Cleaning method
A high-pH organic solvent-based cleaning composition effectively removes pesticide residues from spraying machines, addressing contamination and phytotoxicity concerns by significantly reducing residue levels.
Patent Information
- Application Number
- PCT/JP2024/045926
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-12-27
- Filing Date
- 2024-12-25
- Publication Date
- 2025-07-03
AI Technical Summary
Existing cleaning methods for pesticide spraying machines are inadequate in effectively removing pesticide residues, leading to potential contamination of harvested products and phytotoxicity issues.
A high-pH liquid composition containing an organic solvent is used to clean pesticide spraying machines, with specific solvents like solvent naphtha and cyclohexanone, and alkalis such as sodium hydroxide or tetrabutylammonium hydroxide, to break down and remove pesticide residues.
The method effectively reduces pesticide residues on spraying machines by up to 50% or more, ensuring compliance with safety standards and preventing phytotoxicity.
Smart Images

Figure JPOXMLDOC01-APPB-T000001 
Figure JPOXMLDOC01-APPB-T000002 
Figure JPOXMLDOC01-APPB-T000003
Abstract
Description
Cleaning method
[0001] The present invention relates to a cleaning method.
[0002] Pesticide sprayers are commonly used to spray pesticides. Sprayers used for pesticide spraying usually contain residual pesticides. Using a sprayer containing residual pesticides can result in unintentional spraying of pesticide residues, which can cause problems. Examples of such problems include pesticide residues in harvested agricultural products exceeding standard limits, or, if the pesticide is a herbicide, causing damage to crops. Therefore, it is desirable to properly clean sprayers used for pesticide spraying. However, known cleaning methods are not always complete, and new cleaning methods are needed. Methods for cleaning pesticide sprayers generally include methods that inactivate active ingredients through oxidation-reduction reactions (Patent Document 1), methods that inactivate active ingredients with acids or alkalis (Non-Patent Document 1), and methods that use surfactants (Non-Patent Document 2).
[0003] U.S. Patent No. 9,657,258
[0004] Valent Tank Cleaner Safety Data SheetAll Clear Safety Data Sheet
[0005] An object of the present invention is to provide a new method for cleaning articles on which active ingredients of agricultural chemicals remain.
[0006] The present inventors have found that pesticide residues can be effectively removed from articles on which the active ingredients of pesticides remain by using a high pH liquid composition containing an organic solvent. The present invention includes the following [1] to
[11] .
[0007] [1] A method for cleaning an article on which an active ingredient of a pesticide remains, comprising contacting the article with a cleaning liquid composition containing an organic solvent and having a pH of 10 or higher. [2] The method according to [1], wherein the article is a pesticide sprayer. [3] The method according to [1], wherein the organic solvent is solvent naphtha. [4] The method according to [1], wherein the organic solvent is cyclohexanone. [5] The method according to [1], wherein the organic solvent is tetrahydrofuran. [6] The method according to [1], wherein the cleaning liquid composition contains an inorganic alkali. [7] The method according to [1], wherein the cleaning liquid composition contains an alkali metal hydroxide. [8] The method according to [1], wherein the cleaning liquid composition contains an organic alkali. [9] The method according to [1], wherein the cleaning liquid composition contains tetrabutylammonium hydroxide.
[10] A cleaning liquid composition containing an organic solvent and tetrabutylammonium hydroxide.
[11] Use of a cleaning liquid composition containing an organic solvent and having a pH of 10 or higher for cleaning an article on which an active ingredient of a pesticide remains.
[0008] The present invention makes it possible to effectively clean articles on which active ingredients of agricultural chemicals remain.
[0009] The cleaning method of the present invention (hereinafter sometimes referred to as the method of the present invention) comprises contacting an article on which an active ingredient of a pesticide (hereinafter sometimes referred to as the active ingredient) remains with a cleaning liquid composition containing an organic solvent and having a pH of 10 or higher (hereinafter sometimes referred to as the composition of the present invention).
[0010] Articles on which active ingredients remain are usually those with which pesticides come into contact or adhere when used, such as pesticide sprayers, protective clothing, goggles, gloves, stirring rods, measuring cups, pesticide containers (storage containers for pesticide distribution and containers for temporarily storing spray liquid used in pesticide spraying), etc. When the article is a pesticide sprayer, the parts of the pesticide sprayer on which active ingredients remain are the components that make up the pesticide sprayer and that usually come into contact with or adhere to the spray liquid, including tanks, pipes, hoses, O-rings, strainers, nozzles, etc. The tank is usually made of polyethylene or polypropylene, the hose is usually made of synthetic rubber (e.g., EPDM), polyurethane, or polyvinyl chloride, and the pipe and strainer are usually made of stainless steel.
[0011] Examples of organic solvents contained in the composition of the present invention include aliphatic hydrocarbons (hexane, 1-hexene, cyclohexane, octane, isooctane, 1-heptene, d-limonene, pinene, heptane, hexadecane, etc.), aromatic hydrocarbons (alkylbenzenes (toluene, xylene, isopropylbenzene, p-diethylbenzene, etc.), alkylbenzene derivatives, alkylnaphthalenes, alkylnaphthalene derivatives, tetrahydronaphthalene, etc.), chlorinated hydrocarbons (monochloroethylene, dichloroethylene, trichloroethylene, tetrahydronaphthalene, etc.), and the like. trichloroethylene, dichloromethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,2-dichloropropane, etc.), ketones (cyclohexanone, cyclopentanone, acetone, 2-heptanone, isophorone, mesityl oxide, methyl isoamyl ketone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, diacetone alcohol, methylcyclohexanone, etc.), esters (fatty acid esters (ethyl acetate, butyl acetate, amyl acetate, isoamyl acetate, isobornyl acetate, hexyl acetate, acetic acid Heptyl, octyl acetate, isopropyl myristate, methyl octanoate, methyl oleate, methyl laurate, dibutyl adipate, tributyl citrate, dibutyl phthalate, etc.), lactate esters (ethyl lactate, propyl lactate, etc.), carbonate esters (ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, dibutyl carbonate, etc.), esterified polyols (glycerol acetate, glycol acetate, glycerin monoacetate, glycerin diacetate, glycerin triacetate, diethylene glycol abietic acid ester, dipropylene glycol dibenzoate, dipropylene glycol monomethyl ester, etc.), lactones (γ-butyl lactone, etc.)), ethers (1,4-dioxane, tetrahydrofuran, dipropylene glycol methyl ether, ethylene glycol methyl ether, propylene glycol methyl ether, etc.), amides (N-octyl-caprolactam, N-dodecyl-caprolactam, N,N-dimethylformamide, fatty acid dimethylamides (N,N-dimethylacetamide, N,N-dimethyldecanamide, N,N-dimethyloctanamide, etc.), alkylpyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone, etc.), lactams (α-lactam, β-lactam, γ-lactam, δ-lactam, etc.), alcohols (methanol, ethanol, butanol, propanol, isopropanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexanol, hexylene glycol, cyclohexanol, phenol, benzyl alcohol, methoxypropanol (1-methoxy-2-propanol), tetrahydrofurfuryl alcohol, furfuryl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol, hexylene glycol, ethylene glycol methyl ether, diethylene glycol methyl ether, diethylene glycol Examples of suitable solvents include butyl ether, triethylene glycol, propylene glycol methyl ether, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol monomethyl ether, and glycerin; mineral oils (solvent naphtha, petroleum ether, kerosene, diesel oil, paraffin, and olefins); plant-derived oils (palm oil, rapeseed oil, castor oil, coconut oil, soybean oil, and derivatives thereof); animal-derived oils (sardine oil, saury oil, whale oil, and derivatives thereof); dimethyl sulfoxide, silicone oil, acetonitrile, propanenitrile, acid anhydrides (such as acetic anhydride), and 1,3-dimethyl-2-imidazolidinone. Solvent naphtha, cyclohexanone, and tetrahydrofuran are particularly preferred.
[0012] Solvent naphtha is an aromatic oil with a boiling point range of approximately 120 to 300°C obtained by fractional distillation of coal tar-based diesel oil. Industrial products include Aromatic 200, Aromatic 200ND, Aromatic 150, Aromatic 150ND, and Aromatic 100 manufactured by ExxonMobil Chemical Corporation, as well as general-purpose petroleum benzine.
[0013] The amount of organic solvent contained in the composition of the present invention is usually 1 to 50% (v / v), and specific amounts of organic solvent in the composition of the present invention include 2% (v / v), 3% (v / v), 4% (v / v), 5% (v / v), 8% (v / v), 10% (v / v), 15% (v / v), 20% (v / v), 30% (v / v), and 40% (v / v).
[0014] The pH of the composition of the present invention is 10 or higher. The pH of the composition of the present invention is usually in the range of 10 to 15, specifically 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, and 14.5. The pH of the composition of the present invention is determined primarily by the amount of alkali contained in the composition of the present invention, i.e., the alkali concentration in the composition of the present invention. The pH is measured by a conventional method using test paper or an electric meter.
