CN101146449A - Agrochemical composition - Google Patents
Agrochemical composition Download PDFInfo
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- CN101146449A CN101146449A CNA2006800097091A CN200680009709A CN101146449A CN 101146449 A CN101146449 A CN 101146449A CN A2006800097091 A CNA2006800097091 A CN A2006800097091A CN 200680009709 A CN200680009709 A CN 200680009709A CN 101146449 A CN101146449 A CN 101146449A
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Abstract
A particulate agricultural-chemical composition obtained by aggregating and coating a powdery agricultural chemical with a thermoset resin. The composition enables the agricultural-chemical active compound to be sustainedly released. The agricultural-chemical composition, which contains an agricultural-chemical active compound in a sustained-release form, can be produced by mixing a powdery agricultural chemical with a first liquid ingredient serving as a raw material for a thermoset resin, subsequently adding to the mixture a second liquid ingredient serving as a raw material for the thermoset resin, and reacting the first liquid ingredient with the second liquid ingredient to yield the thermoset resin.
Description
Technical field
The present invention relates to a kind of composition pesticide, described composition pesticide contains the active component that is in the controllable release form.
Background technology
Conventionally proposed various formulation of pesticides, described formulation of pesticide can make pesticide activity component obtain lasting release to keep effect, reduces phytotoxicity etc.As the formulation of pesticide of this controllable release, the known pesticide granule that the microcapsules prescription is arranged, be coated with thermosetting resin (JP 11-5704A), by pesticide activity component is mixed the prescription (JP 52-28942A) etc. of acquisition with polyurethane resin.
Summary of the invention
The invention provides a kind of composition pesticide, described composition pesticide contains the pesticide activity component that is in the controllable release form.
And, the invention provides a kind of method that is used to produce composition pesticide, described composition pesticide contains the pesticide activity component that is in the controllable release form.
The present invention relates to a kind of pesticide granule of coating, described pesticide granule obtains by Powdered agricultural chemicals is assembled.This pesticide granule of production for example as described below.That is, production method comprises the step that Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin; To add step wherein subsequently as second liquid component of the raw material that is used for thermosetting resin; By making the reaction of first liquid component and second liquid component to generate the step that thermosetting resin obtains pesticide granule; And also simultaneously or join successively in the pesticide granule that obtains, and make their reactions to coat the step of pesticide granule with thermosetting resin with first liquid component and second liquid component.
In the present invention, Powdered agricultural chemicals can be the independent pesticide activity component that is in powder type, and the powdered composition that normally contains pesticide activity component and thinner, average grain diameter (volume median diameter) is generally equal to or less than 100 μ m, particularly 1 to 100 μ m is preferably 1 to 30 μ m.
Can be by the measurement average grain diameters such as MASTERSIZER2000 of laser diffraction granularmetric analysis device as producing by MALVERN.
As having that pesticide activity component is mentioned usually: solid Pesticidal compound, insect growth are regulated compound, Fungicidal compounds, herbicides compounds, plant growth regulating compound, pest repellant etc., and its instantiation comprises the compound that shows below.These compounds are solids under normal temperature (20 ℃), yet, the higher compound of fusing point preferably, its for example 50 ℃ be solid.
