plants can then be placed in a greenhouse. After the predicted period of time, the treated leaves were washed sequentially with water, decyl alcohol and dichloromethane. Finally burn the blades. The amount of carbon 14 in the laundry and the combustibles was determined by LSC (liquid scintillation counting). The percentage distribution of the residue from the applied dose of C-14 Compound A-1 in cotton leaves 128803.doc -57-200838420 was then determined. The results of the leaf absorption test of Preparation Example 6 showed that about 27% of the fine 1 after 14 days was absorbed into the cotton leaves with the labeled compound A-1 of the backing. Therefore, after the aqueous emulsion of the concentrate was applied to the surface of the cotton leaf, excellent penetration through the wax layer of the blade was observed.

128803.doc -58-

Claims (1)

200838420 X. Patent application scope: 1 · A liquid pesticide concentration formulation in the form of a emulsifiable concentrate or a microemulsion concentrate, which comprises: a) a stupid base of a formula A of a carbaryl compound·· Η Η Wherein R and R are each independently a mouse, a halogen, a nitrogen group, a C1-C4 alkyl group, a CrC4 alkoxy group, a Cl-C4 haloalkyl group or (^-(:4_alkoxy group and R3 is a CpC4 oxygenated group). a group, C^C: a 4-haloalkyl group or a C1-C4 haloalkoxy group, or an agriculturally acceptable salt thereof; - b) as one of an organic solvent or a plurality of indoleamines of the formula b1, R5 R4 — CO(b1) V • wherein R4 is C6-C20 alkyl, C6-C20 alkenyl or C6-C20 alkynyl, and R5 and R6 are each independently hydrogen or C--C4 alkyl, and • c) Or a variety of surfactants. 2. A formulation according to claim 1 which comprises: a) from 1 to 65% by weight of the total weight of the compound A; b) from 15 to 80% by weight based on the total weight of the formulation One or more of the guanamines of the formula bl; c) from 0.1 to 30 weight based on the total weight of the formulation. One or more interfaces 128803.doc 200838420 Surfactant. 3. A formulation according to claim 1 or 2 which comprises a phenylhalocarbazone compound of the formula A in an amount of from 20 to 40% by weight, based on the total weight of the formulation. 4. A formulation according to claim 1 or 2 wherein R4 is C6-C12 alkyl and R5 and r6 are CVCU alkyl. 5. A formulation according to claim 1 or 2 which comprises from 30 to 65% by weight, based on the total weight of the formulation, of the guanamine of the formula bl. 6. The formulation of claim 1 or 2, further comprising one or more organic solvents (b2) selected from the group consisting of aromatic cigarettes, CrCw aliphatic ketones, CVCm cycloaliphatic ketones, and Ci-Cw aromatic ketones. 7. The formulation of claim 6, wherein the amount of the solvent (b2) is in the range of 5 to 20% by weight based on the total weight of the formulation. *8. The formulation of claim 1, wherein the surfactant (c) comprises at least one nonionic surfactant. 9. The formulation of claim 1, wherein the surfactant (c) comprises at least one nonionic surfactant and at least one anionic surfactant. 10. The formulation of claim 8 or 9, wherein the nonionic surfactant package 3 has at least one poly(ethylene oxide) moiety and at least one source. ~_ Stretching base oxide and / or styrene oxide scales :: ionic block copolymer. <Non-11. The formulation of claim 8 or 9, comprising an alkylene or alkylphenol ether substrate 0 wherein the nonionic surfactant package comprises ethylene oxide-propylene oxide block copolymerization 128803.doc 200838420 12·如晴A formulation comprising 2, 8 or 9 comprising one or more other active ingredients for crop protection selected from the group consisting of acaricides, scutellaria, antecedents, and avians Aricide, fungicide, bird repellent, chemical sterilant, fertilizer, fungicide, herbicide, herbicide, whole insecticide, insect repellent, insecticide, mammalian repellent, agent, mating Interfering agents, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, synergists and virucides. The use of a formulation according to any one of claims 1 to 12 for combating a pest organism selected from an arthropod or nematode pest. 14. A method of combating a pest organism selected from an arthropod or nematode pest, comprising a plant that causes the pest, its habitat, breeding area, food source, harmful organism to grow or possibly grow , plant, soil, area, material, or environment, or material, plant, seed, soil, surface, or door that is to be protected from attack or invasion by harmful organisms, as valid in claims i to 〖2 The formulation of any of the formulations or the aqueous formulation obtained by diluting the formulation of any of the items 1 to 12 with water. 15. Use of a formulation as claimed in item -12 to _ to protect crops against harmful, biological attack and invasion selected from arthropod or nematode pests. 16·- (4) A method for protecting crops from attack or invasion by a pest selected from an arthropod or a nematode pest, the method comprising causing the crop to have an effective amount as claimed in items 1 to 19 by The formulation is contacted with an aqueous formulation obtained by diluting a formulation such as any of the ingredients with water. 128803.doc 200838420 17· - Protecting seeds from love selected from ~ Biological attack or inflicting harmful effects on worms or nematode pests as requested in items 1 to !: 中任: This method contains seeds and is effective The formulation of the amount is contacted with an aqueous formulation obtained by diluting the formulation of any one of claims 1 to 12 with water. 18- Seeds are treated with a formulation as claimed in any one of claims 1 to 12. I28803.doc -4- 200838420 VII. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure·· 8. If there is a chemical formula in this case, please reveal the most A chemical formula that shows the characteristics of the invention: 128803.doc