[0015] The alkali contained in the composition of the present invention includes inorganic alkali and organic alkali. Inorganic alkali includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and ammonia. Organic alkali includes amines and their salts, including ammonium salts such as tetrabutylammonium hydroxide, tributylmethylammonium hydroxide, and choline hydroxide. Sodium hydroxide, potassium hydroxide, and tetrabutylammonium hydroxide are particularly preferred.
[0016] The amount of alkali contained in the composition of the present invention is usually 0.1 to 100 mM, specifically 0.2 mM, 0.4 mM, 0.8 mM, 1 mM, 2 mM, 4 mM, 6 mM, 8 mM, 10 mM, 20 mM, 40 mM, 60 mM, and 80 mM. When the alkali is sodium hydroxide, potassium hydroxide, or tetrabutylammonium hydroxide, the amount is usually 0.1 mM or more, and when the alkali is ammonia, the amount is usually 40 mM or more. The amount of alkali contained in the composition of the present invention can also be expressed in normality, and is usually 0.03 to 2N.
[0017] Preferred combinations of organic solvent and alkali for use in the composition of the present invention are listed below. The numbers in parentheses after the organic solvent and alkali indicate the amount (concentration) contained in the composition of the present invention, with the units being volume % (v / v%) for the organic solvent and mM for the alkali. Solvesso 200ND listed below is a solvent naphtha manufactured by ExxonMobil. Solvesso 200ND (1, 2, 5) + Sodium hydroxide (50, 100, 150, 200) Solvesso 200ND (1, 2, 5) + Potassium hydroxide (50, 100, 150, 200) Solvesso 200ND (1, 2, 5) + Tetrabutylammonium hydroxide (50, 100, 150, 200) Solvesso 200ND (1, 2, 5) + Ammonia (50, 100, 150, 200) Cyclohexanone (1, 2, 5) + Potassium hydroxide (50, 100, 150, 200) Cyclohexanone (1, 2, 5) + Sodium hydroxide (50, 100, 150, 200) Cyclohexanone (1, 2, 5) + tetrabutylammonium hydroxide (50, 100, 150, 200) Cyclohexanone (1, 2, 5) + ammonia (50, 100, 150, 200) Tetrahydrofuran (1, 2, 5) + potassium hydroxide (50, 100, 150, 200) Tetrahydrofuran (1, 2, 5) + sodium hydroxide (50, 100, 150, 200) Tetrahydrofuran (1, 2, 5) + tetrabutylammonium hydroxide (50, 100, 150, 200) Tetrahydrofuran (1, 2, 5) + ammonia (50, 100, 150, 200)
[0018] In the method of the present invention, contacting an article with the composition of the present invention includes both immersing the article itself in the composition of the present invention and placing the composition of the present invention inside the article. When contacting the article with the composition of the present invention, the composition of the present invention may be contacted while the composition of the present invention is flowing or while the flow of the composition of the present invention is stopped. In either case, physical stimulation (friction, abrasion, shaking) may be applied. The pressure during contact may be atmospheric pressure, but pressurization may also be applied when the composition of the present invention is placed inside the article. In addition, it is preferable to rinse the article with water before contacting the composition of the present invention.
[0019] When the article is a pesticide sprayer, the tank is typically located upstream, the hose and pipe are located midstream (in any order), and the nozzle is located downstream. The top, middle, and bottom directions generally refer to the direction of flow of the spray solution during spraying. The space through which the spray solution moves during spraying is called the spray line. In the method of the present invention, the composition of the present invention is typically first placed in a tank, discharged from the nozzle by natural flow or pressure, and then the nozzle is closed, allowing the composition of the present invention to remain in the spray line for a certain period of time. The composition of the present invention is typically prepared by mixing predetermined amounts of organic solvent and water with an amount of alkali to achieve a pH of 10 or higher. In the method of the present invention, when the composition of the present invention is placed in a tank, a pre-prepared composition of the present invention may be added to the tank, or the organic solvent, alkali, and water may be added separately to prepare the composition of the present invention inside the tank. Alternatively, a composition containing an organic solvent and alkali (a premix formulation) and water may be added separately to prepare the composition of the present invention inside the tank. The order of adding materials when preparing the composition of the present invention is not particularly limited, but it is preferable to add water (part or all of the final required amount) first. During preparation, agitation is usually carried out to ensure that the ingredients are uniform.
[0020] When the organic solvent is poorly soluble in water, it is possible to mix it with a specific surfactant as an emulsifier to make it compatible with water. In this case, it is desirable to mix the organic solvent and surfactant in advance.
[0021] The time for which the composition of the present invention is allowed to remain in the spray line is typically 1 to 48 hours, preferably 4 to 12 hours, and more preferably 6 to 8 hours. The spray line may be pressurized for all or part of that time, and the pressure is typically in the range of 10 to 100 PSI, preferably 30 to 50 PSI. Some pesticide applicators have a function for recirculating the encapsulated liquid from downstream to upstream of the spray line (recirculation), and recirculation may be performed for all or part of that time. When the composition of the present invention is allowed to remain in the spray line, the spray line may be completely filled with the composition of the present invention, or the composition of the present invention may be present only partially. For example, the hose may be completely filled but the tank may be mostly empty.
[0022] After allowing the composition to remain in the spray line for a certain period of time, the composition is expelled from the nozzle by gravity or under pressure, after which the spray line may optionally be rinsed with running water.
[0023] In the method of the present invention, the residual level of the active ingredient on the article after washing is lower than that before washing. The level achieved varies depending on the active ingredient, the article, and the contact time between the article and the composition of the present invention, but the residual rate is usually 0.1 to 50% of that before washing. Specific washing levels include residual rates of 0.2%, 0.3%, 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, and 40% of that before washing. These levels may be confirmed by chemical analysis or bioassay using test organisms.
[0024] Examples of pesticide sprayers to be cleaned in the method of the present invention include backpack carbon dioxide sprayers, backpack power sprayers, boom sprayers, speed sprayers, and pesticide spraying drones, with boom sprayers being particularly preferred. Boom sprayers may be self-propelled or towed by a tractor. The size of the pesticide sprayer is not particularly limited, but is typically 1 L to 10,000 L, preferably 200 to 5,000 L, and more preferably 1,000 to 3,000 L, in terms of tank capacity.
[0025] In the method of the present invention, examples of the active ingredient of the agricultural chemical include herbicides, fungicides, insecticides, and safeners. These active ingredients may remain on the article, but independently, if the article is a pesticide sprayer, they may also be sprayed by the sprayer after washing. Examples of herbicides include the following: 2,3,6-TBA (2,3,6-trichlorobenzoic acid), 2,3,6-TBA dimethylammonium, 2,3,6-TBA lithium salt, 2,3,6-TBA potassium salt, 2,3,6-TBA sodium salt, 2,4-D, 2,4-D choline salt, 2,4-D biproamine, 2,4-D doboxyl, 2,4-D 2-ethylhexyl, 2,4-D 3-butoxypropyl (2,4-D-3-butoxypropyl), 2,4-D ammonium (2,4-D-ammonium), 2,4-D butotyl (2,4-D-butyl), 2,4-D butyl (2,4-D-butyl), 2,4-D diethylammonium (2,4-D-diethylammonium), 2,4-D dimethylammonium (2,4-D-dimethylammonium), 2,4-D diolamine (2,4-D-diolamine), 2,4-D dodecylammonium (2,4-D-dodecylammonium), 2 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl2,4-D-octyl, 2,4-D-pentyl, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 2,4-DB, 2,4-DB choline salt), 2,4-DB-biproamine, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, ACN (2-amino-3-chloronaphthalene), phthalene-1,4-dione), alachlor, allidochlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralid choline salt,Aminopyralid potassium salt (aminopyralid-potassium), aminopyralid Trypromine (aminopyralid-tripromine), amiprophos-methyl, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, benquitrione, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benthiocarb, benzfendizone, benzobicyclon, benzofenap nzofenap), benzthiazuron, bialaphos, bicyclopyrone, bifenox, bipyrazone, bispyribac, bispyribac-sodium, bixlozone, broclozone, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butyrate, cafenstrole, carbetamide,Carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben, chloridazon, chlorimuron, chlorimuron-ethyl, chlorbromuron, chlorotoluron, chloroxuron, chlorpropham, chlorsulfuron on), chlorthal-dimethyl, chlorthiamid, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid choline salt choline salt), clopyralid methyl, clopyralid olamine salt, clopyralid potassium salt, clopyralid tris(2-hydroxypropyl)ammonium, cloransulam, cloransulam methyl, cumyluron, cyanazine, cyclopyranyl, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl,Cypyrafluone, daimuron, dalapon, dazomet, desmedipham, desmetryn, di-allate, dicamba, dicamba choline salt, dicamba-biproamine, dicamba amine salt -trolamine), dicamba-diglycolamine, dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium, dichlobenil, dichlorprop, dichlorprop choline salt), dichlorprop-biproamine, dichlorprop-etexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P choline salt, dichlorprop-P-biproamine, dichlorprop-P-etexyl,Dichlorprop-P-dimethylammonium, dichlorprop potassium salt, dichlorprop sodium salt, diclofop, diclofop-methyl, diclosulam, difenoxuron, difenzoquat, difenzoquat methyl sulfate metilsulfate, diflufenican, diflufenzopyr, diflufenzopyr sodium salt, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimepiperate, dinitramine, dinoseb, dinoterb, dioxopyritrione, diphenamid, diquat, diquat-dibromide, DSMA (disodium methylarsonate), dithiopyr, diuron, DNOC (2-methyl-4,6-dinitrophenol), esprocarb, epirifenacil, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethidimuron, ethofumesate, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid,Fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, fenuron, feproxydim, fentrazamide, Flamprop-M, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, fluazola te), flucarbazone, flucarbazone sodium salt (flucarbazone-sodium), flucetosulfuron (flucetosulfuron), fluchloraminopyr (fluchloraminopyr), fluchloraminopyr-tefuryl (fluchloraminopyr-tefuryl), flufenacet (flufenacet), flufenoximacil (flufenoximacil), flufenpyr (flufenpyr), flufenpyr-ethyl (flufenpyr-ethyl), flumetsulam (flumetsulam), flumetsulam (flumetsulam), flumiclorac (flumiclorac), flumiclorac-pentyl (flumiclorac-pentyl), flumioxazin (flumioxazin), fluometuron (fluometuron), fluoroglycofen-ethyl (fluoroglycofen-ethyl), flupoxam (flupoxam), flupropanate (flupropanate), flupyrsulfuron (flupyrsulfuron),Flupyrsulfuron-methyl-sodium, flurenol, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, flusulfinam, fluthiacet, fluthiacet-methyl, Fomesafen, fomesafen sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate choline salt), glyphosate isopropylammonium salt (glyphosate-isopropylammonium), glyphosate biproamine salt (glyphosate-biproamine), glyphosate ammonium salt (glyphosate-ammonium), glyphosate diammonium salt (glyphosate-diammonium), glyphosate potassium salt (glyphosate-potassium), glyphosate sodium salt (glyphosate-sodium), glyphosate trimesium salt (glyphosate-trimesium), halauxifen, halauxifen-benzyl, halauxifen-methyl, halosafen, halosulfuronHalosulfuron-methyl, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, hexazinone, icafolin, icafolin methyl in-methyl), imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazamox-sodium, imazapic, imazapic-ammonium, imazapyr, imazapyr-ammonium um), imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, indolauxipyr, indolauxipyr-cyanomethyl, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil-octanoate, ipfencarbazone,Iptriazopyrid, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA (2-(4-chloro-2-methylphenoxy)acetic acid), MCPA choline salt salt), MCPA-biproamine, MCPA-etexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-sodium, MCPA-trolamine, MCPB (4-(4-chloro-2-methylphenoxy)butanoic acid), MCPB choline salt), MCPB-biproamine, MCPB-ethyl, MCPB-methyl, MCPB sodium salt, mecoprop, mecoprop choline salt, mecoprop-biproamine, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium,Mecoprop diolamine salt (mecoprop-diolamine), mecoprop ethadyl, mecoprop isoctyl, mecoprop methyl, mecoprop potassium salt (mecoprop-potassium), mecoprop sodium salt (mecoprop-sodium), mecoprop trolamine salt (mecoprop-trolamine), mecoprop P (mecoprop-P), mecoprop P choline salt (mecoprop-P), mecoprop P 2-Ethylhexyl (mecoprop-P-2-ethylhexyl), mecoprop-P dimethylammonium (mecoprop-P-dimethylammonium), mecoprop-P isobutyl (mecoprop-P-isobutyl), mecoprop-P potassium salt (mecoprop-P-potassium), mefenacet, mesosulfuron, mesosulfuron-methyl, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron enzthiazuron), methiozolin (methiozolin), methyldymron (methyldymron), metobromuron (metobromuron), metolachlor (metolachlor), metosulam (metosulam), metoxuron (metoxuron), metproxybicyclone (metproxybicyclone), metribuzin (metribuzin), metsulfuron (metsulfuron), metsulfuron-methyl (metsulfuron-methyl), molinate (molinate), monolinuron (monolinuron), naproanilide (naproanilide), naproxamide (napropamide), naproxamide M (napropamide-M), naptalam (naptalam),Neburon, nicosulfuron, norflurazon, oleic acid, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, paraquat-dichloride, pebulate, pelargonic acid acid), pendimethalin, penoxsulam, pentanochlor, pentoxazone, pethoxamid, phenisopham, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine , profluazol, propoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone sodium salt, propyrisulfuron, propyzamide, prosulfocarb,Prosulfuron, pyraclonil, pyraquinate, pyraflufen-ethyl, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb b), pyridafol, pyridate, pyriflubenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, Quinclorac (quinclorac), quinmerac (quinmerac), quizalofop (quizalofop), quizalofop-ethyl (quizalofop-ethyl), quizalofop-tefuryl, quizalofop P (quizalofop-P), quizalofop P-ethyl (quizalofop-P-ethyl), quizalofop P-tefuryl (quizalofop-P-tefuryl), rimisoxafen (rimisoxafen), rimsulfuron (rimsulfuron), saflufenacil (saflufenacil), sethoxydim (sethoxydim), EPTC (S-ethyl N,N-dipropylcarbamothioate), siduron (siduron), simazine (simazine), simetryn (simetryn), S-metolachlor (S-metolachlor), MSMA (sodium hydrogen methylarsonate), sulcotrione, sulfentrazone,Sulfometuron, sulfometuron-methyl, sulfosulfuron, swep, TCA (2,2,2-trichloroacetic acid), TCA ammonium, TCA calcium, TCA ethadyl, TCA magnesium, TCA sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thaxtomin A A), thenylchlor, thiazopyr, thidiazimin, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiafenacil, thiocarbazil, tolpyralate, topramezone, tralco tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium,Tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tripyrasulfone, tritosulfuron, vernalate late), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(methylthio)-4-(trifluoromethyl)benzamide, 2-methyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(methanesulfonyl)-4-(trifluoromethyl)benzamide, 1-{2-chloro-6-[(5-chloropyrimidin-2-yl)oxy]phenyl}-4,4,4-trifluorobutan-1-one. Examples of safeners include the following. Allidochlor, benoxacor, cloquintocet, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dimepiperate, disulfoton, daimuron, fenchlorazole, fenchlorazole-ethyl, fenclorim, flurazole, furilazole, fluxofenim, hexim,Isoxadifen, isoxadifen-ethyl, Jiecaowan, Jiecaoxi, mecoprop, mefenpyr, mefenpyr-ethyl, mefenpyr-diethyl, mephenate, metcamifen, oxabetrinil, 1,8-naphthalic anhydride, 1,8-octamethylene diamine, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (AD-67), 2-(4-chloro-2-methylphenoxy)acetic acid (MCPA), CL-304415 (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic MG191 (2-(dichloromethyl)-2-methyl-1,3-dioxolane), MG-838 (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate), PPG-1292 (2,2-dichloro-N-(1,3-dioxan-2-ylmethyl)-N-(2-propenyl)acetamide), R-28725 (3-(dichloroacetyl)-2,2-dimethyl-1,3-oxazolidine), R-29148 (3-(dichloroacetyl)-2,2,5-trimethyl-1,3-oxazolidine), TI-35 (1-(dichloroacetyl)azepane). Examples of insecticides include abamectin, acephate,Acequinocyl, acetamiprid, acetoprole, acrinathrin, acinonapyr, afidopyropen, afoxolaner, alanycarb, aldicarb, allethrin, alpha-cypermethrin, alpha-endosulfan, aluminum phosphide, amitraz, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azocyclotin, and bark of Celastrus angulatus. angulatus), bendiocarb, benfluthrin, benfuracarb, bensultap, benzoximate, benzpyrimoxan, beta-cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin, bilobalide, bioallethrin, bioresmethrin, bistrifluron, borax, boric acid acid), broflanilide, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, cadusafos, calcium cyanide,Calcium phosphide, carbaryl, carbofuran, carbosulfan, cartap hydrochloride, cartap, cevadine, chinomethionate, chlorantraniliprole, chlordane, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezine, clothianidin, concanamycin A A), coumaphos, cryolite, cyanophos, cyantraniliprole, cyclaniliprole, cyclobutrifluram, cycloprothrin, cycloxaprid, cyenopyrafen, cyetpyrafen, cyflumetofen, cyfluthrin, cyhalodiamide, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin, cyproflanilide , cyromazine, dazomet, deltamethrin, demeton-S-methyl,Diafenthiuron, diatomaceous earth, diazinon, dichlorvos, dichloromezotiaz, dicofol, dicrotophos, diflovidazin, diflubenzuron, dimefluthrin, dimethoate, dimethylvinphos, diimpropyridaz, dinotefuran, disodium octaborate, disulfoton, DNOC (2-methyl-4,6-dinitrophenol), doramectin, dried leaves of Dryopteris filix-mas), emamectin benzoate, empenthrin, endosulfan, EPN (O-ethyl O-(4-nitrophenyl) phenylphosphonothioate), epsilon-metofluthrin, epsilon-momfluorothrin, esfenvalerate, ethifencarb, ethion, ethiprole, ethoprophos, etofenprox, etoxazole, Artemisia