Pesticidal compound and insect growth are regulated compound and are comprised pyrethroid compound, as decis, tralomethrin, acrinathrin and tetramethrin; Carbamate compounds is as unden, Mobucin, Meobal, meta-tolyl-N-methylcarbamate (MTMC), XMC, carbaryl, phonetic mite prestige (pyrimicarb), carbofuran, Methomyl and ABG-6215 (phenoxycarb); Organic phosphorus compound is as orthene, trichlorfon 98, tetrachlorvinphos, N-nitrosodimethylamine, pyridaphethione, azinphos ethyl and azinphos-methyl; Carbamide compound, as diflubenzuron, chlorine tick pyridine urea (chlorofluazuron), the Acarus tritici urea, fluorine bell urea, flufenoxuron, flucycloxuron, fly eradication amine, the butyl ether urea, Hexythiazox, the fluorine uride, the fluorobenzene urea, kill the bell urea, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-(6-iodo-3-pyridine radicals methoxyl group) pyridazine-3 (2H)-ketone, 1-(2, the 6-difluoro benzoyl)-and 3-[2-fluoro-4-(trifluoromethyl) phenyl) urea, 1-(2, the 6-difluoro benzoyl)-3-[2-fluoro-4-(1,1,2,3,3,3-hexafluoro propoxyl group) phenyl] urea, 2-tertbutylimido-3-isopropyl-5-phenyl-3,4,5,6-tetrahydrochysene-2H-1,3,5-thiadiazine (thiadiazon)-4-ketone and 1-(2, the 6-difluoro benzoyl)-3-[2-fluoro-4-(1,1,2,2-tetrafluoro ethyoxyl) phenyl] urea; Intend new nicotinate (neonicotinoid) compound, as Imidacloprid, Acetamiprid, thiophene worm amine, Nitenpyram and diacloden; The two prestige of cartap, Buprofezin, thiocyclam, bensultap, ABG-6215, fenazaquin (fenezaquin), azoles mite ester, pyridaben, Hydramethylnon Bait, sulphur, capillary, azoles mite ester, pyrrole aphid ketone, pyrimidifen, worm hydrazides, tebufenpyrad, triaguron, indenes worm prestige, sulfluramid, more visit rhzomorph, ivermectin (ivermectin), boric acid, paracide etc.
Fungicidal compounds comprises benzimidazole compound, as benomyl, carbendazim, probenazole and thiophanate-methyl and their precursor; The phenyl carbamate compound is as the mould prestige of second; Dicarboxyl imines (dicarboxyimide) compound is as procymidone, iprodione and vinclozolin; Azole compounds is as alkene azoles alcohol, probenazole, epoxy azoles alcohol (epoxyconazole), Tebuconazole, Difenoconazole, Cyproconazole, Flusilazole and triazolone; The acyl group alanine compound is as metalaxyl; Benzamide compound is as fluorine pyrrole bacterium amine (furametpyr), mebenil, flutolanil and trifluzamide; Organic phosphorus compound is as methyl trichloroethyl phosphate (triclofos-methyl), phosethyl-Al and Ppyrazophos; The anilino-pyrimidine compound is as phonetic mould amine, mepanipyrim and cyprodinil; The cyanopyrrole compound is as fludioxonil and fenpiclonil; Antibiotic is as blasticidin S (blastocidin S), kasugarnycin, polyoxin and valida; Methoxy acrylate and methoxy propyl enamides are as Fluoxastrobin, kresoxim-methyl and SSF 126; White bacterium is clear, mancozeb, captan, folpet, tricyclazole, pyroquilon, probenazole, Rabcide (fthalide), frost urea cyanogen, dimethomorph, Acibenzolar-S-methyl oxazole bacterium ketone oxolinic acid, fluazinam, ferimzone, two chlorine zarilamids, 4-chloro-3-methyl-2 (3H)-benzothiazolone (chlobenthiazone), isoamyl diketone (isovaledione), the tetrachloro isophthalonitrile, sulfo-phthalimide oxygen base biphenyl oxygen arsine (thiophthalimideoxybisphenoxyarsine), carbamic acid 3-iodo-2-propyl group butyl ester, p-hydroxybenzoate, dehydro sodium acetate, potassium sorbate etc.