absinthium extract, Cassia nigricans extract, Clitora ternatea extract ternatea), extract of Pyrethrum,Comfrey extract (extract of Symphytum officinale), stinging nettle extract (extracts or simulated blend of Chenopodium ambrosioides), tansy extract (extract of Tanacetum vulgare), nettle extract (extract of Urtica dioica), mistletoe extract (extract of Viscum album), famphur, fenamiphos, fenazaquin, fenbutatin oxide oxide), fenitrothion, fenmezoditiaz, fenobucarb, fenoxycarb, fenpropathrin, fenpyroximate, fenthion, fenvalerate, fipronil, flometoquin, flonicamid, fluacrypyrim, fluazaindolizine, fluazuron, flubendiamide, fluchlordinilipro fluchlordiniliprole, flucycloxuron, flucythrinate, fluensulfone, flufenprox, flufenoxuron, flufiprole, flumethrin, flupentiofenox, fluopyram, flupiroxystrobin, flupyradifurone, flupirimin, fluralaner, fluvalinate,Fluxametamide, formetanate, fosthiazate, furamethrin, furathiocarb, gamma-cyhalothrin, ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, ginkgolide M, GS-omega / kappa HXTX-Hv1a peptide peptide), halfenprox, halofenozide, heptafluthrin, heptenophos, hexaflumuron, hexythiazox, potassium salt of hop beta acid , hydramethylnon (hydramethylnon), hydroprene (hydroprene), imicyafos (imicyafos), imidacloprid (imidacloprid), imidaclothiz (imidaclothiz), imiprothrin (imiprothrin), indazapyroxamet (indazapyroxamet), indoxacarb (indoxacarb), isocycloseram (isocycloseram), isofenphos (isofenphos), isoflualanan (isoflualanam), isoprocarb (isoprocarb), isopropyl O- (methoxyaminothiophosphoryl) salicylate (isopropyl-O- (methoxyaminothiophosphoryl) salicylate), isoxathion (isoxathion), ivermectin (ivermectin), kadesrin (kadesrin), kappa tefluthrin (kappa- tefluthrin), kappa-bifenthrin, kinoprene, lambda-cyhalothrin,Ledprona (ledprona), lenoremycin (lenoremycin), lepimectin (lepimectin), lime sulfur (lime sulfur), lotilaner (lotilaner), lufenuron (lufenuron), machine oil (machine oil), malathion (malathion), mecarbam (mecarbam), meperfluthrin (meperfluthrin), metaflumizone (metaflumizone), metam (metam), methamidophos (methamidophos), methidathion (methidathion), methiocarb (methiocarb), methomyl (methomyl), methoprene (methoprene), methoxychlor (methoxychlor), methoxyfenozide (methoxyfenozide), methyl bromide (methyl bromide, metofluthrin, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin oxime, mivorilaner, modoflaner, momfluorothrin, monocrotophos, moxidectin, naled, extract of Azadirachta indica, nicofluprole, nicotine, nicotine sulfate, nitenpyram, novaluron, noviflumuron, oil of the seeds of Chenopodium anthelminticum), omethoate, oxamyl, oxazosulfyl, oxydemeton-methyl, parathion, parathion-methyl,Permethrin, phenothrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphine, phoxim, piperflanilide, pirimicarb, pirimiphos-methyl, potassium cyanide, prallethrin, profenofos, profluthrin, propargite, propetamphos, propoxur, propylene glycol alginate), prothiofos, piflubumide, pymetrozine, pyraclofos, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazone, pyrimidifen, pyriminostrobin, pyriprole, pyriproxyfen, quinalphos, resmethrin, rotenone, ryanodine, sarolaner, Sabadilla seed extract spp.), selamectin, sigma-cypermethrin, silafluofen, sodium borate, sodium cyanide, sodium metaborate, spidoxamat,Spinetoram, spinosad, spirodiclofen, spiromesifen, spiropidione, spirotetramat, sulfiflumin, sulfluramid, sulfotep, sulfoxaflor, sulfur, sulfuryl fluoride, tartar emetic), tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, terbufos, terpene constituents of the extract of chenopodium ambrosioides near ambrosioides, Brand name: Terpenoid blend QRD 460), tetrachlorantraniliprole, tetrachlorvinphos, tetradifon, tetramethrin, tetramethylfluthrin, tetraniliprole, theta-cypermethrin, thiacloprid, thiamethoxam, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap disodium, thiosultap monosodium, tigolaner,Tioxazafen, tolfenpyrad, tralomethrin, transfluthrin, triazamate, triazophos, trichlorfon, trifluenfuronate, triflumezopyrim, triflumuron, trimethacarb, tyclopyrazoflor, umifoxolaner, vamidothion, veratridine, Quassia amara wood extract, 3,5-dimethylphenyl N-methylcarbamate (XMC), xylylcarb, zeta-cypermethrin, zinc phosphide phosphide), N-[3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropanesulfinyl)propanamide (1477923-37-7), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide (1241050-20-3), 3-methoxy-N-(5-{5-(trifluoromethyl)-5-[3- (trifluoromethyl)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}indan-1-yl)propanamide (1118626-57-5), 2-({2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (1445683-71-5), N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide,N-{4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl}-1-methyl-4-(methanesulfonyl)-3-(1,1,2,2,2-pentafluoroethyl)-1H-pyrazole-3-carboxamide (1400768-21-9), N-[3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl]-2-(methanesulfonyl)propanamide (2396747-83-2), N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazolinone] N-({2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,4-triazolidine-1-yl)sulfonyl]-N-ethyl-3-(methanesulfonyl)propanamide, 1,4-dimethyl-2-[2-(pyridin-3-yl)-2H-indol-5-yl]-1,2,4-triazolidine-3,5-dione (2171099-09-3), 2-isopropyl-5-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]-1,3,4-thiadiazole (2058052-95-0), N-({2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4, 5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methyl)cyclopropanecarboxamide, 7-fluoro-N-[1-(methylsulfanyl)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide, 7-fluoro-N-[1-(methanesulfinyl)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide, 7-fluoro-N-[1 -(methanesulfonyl)-2-methylpropan-2-yl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide, N-[1-(difluoromethyl)cyclopropyl]-2-(pyridin-3-yl)-2H-indazole-4-carboxamide, 2,9-dihydro-9-(methoxymethyl)-2-(pyridin-3-yl)-10H-pyrazolo[3,4-f]pyrido[2,3-b][1,4]oxazepin-10-one (2607927-97-7), Cry1Ab protein from Bacillus thuringiensis (Bacillus thuringiensis Cry1Ab protein),Cry1Ac protein from Bacillus thuringiensis (Bacillus thuringiensis Cry1Ac protein), Cry1Fa protein from Bacillus thuringiensis (Bacillus thuringiensis Cry1Fa protein), Cry1A.105 protein from Bacillus thuringiensis (Bacillus thuringiensis Cry1A.105 protein), Cry2Ab protein from Bacillus thuringiensis (Bacillus thuringiensis Cry2Ab protein), Vip3A protein from Bacillus thuringiensis (Bacillus thuringiensis Vip3A protein), mCry3A protein from Bacillus thuringiensis (Bacillus thuringiensis mCry3A protein), Cry3Ab protein from Bacillus thuringiensis (Bacillus thuringiensis Cry3Ab protein), Bacillus Cry3Bb protein derived from Bacillus thuringiensis, Cry34Ab1 / Cry35Ab1 protein derived from Bacillus thuringiensis, insecticidal protein Tma12 derived from the fern Tectaria macrodonata, insecticidal protein IPD083 derived from the fern Adiantum spp.,Insecticidal protein IPD113 derived from the fern Pteris cretica cv. albolineata or Pteris umbrosa. Fungicides include, for example, acibenzolar-S-methyl, aldimorph, ametoctradin, aminopyrifen, amisulbrom, ammonium salts of phosphorous acid, anilazine, azaconazole, azoxystrobin, and basic copper sulfate. sulfate), benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, benzovindiflupyr, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, Bordeaux mixture, boscalid, bromothalonil, bromuconazole, bupirimate, calcium salts of phosphorous acid acid), captafol, captan, carbendazim, carboxin, carpropamid, chinomethionate, chitin,Chlorinconazide (chloroinconazide), chloroneb (chloroneb), chlorothalonil (chlorothalonil), chlozolinate (chlozolinate), colletochlorin B (colletochlorin B), copper acetate (II) (copper (II) acetate), copper hydroxide (copper (II) hydroxide), basic copper chloride (copper oxychloride), copper sulfate (II) (copper (II) sulfate), coumoxystrobin (coumoxystrobin), cyazofamid (cyazofamid), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), cyproconazole (cyproconazole), cyprodinil (cyprodinil), diclobentiazox (dichlobentiazox), dichlofluanid (dichlofluanid), diclocymet (diclocymet), diclomezine (diclomezine), dicloran (dicloran), Diethofencarb, difenoconazole, diflumetorim, dimethachlone, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, dipotassium hydrogen phosphite hydrogenphosphite), dipymetitrone, dithianon, dodecylbenzenesulphonic acid bisethylenediamine copper(II) salt, dodemorph, dodine, edifenphos, enoxastrobin, epoxiconazole, etaconazole,Ethaboxam, ethirimol, etridiazole, tea tree extract (extract of Melaleuca alternifolia), giant knotweed extract (extract of Reynoutria sachalinensis), extract of the cotyledons of lupine plantlets ("BLAD"), garlic extract (extract of Allium sativum), horsetail extract (extract of Equisetum arvense), nasturtium extract (extract of Tropaeolum majus), famoxadone, fenamidone, phenaminestrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide hydroxide), ferbam, ferimzone, florylpicoxamid, fluazinam, flubeneteram, fludioxonil, flufenoxadiazam, flufenoxystrobin, fluindapyr, flumethylsulforim, flumorph, fluopicolide, fluopimomide,Fluopyram, fluoroimide, fluoxapiprolin, fluoxastrobin, fluoxytioconazole, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl, fosetyl Aluminum (fosetyl-aluminium), fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine acetate, iminoctadine albesilate trialbesilate), inpyrfluxam, iodocarb, ipconazole, ipfentrifluconazole, ipflufenoquin, iprobenfos, iprodione, iprovalicarb, isofetamide, isofetamide, isoflucypram, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, laminarin, leaves and bark of quercus,Mancozeb, mandestrobin, mandipropamid, maneb, mefentrifluconazole, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metarylpicoxamid, metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, methyltetraprole, mineral oils, myclobutanil, naftifine, neem extract indica), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate, oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron, penflufen, penthiopyrad, phenamacril, phosphorous acid , phthalide, picarbutrazox, picoxystrobin, piperalin,Polyoxins, potassium hydrogencarbonate, potassium dihydrogenphosphite, probenazole, prochloraz, procymidone, propamidine, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin robin, pyraoxystrobin, pyrapropoyne, pyraziflumid, pyrazophos, pyribencarb, pyributicarb, pyridaclomethyl, pyrifenox, pyrimethanil, pyrimorph, pyriophenone, pyrisoxazole, pyroquilon, Quillajaceae plant extract extract), quinconazole, quinofumelin, quinoxyfen, quintozene, saccharin, saccharin sodium, saccharin potassium, saccharin calcium, saccharin ammonium, saccharin salt, saponins of Chenopodium quinoa, seboctylamine,Sedaxane, silthiofam, simeconazole, sodium hydrogencarbonate, sodium salts of phosphorous acid, spiroxamine, streptomycin, sulfur, tebuconazole, Tebufloquin, teclofthalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, thymol, tiadinil, tolclofos-methyl, tolfenpyrad, tolprocarb, tolfluani Tolylfluanid, triadimefon, triadimenol, triazoxide, triclopyricarb, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, vinclozolin, mustard powder, zineb, zinc thiazole, ziram, zoxamide,3-(Difluoromethyl)-N-methoxy-1-methyl-N-[(1R)-1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide (1639015-48-7), 3-(Difluoromethyl)-N-methoxy-1-methyl-N-[(1S)-1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide (1639015-49-8), 3-(Difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide amide (141573-94-6), 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethylindan-4-yl]-1-methylpyrazole-4-carboxamide (1513466-73-3), N'-[4-({3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl}oxy)-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide (1202781-91-6), N'-{4-[(4,5-dichlorothiazol-2-yl)oxy]-2,5-dimethylphenyl Nyl}-N-ethyl-N-methylmethanimidamide (929908-57-6), N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylmethanimidamide (1052688-31-9), N'-[5-chloro-4-(2-fluorophenoxy)-2-methylphenyl]-N-ethyl-N-methylmethanimidamide (2055589-28-9), N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylmethanimidamide (2055756-21-1) , N'-(2-chloro-4-phenoxy-5-methylphenyl)-N-ethyl-N-methylmethanimidamide (2062599-39-5), N'-[4-(1-hydroxy-1-phenyl-2,2,2-trifluoroethyl)-2-methyl-5-methoxyphenyl]-N-isopropyl-N-methylmethanimidamide (2101814-55-3), N'-[5-bromo-6-(1-methyl-2-propoxyethoxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylmethanimidamide (1817828-69-5),4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine (1362477-26-6), 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline (1257056-97-5), (2Z)-3-amino-2-cyano-3-phenylacrylate ethyl (39491-78-6), N-[(2-chlorothiazol-5-yl)methyl]-N-ethyl-6-methoxy-3-nitropyridin-2-amine (1446247-98-8), α-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4 -isoxazolyl]-3-pyridinemethanol (1229605-96-2), (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol (1229606-46-5), (αR)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol (1229606-02-3), 5-(4-chlorobenzyl) -2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1394057-11-4), (1R,2S,5S)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801930-06-2), (1S,2R,5R)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazo (1R,2R,5R)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801930-07-3), (1R,2R,5R)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801919-53-8), (1S,2S,5S)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801919-54-9),(1R,2R,5S)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801919-55-0), (1S,2S,5R)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801919-56-1), (1R,2S,5R)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl) Cyclopentanol (1801919-57-2), (1S,2R,5S)-5-(4-chlorobenzyl)-2-chloromethyl-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801919-58-3), 2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1394057-13-6), (1R,2S,5S)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4- (1S,2R,5R)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801930-08-4), (1S,2R,5R)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1801930-09-5), (1R,2R,5R)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-08-4), (1S,2S,5S)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-08-4), (1R,2R,5S)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-10-8), (1R,2R,5S)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-13-1), (1S,2S,5R)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-16-4),(1R,2S,5R)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-20-0), (1S,2R,5S)-2-chloromethyl-5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol (1638898-24-4), methyl = 3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H- 1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (1791398-02-1), methyl (1R,2S,3S)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2080743-90-2), methyl (1S,2R,3R)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-yl Methyl (1R,2R,3R)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2080743-91-3), Methyl (1R,2R,3R)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2080743-92-4), Methyl (1S,2S,3S)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate methyl (1R,2R,3S)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2080743-94-6), methyl (1S,2S,3R)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2080743-95-7),Methyl (1R,2S,3R)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2081061-22-3), Methyl (1S,2R,3S)-3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate (2081061-23-4), 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)-1-[1-(4-bromo-2,6-difluorophenoxy)cyclopropyl]ethanol (2019215-86-0), 1-(2,4-difluorophenyl)-2- (1H-1,2,4-triazol-1-yl)-1-[1-(4-chloro-2,6-difluorophenoxy)cyclopropyl]ethanol (2019215-84-8), 1-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]-1H-imidazole-5-carbonitrile (2018316-13-5), 1-[2-(1-chlorocyclopropyl)-3-(2,3-difluorophenyl)-2-hydroxypropyl]-1H-imidazole-5- Carbonitrile (2018317-25-2), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol (2082661-43-4), 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol (2082660-27-1), methyl = ({2-methyl-5-[1-(4 -methoxy-2-methylphenyl)-1H-pyrazol-3-yl]phenyl}methyl)carbamate (1605879-98-8), 2-(difluoromethyl)-N-[1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1616239-21-4), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1616239-33-8),2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1847460-02-9), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1952305-97-3), 2-(difluoromethyl)-N-[3-propyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1847460-05-2), 2-(Difluoromethyl)-N-[(3R)-3-propyl-1,1-dimethyl-2,3-dihydro-1H-inden-4-yl]pyridine-3-carboxamide (1952306-00-1), (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide (1445331-27-0), (2E,3Z)-5-{[1-(2,4-dichlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpenta- 3-enamide (1445331-54-3), 5-chloro-4-({2-[6-(4-chlorophenoxy)pyridin-3-yl)ethyl]amino}-6-methylpyrimidine (1605340-92-8), N-[1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (2132414-04-9), N-[(1S)-1-benzyl -1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-[1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide (2132414-00-5), N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide ( 2132414-01-6), N-[(1R)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (2132414-06-1), 4,4-dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one (2098918-25-1),5,5-dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one (2098918-26-2), N-ethyl-2-methyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, N,2-dimethoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, N-methoxy-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)cyclopropanecarboxamide, N-methoxy-N'-methyl N-acetyl-2-(ethanesulfonyl)-N-[2-(methoxycarbonyl)-4-(trifluoromethoxy)phenyl]-4-(trifluoromethyl)benzamide (2043675-28-9), 3-(4-bromo-7-fluoroindol-1-yl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, 3-(7-bromoindol-1-yl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, 3-(7-bromo-4-fluoroindol-1-yl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, 3-(3,5-dichloropyridin-2-yl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, 3-(3,5-dichloropyridin-2-yl)butan-2-yl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate,(1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, (1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate, (1S)-1-[1-(naphthalen-1-yl)cyclopropyl]ethyl N-{[3-(acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate, N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)cyclopropanecarboxamide, N-allyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)acetamide, N-allyl-N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)acetamide