Herbicides compounds comprises triaizine compounds, as atrazine and piperazine humulone; Carbamide compound, as lie prostrate careless dragon and isoproturon; The hydroxy benzonitrile compound is as Brominal and ioxynil; 2,6-dinitro benzene amines is as pendimethalin and trefanocide; The aryloxy group chain acid compound, as 2,4-drips, dicamba, fluroxypyr and 2-methyl-4-chloropropionic acid; Solsonylurea compounds is as bensulfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuronmethyl and AC322140; Imidazolidinone compound is as imidazoles nicotinic acid, imazaquin and imazethapyr; Two careless ethers, bisthiobac-sodium, acifluorfen, sulfentrazone, white grass are withered, Flumetsulam (flumeturam), triflusulfuronmethyl, fenoxaprop, diflufenican, norflurazon, isoxazole humulone, careless fourth phosphorus ammonium (ammonium glufosinate), glyphosate, bentazone, mefenacet, Stam F-34, flufenacet, Flumiclorac pentyl, flumioxazin etc.
Plant growth regulating compound comprises maleic acid hydrazide, chlormequat (chlormequat), ethephon, gibberellin, first piperazine, Thidiazuron, inabenfide, inferior thiometan, uniconazole P etc.Pest repellant comprises 1S, 3R, 4R, 6R-carane-3,4-glycol, 2,5-pyridinedicarboxylic acid dipropyl etc.
In the present invention, even under the situation of liquid pesticidal active component, also can promptly be in the composition that is fixed on the form of powder on the thinner with it as Powdered agricultural chemicals.
Thinner is the solid carrier that is used for Powdered agricultural chemicals, and comprises mineral carrier, and kaolin mineral for example is as kaolinite, dickite, nacrite and halloysite (halocite); Serpentine is as chrysolite, lizardite (lizartite), antigorite and pictoamesite; The imvite mineral are as the imvite of sodium type, the imvite of calcium type and the imvite of magnesium type; Montmorillonite is as saponite, hectorite (hectrite), sauconite and hyderite; Mica group is as pyrophyllite, talcum, agalmatolite, muscovite, phengite, sericite and illite; Silica is as cristobalite, amorphous silica and quartz; Magnesium silicate hydrate is as attapulgite and sepiolite; Sulfate mineral is as gypsum; Dolomite, calcium carbonate, zeolite, boiling stone, travertine, vermiculite, LAPONITE (laponite), float stone, diatomite, acid clay, carclazyte etc.These can be used in combination separately or with two or more.
Except that pesticide activity component, Powdered agricultural chemicals can also contain the auxiliary agent that is useful on agricultural chemicals, as thinner, surfactant, stabilizing agent, colouring agent, spices etc.
Surfactant comprises non-ionic surface active agent, as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensation product, the polyoxyethylene sorbitan aliphatic ester, polyoxyethylene glyceryl mono fatty acid ester, the polyoxypropylene glycol mono fatty acid ester, Polyoxyethylene Sorbitol Fatty Acid Esters, castor oil derivatives, polyoxyethylene fatty acid ester, higher fatty acid glyceride, sorbitan aliphatic ester, sucrose fatty ester, the polyoxyethylene polyoxypropylene block polymer, the polyoxyethylene fatty acid amide, alkylolamides and polyoxyethylene alkyl amine; Cationic surfactant, as alkylamine hydrochloride (for example, the dodecyl amine hydrochlorate), alkyl quaternary ammonium salts (for example, dodecyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl adjoin pyridine salt, alkyl isoquinolinium salt, dialkyl group alkylbenzyldimethylasaltsum saltsum), benzethonium chloride and poly-alkylvinylpyridines salt; Anion surfactant, as fatty acid sodium salt (for example, sodium palmitate), the sodium salt of ether carboxylic acid (for example, the polyoxyethylene lauryl ether carboxylic acid sodium), the amino condensation compound of higher fatty acid (for example, sodium N-lauroyl sarcosinate, the N-sodium lauroyl glutamate), the higher fatty acid sulfonated ester (for example, senior alkyl sulfonate, lauryl sulfonate), dialkyl sulfosuccinates (for example, the dioctyl sulfosuccinate), high fatty acid amide sulfonate (for example, oleamide sulfonate), alkylaryl sulfonates (for example, neopelex, diisopropyl naphthalene sulfonate), the formalin condensation product of alkylaryl sulfonates, higher alcohol sulfate salt (for example, pentadecane-2-sulphate), polyxyethylated phosphate (for example, two polyoxyethylene lauryl ether phosphate), styrene-maleic acid salt copolymer etc.; Amphoteric surfactant, as N-lauryl alanine, N, N, N-trimethyl alanine, N, N, N-trihydroxy ethylamino propionic acid, N-hexyl-N, N-dimethylamino acetate, 1-(2-carboxyethyl) pyridine betaine and lecithin.