N-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, 3,3,3-trifluoro-N-({2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, 3,3,3-trifluoro-N-({2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, 3,3,3-trifluoro-N-({3- fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, 3,3,3-trifluoro-N-({2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide, N-({2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)propanamide N-methyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea, N,N-diethyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea, N-methyl-N'-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)urea,1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)pyrrolidin-2-one, 1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)piperidin-2-one, 4-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)morpholin-3-one, 2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one, 3,3-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one, phenyl]phenyl}methyl)piperidin-2-one, 2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1,2-oxazinan-3-one, 1-({3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)azepan-2-one, 4,4-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)pyrrolidin-2-one, 5-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)pyrrolidin-2-one, ethyl 1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxylate, N-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide, N-propyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxylate N-methoxy-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide, N-methoxy-N-methyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-pyrazole-4-carboxamide,N,N-dimethyl-1-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)-1H-1,2,4-triazol-3-amine, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propanoate, ethyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propanoate, methyl 2-[2-(trifluoromethyl)-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propanoate, 1-(2,3-dimethylpyridin-5-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, 1-[2-(difluoromethyl)-3-methylpyridin-5-yl]-4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinoline, 2,2-difluoro-N-[6-({[1-(1-methyl-1H-tetrazol-5-yl)benzimidazol-2-yl]oxy}methyl)pyridin-2-yl]-2-phenoxyacetamide, 1-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]-1H-imidazole-5-carbonitrile, ethyl 1-[(4-{[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy}phenyl)methyl]-1H-pyrazole-4-carboxylate, ethyl 1-[(4-{[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy}phenyl)methyl]-1H-pyrazole-4-carboxylate, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide,6-chloro-N-[2-(2-chloromethylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide, 2-[cyano(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-[cyano(2,6-difluoropyridin-4-yl)amino]-N-(spiro[3.4]octan-1-yl)-5-methyl-4-carboxamide, 2-[cyano(2,6-difluoropyridin-4-yl)amino]-N-hexyl-5-methyl-4-carboxamide, 2-[acetyl(2,6-difluoropyridin-4-yl)amino]- 2-[(2-methoxyacetyl)(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-[(2-methylpropanoyl)(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-[(2-methylpropanoyl)(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-[(2,6-difluoropyridin-4-yl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide )amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-{[(oxetan-3-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-{[(oxolan-3-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 2-{[(oxan-3-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide -4-yl)carbonyl](2,6-difluoropyridin-4-yl)amino}-N-(2,2-dimethylcyclobutyl)-5-methyl-4-carboxamide, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)ethyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine,5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(6-chloropyridin-3-yl)ethyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine, methyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-N-[1-(2-fluoro-3-methoxyphenyl)cyclopropyl]pyrimidin-2-amine, 5-[5-(difluoromethyl)-1,3,4-oxadiazol-2-yl]-2-{[1-(2,6-difluorophenyl)cyclopropyl]oxy}pyrimidine, 3-[3-(3-cyclo (5S)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, (5S)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, 3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(4-bromo -2-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, 3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, (5S)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine,(5R)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-[(2-chloro-4-methylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}-3-methylbutan-2-yl)-2-methylpropanamide, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dihydropyrimidin-1(2H)-yl} oxo-3,6-dihydropyrimidin-1(2H)-yl}-3-methylbutan-2-yl)-2,2-dimethylpropanamide, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide, N-((2S)-1-{3-[2-(2-methoxyphenyl)-2-hydroxyethyl]-5-[(E)-1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide, N-((2S)-1-{3-[2-(5-fluoro-2-methoxyphenyl)-2-(2-cyanoethoxy)ethyl]-5-[1-(isopropoxyimino)ethyl]-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl}propan-2-yl)-2-methylpropanamide, methyl ({5-[1-(2,6-difluoro-4-isopropylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)carbamate, methyl ({5-[1-(2,6-difluoro-4-cyclopropylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)carbamate, methyl ({5-[1-(2,6-difluoro-4-methoxyphenyl)-1H-pyrazol-3-yl]-2-methylphenyl}methyl)carbamate,Methyl (Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyprop-2-enoate, Methyl (Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxyprop-2-enoate, Methyl (Z)-2-[(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy)-3-methoxyprop-2-enoate, 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinoline, 1-(pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-fluoro-3,3-dimethylisoquinolin-4(3H)-one, methyl (2Z)-3-methoxy-2-[(4-methyl[1,1'-biphenyl]-3-yl)oxy]prop-2-enoate.
[0026] Examples of active ingredients that may remain on an article and that can be effectively cleaned by the method of the present invention include epirifenal and butafenacil. When the article is a pesticide sprayer, examples of active ingredients that can be sprayed by the pesticide sprayer after cleaning by the method of the present invention include glyphosate potassium salt, dicamba diglycolamine salt, 2,4-D triethanolamine salt, and clethodim.
[0027] The pesticides sprayed by the pesticide sprayer before and after washing by the method of the present invention are usually pesticide formulations that are mixed with water to prepare a spray solution. Preferred formulations of such formulations include aqueous suspension concentrates, oil dispersions, wettable powders, water-dispersible granules, granules, oil-in-water emulsions, water-in-oil emulsions, soluble liquids, and emulsifiable concentrates. The preferred formulations of epirifenacil, butafenacil, and clethodim are emulsifiable concentrates, and the preferred formulations of glyphosate potassium salt, dicamba diglycolamine salt, and 2,4-D triethanolamine salt are water-soluble liquids.
[0028] In the method of the present invention, the composition of the present invention may be used in combination with an existing detergent. Examples of detergents that can be used in combination include surfactants, hydrogen peroxide, and sodium chlorate. Examples of surfactants include: carboxylic acids: fatty acid salts (octanoates, decanoates, laurates, myristates, palmitates, stearates, behenates, oleates, polyoxyethylene alkyl ether carboxylates (laureth-3-carboxylates, α-(carboxymethyl)-ω-(dodecyloxy)poly(oxyethylene) salts, etc.), N-acyl sarcosinates (N-lauroyl sarcosinates, etc.), N-acyl glutamates (N-lauroyl glutamates, etc.), polycarboxylic acids, and the like. Phosphonates (polyacrylates, polyvinyl acetates, comb polymers of polyacid salts, and their derivatives, etc.), sulfonic acids: alkylsulfonic acids and their salts (dodecylsulfonates, etc.), alpha-olefin sulfonates (alkene (C14-18) hydroxysulfonates, alkapolyene (C12-20) hydroxysulfonates, alkene (C14-18) hydroxysulfonates, alkene (C12-20) hydroxysulfonates, tetradecene-1-sulfonates, α-olefin (C14-16) sulfonates, etc.), alkylbenzenesulfonates (decylbenzenesulfonate, dodecylbenzenesulfonate, tridecylbenzenesulfonate, diphenylsulfonate, etc.), alkylnaphthalenesulfonates (naphthalenesulfonate, 6-methyl-2-naphthalenesulfonate, dibutylnaphthalenesulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonate, diisopropylnaphthalenesulfonate, tri isopropyl naphthalenesulfonate, 1-isopropyl 2-naphthalenesulfonate, etc.), sulfosuccinic acid, monoalkyl sulfosuccinates, dialkyl sulfosuccinates (di(2-ethylhexyl) sulfosuccinate, etc.), N-methyl-N-acyltaurates (oleoyl methyl taurate, etc.), ligninsulfonates, alkylphenolsulfonates, naphthalenesulfonate-formaldehyde condensates, benzimidazole sulfonates and their derivatives;Sulfate esters: alkyl sulfates (hexyl sulfate, heptyl sulfate, octyl sulfate, lauryl sulfate, diethanol lauryl sulfate, hexadecyl sulfate, octadecyl sulfate, etc.), polyoxyethylene alkyl ether sulfate and its salts (laureth-3-sulfate, polyoxyethylene monotridecyl ether sulfate, α-sulfo-ω-hydroxyalkyl(C6-10)ether poly(oxyethylene) salts, etc.), polyoxyethylene alkyl phenyl ether sulfates (poly(oxyethylene) 2-decylphenyl ether sulfate, poly(oxyethylene) 3-decylphenyl ether sulfate, α-sulfo-ω-[2,4-bis(1,1,3,3-tetramethylbutyl)phenoxy]poly(oxyethylene) salts, etc.), polyoxypropylene alkyl ether sulfates, lignosulfite waste liquor, and derivatives thereof; Phosphate esters: alkyl phosphates (propyl phosphate, hexadecyl phosphate, lauryl phosphate, dioctyl phosphate, etc.), polyoxyethylene alkyl ether phosphates (polyoxyethylene decyl phosphate, α-phosphono-ω-butoxypoly(oxyethylene), etc.), polyoxyethylene alkylphenyl ether phosphates (α-(dinonylphenyl)-ω-hydroxypoly(oxyethylene) phosphate, α-(dodecylphenyl)-ω-hydroxypoly(oxyethylene) phosphate, α-(nonylphenyl)-ω-hydroxypoly(oxyethylene) phosphate, etc.), polyoxypropylene alkyl ether phosphates, and derivatives thereof; Alcohols: aromatic alcohols (alkylphenols (allylphenol, octylphenol, nonylphenol, octylcresol, etc.), acylphenols, etc.), aliphatic alcohols (isotridecyl alcohol, oleyl alcohol, cetyl alcohol, etc.), polyhydric alcohols (polysaccharides, starch, starch derivatives, sucrose, alkyl polyglucosides, sorbitan, ethoxylated sorbitan, cellulose derivatives, gum arabic, etc.), synthetic polymers (polyvinyl alcohol, polyethylene glycol, etc.);Amides: alkanolamides (fatty acid alkanolamides (lauric acid diethanolamide, etc.), fatty acid glucamides (alkoxylated propylene oxide fatty acid glucamides, etc.), alkoxylated amides (polyoxyethylene oleic acid amide, polyoxyethylene stearic acid amide, etc.), synthetic polymers (polyvinylpyrrolidone, etc.); amines: alkoxylated amines (polyoxyethylene oleylamine, α,α'-[(9-octadecenylimino)di2,1-ethanediyl]bis(ω-hydroxy)polyoxyethylene, etc.); esters: fatty acid esters (fatty acid esters of polyols, monoglycerides, phospholipids, etc.), sugar-derived esters (sucrose fatty acid esters (sucrose stearate diester, etc.), sorbitan fatty acid esters (sorbitan oleic acid monoester, etc.), glucose esters, cellulose esters, etc.), synthetic polymers (vinyl acetate copolymers, polymethacrylic acid, copolymers of methacrylic acid and methacrylic acid esters, etc.); Ethers: alcohol ethoxylates (fatty alcohol ethoxylates (tridecyl alcohol ethoxylate, isooctyl alcohol ethoxylate, lauryl alcohol ethoxylate, hexadecyl alcohol ethoxylate, stearyl alcohol ethoxylate), etc.), alkylphenol ethoxylates (nonylphenol ethoxylate, tristyrylphenol ethoxylate, tributylphenol ethoxylate, octylphenol ethoxylate), arylalkylphenol ethoxylates, arylphenol ethoxylates (monobenzyl biphenol alcohol ethoxylate), alcohol propoxylates (fatty alcohol propoxylates, alkylphenol propoxylates, arylalkylphenol propoxylates), block polymers (block polymers of polyethylene oxide and polypropylene oxide, polyethylene oxide block polymers, polypropylene oxide block polymers, block polymers of alkanol, polyethylene oxide and polypropylene oxide, etc.);Ether esters: polyoxyethylene fatty acid esters (polyoxyethylene castor oil ester, polyoxyethylene stearate, polyoxyethylene beef tallow fatty acid ester, etc.), polyoxyethylene sorbitan fatty acid esters (polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan stearate, etc.), polyoxyethylene fatty acid amine esters, polyoxyethylene rosin esters, polyoxypropylene fatty acid esters (polyoxypropylene castor oil ester, etc.), polyoxypropylene fatty acid amine esters; Carboxylic acids: undecafluorohexanoic acid, etc.;
[0029] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "parts" described below mean % by weight and parts by weight, respectively.
[0030] The methods for preparing the cleaning liquid compositions used in the test examples are as follows. <Comparative Cleaning Liquid Composition 1> Valent Tank Cleaner (aqueous solution of 15-30% sodium hydroxide and 1-5% surfactant blend, manufactured by Valent U.S.A.) was diluted 100 times with water to obtain comparative cleaning liquid composition 1 (hereinafter referred to as comparative cleaning liquid composition 1). The pH of comparative cleaning liquid composition 1 was 12.7. Comparative Cleaning Liquid Composition 2 A mixture (hereinafter referred to as "Mixture X") was obtained from 7.9 parts of Phenylsulfonate CAL (70% n-C12 alkylbenzenesulfonic acid calcium salt (in isobutanol), manufactured by Clariant), 7.9 parts of Emulsogen TS 290 (2,4,6-tri-(1-phenylethyl)-phenol polyglycol ether containing 29 moles of ethylene oxide, manufactured by Clariant), and 84.2 parts of Aromatic 200 ND Fluid (also known as Solvesso 200 ND, Solvent Naphtha (Petroleum), Heavy Aromatic, manufactured by ExxonMobil). Mixture X was mixed with water to obtain a comparative cleaning liquid composition 2 (hereinafter referred to as "Comparative Cleaning Liquid Composition 2"). The concentration of Mixture X in Comparative Cleaning Liquid Composition 2 was 5% (v / v). The pH of Comparative Cleaning Liquid Composition 2 was 8.1. <Comparative Cleaning Liquid Composition 3> Comparative cleaning liquid composition 3 (hereinafter referred to as Comparative Cleaning Liquid Composition 3) was obtained by mixing cyclohexanone with water. The concentration of cyclohexanone in Comparative Cleaning Liquid Composition 3 was 5% (v / v). The pH of Comparative Cleaning Liquid Composition 3 was 8.0. <Comparative Cleaning Liquid Composition 4> A 150 mM aqueous solution of tetrabutylammonium hydroxide was prepared to obtain Comparative Cleaning Liquid Composition 4 (hereinafter referred to as Comparative Cleaning Liquid Composition 4). The pH of Comparative Cleaning Liquid Composition 4 was 13.3. <Cleansing Liquid Composition 1 of the Present Invention> Valent Tank Cleaner, Mixture X, and water were mixed in a volume ratio of 1:5:94 to obtain a cleaning liquid composition of the present invention (hereinafter referred to as Cleaning Liquid Composition 1 of the present invention). The pH of the present cleaning liquid composition 1 was 12.7.<Cleaning Liquid Composition 2 of the Present Invention> A cleaning liquid composition of the present invention (hereinafter referred to as "Cleaning Liquid Composition 2 of the Present Invention") was obtained by mixing 157.9 mM aqueous tetrabutylammonium hydroxide solution and cyclohexanone in a volume ratio of 95:5. The concentration of tetrabutylammonium hydroxide in Cleaning Liquid Composition 2 of the Present Invention was 150 mM, and the pH of Cleaning Liquid Composition 2 of the Present Invention was 13.3. <Cleaning Liquid Composition 3 of the Present Invention> A cleaning liquid composition of the present invention (hereinafter referred to as "Cleaning Liquid Composition 3 of the Present Invention") was obtained by mixing Valent Tank Cleaner, cyclohexanone, and water in a volume ratio of 1:5:94. The pH of Cleaning Liquid Composition 3 of the Present Invention is shown in Table 4. <Cleaning Liquid Composition 4 of the Present Invention> A cleaning liquid composition of the present invention (hereinafter referred to as "Cleaning Liquid Composition 4 of the Present Invention") was obtained by mixing 157.9 mM aqueous tetrabutylammonium hydroxide solution and Mixture X in a volume ratio of 95:5. The pH of Cleaning Liquid Composition 4 of the Present Invention is shown in Table 8. <Cleaning Liquid Composition 5 of the Present Invention> Valent Tank Cleaner, tetrahydrofuran, and water were mixed in a volume ratio of 1:5:94 to obtain a cleaning liquid composition of the present invention (hereinafter referred to as Cleaning Liquid Composition 5 of the Present Invention). The pH of Cleaning Liquid Composition 5 of the Present Invention is shown in Table 8. <Cleaning Liquid Composition 6 of the Present Invention> A 157.9 mM aqueous solution of tetrabutylammonium hydroxide, tetrahydrofuran, and water were mixed in a volume ratio of 95:5 to obtain a cleaning liquid composition of the present invention (hereinafter referred to as Cleaning Liquid Composition 6 of the Present Invention). The pH of Cleaning Liquid Composition 6 of the Present Invention is shown in Table 8. <Cleaning Liquid Compositions 7 to 9 of the Present Invention> A 50, 100, or 200 mM aqueous solution of sodium hydroxide and Mixture X were mixed in a volume ratio of 95:5 to obtain cleaning liquid compositions of the present invention (hereinafter referred to as Cleaning Liquid Compositions 7 to 9 of the Present Invention, respectively). The pH of Cleaning Liquid Compositions 7 to 9 of the Present Invention is shown in Table 9. <Detergent Liquid Composition 10 of the Present Invention> A 50 mM aqueous solution of tetrabutylammonium hydroxide and cyclohexanone were mixed in a volume ratio of 95:5 to obtain a detergent liquid composition of the present invention (hereinafter referred to as detergent liquid composition 10 of the present invention). The pH of detergent liquid composition 10 of the present invention is as shown in Table 9.
[0031] The method for preparing a 55 g / L emulsifiable concentrate of epirifenacil used in the test examples is as follows: 5.39 parts of epirifenacil, 7.5 parts of Phenylsulfonat CAL (70% n-C12 alkylbenzenesulfonic acid calcium salt in isobutanol, manufactured by Clariant), 7.5 parts of Emulsogen TS 290 (2,4,6-tri-(1-phenylethyl)-phenol polyglycol ether containing 29 mol of ethylene oxide, manufactured by Clariant), and 79.61 parts of Aromatic 200 ND Fluid (Solvent Naphtha (Petroleum), Heavy Aromatic, manufactured by ExxonMobil) were thoroughly mixed to obtain a 55 g / L emulsifiable concentrate.