Stabilizing agent comprises for example phenolic antioxidant, amine antioxidant, Phosphorus antioxidant, sulphur class antioxidant, ultraviolet absorber, epoxidized vegetable oil, as epoxidised soybean oil, epoxidized linseed and epoxidation rapeseed oil; Acidic isopropyl phosphate, atoleine, 1,2 ethylene glycol etc.
Colouring agent comprises for example rhodamine, as rhodamine B and yellow rhodamine (solar rhodamine) and colorant, as Yellow No.4, Blue No.1 and Red No.2, and spices comprises for example ester spices, as ethyl acetoacetate, cognac oil (ethyl enantate), ethyl cinnamate and isoamyl acetate; Organic acid spices is as caproic acid and cinnamic acid; Alcohol spices is as cinnamyl alcohol, geraniol, citral and decyl alcohol; Aldehyde is as vanillin, piperonal and perillaldehyde (perilaldehyde); Ketone spices is as maltol and methyl betanaphthyl ketone, menthol etc.
When Powdered agricultural chemicals comprised thinner, the amount of the pesticide activity component in Powdered agricultural chemicals was generally 1 to 95 weight %, was preferably 10 to 90 weight %, and the amount of thinner is generally 5 to 99 weight %, was preferably 10 to 90 weight %.When Powdered agricultural chemicals comprised the auxiliary agent that is used for agricultural chemicals, the total amount that is used for the auxiliary agent of agricultural chemicals was generally 1 to 30 weight %, is preferably 2 to 20 weight %.
By mixing and pulverizing pesticide activity component, where necessary thinner, the auxiliary agent that is used for agricultural chemicals where necessary as surfactant, stabilizing agent, colouring agent, spices etc., obtains Powdered agricultural chemicals in addition.In addition, can also be ground into pulverous component in advance by mixing and obtain Powdered agricultural chemicals.
As the thermosetting resin that is used for fixing Powdered agricultural chemicals, that mentions has: urea resin, carbamate-urea resin, epoxy resin etc., and in the present invention, preferred especially carbamate resins.
The average grain diameter of pesticide granule of the present invention (volume median diameter) is generally 1 to 200 μ m, is preferably 10 to 200 μ m, more preferably 20 to 150 μ m.Can pass through the laser diffraction granularity analyzer, measure average grain diameter as MASTERSIZER 2000 grades of producing by MALVERN.
Usually by making two kinds of different liquid component reactions obtain thermosetting resin, and produce pesticide granule of the present invention: Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin by for example following method, to add wherein as second liquid component of the raw material that is used for thermosetting resin then, make the reaction of first liquid component and second liquid component to generate thermosetting resin, in addition where necessary, simultaneously or add first liquid component and second liquid component successively, and make their reactions to generate thermosetting resin.By regulating the amount of first liquid component and second liquid component, the thickness that can regulate the clad of being made by thermosetting resin changes to the degree that needs with the degree with controllable release.First liquid component and second liquid component are not necessarily limited to only be made up of a kind of component separately, and can be mixtures.
When thermosetting resin was carbamate resins, a kind of in first liquid component and second liquid component was polyalcohol, and another kind is a PIC.