[0032] The method for preparing a 50 g / L butafenacil emulsion used in the test examples is as follows: 4.9 parts of butafenacil, 7.5 parts of Phenylsulfonat CAL (70% n-C12 alkylbenzenesulfonic acid calcium salt (in isobutanol), manufactured by Clariant), 7.5 parts of Emulsogen TS 290 (2,4,6-tri-(1-phenylethyl)-phenol polyglycol ether containing 29 moles of ethylene oxide, manufactured by Clariant), and 80.1 parts of Aromatic 200 ND Fluid (Solvent Naphtha (Petroleum), Heavy Aromatic, manufactured by ExxonMobil) were thoroughly mixed to obtain a 50 g / L butafenacil emulsion.
[0033] Test Example 1: An EPDM hose (Good Year HORIZON 200 PSI WP Lot. 10.20.50B) with an inner diameter of ¾ inch was cut to a length of 15 cm and filled with a liquid (epirifenacil concentration: 143 ppm, 20 g / ha, estimated for a spray water volume of approximately 140 L / ha) prepared by mixing a 55 g / L emulsion of epirifenacil with a 1% aqueous dilution of Agri-Dex (paraffin-based petroleum + polyol fatty acid ester + polyethoxylated polyol fatty acid ester emulsifier, Helena Agri-Enterprises, LLC). The liquid was left standing at 30°C for 24 hours to obtain several contaminated hoses. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and left standing at 30°C for 24 hours. The liquid cleaning composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A 0.25% solution of Induce (an alkylaryl polyoxyalkane ether + alkanolamide + dimethylsiloxane + fatty acid, manufactured by Helena Agri-Enterprises, LLC) diluted with water, simulating the spray solution to be used in the subsequent process, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed onto American cotton plants at the cotyledon stage grown in pots at a spray rate of 15 gallons per acre (approximately 140 L / ha). Seven days after spraying, the herbicidal efficacy was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 1. The cleaning efficacy is expressed in Table 1 as the low level of phytotoxicity. By washing with the liquid cleaning composition of the present invention, phytotoxicity to cotton plants was significantly reduced.
[0034]
[0035] Test Example 2: Multiple contaminated hoses were obtained in the same manner as in Test Example 1. After rinsing the inside of the hose with tap water for 20 seconds, a predetermined cleaning liquid composition was filled into the hose as a cleaning step and allowed to stand at 30°C for 48 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. Then, a 0.83% volume of SelectMax (clethodim 116 g / L, manufactured by Valent) and a 1% volume of a water-diluted solution of Agri-Dex, simulating the spray solution to be used in the subsequent step, were filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on American cotton plants at the cotyledon stage grown in pots at a spray water rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 2. The cleaning effect is expressed as the reduction of phytotoxicity in Table 2. By cleaning with the liquid cleaning composition of the present invention, phytotoxicity to cotton was significantly reduced.
[0036]
[0037] Test Example 3: Multiple contaminated hoses were obtained in the same manner as in Test Examples 1 and 2. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and allowed to stand at 30°C for 24 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. After that, a water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent step, was filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on foliage at the cotyledon stage of American cotton grown in pots at a spray water rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 3. The cleaning effect is expressed in Table 3 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to cotton was significantly reduced.
[0038]
[0039] Test Example 4: An EPDM hose (Good Year HORIZON 200PSI WP Lot. 10.20.50B) with an inner diameter of ¾ inch was cut to a 15 cm length and filled with a liquid (butafenacil concentration: 143 ppm, 20 g / ha, estimated for a spray volume of approximately 140 L / ha) prepared by mixing a 50 g / L emulsion of butafenacil with a 1% aqueous dilution of Agri-Dex (paraffin-based petroleum + polyol fatty acid ester + polyethoxylated polyol fatty acid ester emulsifier, Helena Agri-Enterprises, LLC). The liquid was left at 30°C for 24 hours to obtain several contaminated hoses. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and left at 30°C for 14 hours. The liquid cleaning composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent process, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed onto American cotton plants at the cotyledon stage grown in pots at a spray water rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 4. The cleaning effect is expressed in Table 4 as low phytotoxicity. By washing with the liquid cleaning composition of the present invention, phytotoxicity to cotton plants was significantly reduced.
[0040]
[0041] Test Example 5: Several contaminated hoses were obtained in the same manner as in Test Example 4. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and allowed to stand at 30°C for 14 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent step, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on soybeans at the primary leaf stage grown in pots at a spray water volume of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 5. The cleaning effect is expressed in Table 5 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to soybeans was significantly reduced.
[0042]
[0043] Test Example 6 An EPDM hose (Good Year HORIZON 200 PSI WP Lot. 10.20.50B) with an inner diameter of ¾ inch was cut to a 15 cm length and filled with a liquid (4000 ppm as dicamba acid, 560 g / ha, simulating a spray water volume of approximately 140 L / ha) prepared by mixing XtendiMax (dicamba diglycolamine salt, 350 g / L, manufactured by Monsanto) with a water dilution containing 0.5% volume of Intact (polyethylene glycol, choline chloride, guar gum, surfactant-containing, manufactured by Precision Laboratories) and 0.25% volume of Induce (alkylaryl polyoxyalkane ether + alkanolamide + dimethylsiloxane + fatty acid, manufactured by Helena Agri-Enterprises, LLC). After standing at 30°C for 24 hours, several contaminated hoses were obtained. After rinsing the inside of the hose with tap water for 20 seconds, a predetermined cleaning liquid composition was filled into the hose as a cleaning step and allowed to stand at 30°C for 14 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent step, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on foliage at the cotyledon stage of American cotton grown in pots at a spray water rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 6. The cleaning effect is expressed in Table 6 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to cotton was significantly reduced.
[0044]
[0045] Test Example 7: Multiple contaminated hoses were obtained in the same manner as in Test Example 6. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and allowed to stand at 30°C for 14 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent step, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on soybeans at the primary leaf stage grown in pots at a spray water volume of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 7. The cleaning effect is expressed in Table 7 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to soybeans was significantly reduced.
[0046]
[0047] Test Example 8: Multiple contaminated hoses were obtained in the same manner as in Test Examples 1 to 3. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and allowed to stand at 30°C for 24 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. After that, a water-diluted solution of 0.83% SelectMax and 1% Agri-Dex, simulating the spray solution for the subsequent step, was filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on American cotton plants at the cotyledon stage grown in pots at a spray rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 8. The cleaning effect is expressed in Table 8 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to cotton was significantly reduced.
[0048]
[0049] Test Example 9: Multiple contaminated hoses were obtained in the same manner as in Test Examples 1 to 3. After rinsing the inside of the hose with tap water for 20 seconds, the hose was filled with a predetermined cleaning liquid composition as a cleaning step and allowed to stand at 30°C for 24 hours. The cleaning liquid composition was removed from the hose, and the inside of the hose was again rinsed with tap water for 20 seconds. A water-diluted solution of 0.83% by volume of SelectMax and 1% by volume of Agri-Dex, simulating the spray solution for the subsequent step, was then filled into the hose and allowed to stand at 30°C for 1 hour. The contents were sprayed on foliage at the cotyledon stage of American cotton grown in pots at a spray water rate of 15 gallons / acre (approximately 140 L / ha). Seven days after spraying, the herbicidal effect was visually evaluated [0 (no effect) - 100 (complete death)]. The results are shown in Table 9. The cleaning effect is expressed in Table 9 as the low level of phytotoxicity. By washing with the liquid washing composition of the present invention, phytotoxicity to cotton was significantly reduced.
[0050]
[0051] The present invention makes it possible to effectively clean articles on which pesticide residues remain.
Claims
1. A method for cleaning an article with residual active ingredient of pesticide, the method comprising contacting the article with a cleaning liquid composition having a pH of 10 or more and containing an organic solvent.
2. The method according to claim 1, wherein the article is a pesticide sprayer.
3. The method according to claim 1, wherein the organic solvent is solvent naphtha.
4. The method according to claim 1, wherein the organic solvent is cyclohexanone.
5. The method according to claim 1, wherein the organic solvent is tetrahydrofuran.
6. The method according to claim 1, wherein the cleaning liquid composition contains an inorganic alkali.
7. The method according to claim 1, wherein the cleaning liquid composition contains an alkali metal hydroxide.
8. The method according to claim 1, wherein the cleaning liquid composition contains an organic alkali.
9. The method according to claim 1, wherein the cleaning liquid composition contains tetrabutylammonium hydroxide.
10. A cleaning liquid composition containing an organic solvent and tetrabutylammonium hydroxide.
11. Use of a cleaning liquid composition having a pH of 10 or more and containing an organic solvent for cleaning an article with residual active ingredient of pesticide.
Citation Information
Patent Citations
Washing water for agricultural product and washing thereof
JP1998066553A
Germicidal detergent composition
JP2004315691A
Sterilizer composition for food processing facility or kitchen utensil
JP2016160350A
Method for cleaning rubber surface
JP2017144408A
Agrochemical purification liquid and method of purifying agrochemical using this agrochemical purification liquid
JP2020164653A