Polyalcohol comprises PEPA, PPG, polyacrylic acid polyalcohol, polymethylacrylic acid polyalcohol, lactone PEPA, polycarbonate polyol, natural polyalcohol and their denatured products etc. of condensation.The PEPA of described condensation normally condensation reaction by polyalcohol and binary acid obtains.PPG normally addition polymerization by expoxy propane or oxirane and polyalcohol etc. obtains.Polyacrylic acid polyalcohol and polymethylacrylic acid polyalcohol normally obtain by following reaction: the polymerisation of the condensation reaction of the condensation reaction of the condensation reaction of the condensation reaction of polyacrylic acid and polyalcohol, polymethylacrylic acid and polyalcohol, acrylic acid and polyalcohol, methacrylic acid and polyalcohol, the polymerisation of acrylate monomer or methacrylate monomers.The lactone PEPA is to use polyalcohol, and the ring-opening polymerisation by 6-caprolactone obtains as initator.Polycarbonate polyol normally reaction by glycol and carbonic ester obtains, and polyalcohol comprises methylene glycol, 1,2 ethylene glycol, 1,2-propane diols, 1,4-butanediol, 1,6-hexylene glycol, trimethylolpropane, polytetramethylene glycol, glycerine and their oligomer etc.
As the polyalcohol that uses in the present invention, preferred branched chain polyol, and the mixture of branched chain polyol and straight chain polyalcohol, and among described mixture, preferably such mixture, wherein, based on the hydroxyl that is present in the polyalcohol, the quantity that is derived from the straight chain hydroxyl groups is equal to or less than 60%.Branched chain polyol is the polyalcohol that contains three or more hydroxyls in molecule, and preferably contains the polyalcohol of three hydroxyls in molecule.The straight chain polyalcohol is the polyalcohol that contains two hydroxyls in molecule, and each in the two ends of molecule contains hydroxyl usually.
Preferred above-mentioned straight chain polyalcohol is that the OH equivalent is equal to or less than 100 straight chain polyalcohol, and the OH equivalent is equal to or less than the mixture that 100 straight chain polyalcohol and OH equivalent are equal to or greater than 100 straight chain polyalcohol, and among mixture, preferably such mixture, wherein, based on the hydroxyl that is present in the polyalcohol, be derived from the quantity that the OH equivalent is equal to or greater than 100 straight chain hydroxyl groups and be equal to or less than 60%.The OH equivalent is equal to or less than 100 straight chain polyalcohol and comprises 1,2 ethylene glycol, 1,2-propane diols, 1, ammediol etc.
PIC comprises toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), naphthalene diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI, XDI, 4,4-di-2-ethylhexylphosphine oxide (NSC 87419), trimethyl hexamethylene diisocyanate, 1,3-(isocyanatomethyl) cyclohexane, triphenylmethane triisocyanate, three (phenyl isocyanate base) thiophosphate etc.Can also use the isocyanates and the oligomer thereof of sex change to replace above-mentioned PIC monomer, condition is that they have flowability.The isocyanates of sex change comprises the isocyanates of adduct sex change, the isocyanates of biuret sex change, the isocyanates of isocyanuric acid ester sex change, the isocyanates of block sex change, the isocyanates of prepolymer sex change, the isocyanates of dimerization sex change etc.For the viewpoint of the machinability of controlling reaction and low-vapor pressure and excellence easily, preferred polymethylene polyphenyl isocyanate (MDI of polymerization), it is by making aniline and formalin condensation and the polyamines phosgenation that obtains being obtained.
By making polyalcohol and PIC under heating, for example generate carbamate resins 40 to 100 ℃ of reactions.In this operation, add hardening catalyst where necessary, as organic metallic compound, amine etc.
Hardening catalyst comprises organo-metallic compound, as dibutyltin diacetate, two fourth tin dichloros, dibutyl tin dilaurate, the dibutyl thiostannate, stannous octoate, two lauric acid, two positive hot tin etc., triethylenediamine, N-methylmorpholine, N, N-dimethyl two (dodecyl) amine, the N-dodecyl morpholine, N, the N-dimethyl cyclohexyl amine, N-ethylmorpholine, dimethylethanolamine, N, the N-dimethyl benzyl amine, 1,8-diazabicyclo [5.4.0] endecatylene-7, isopropyl titanate, butyl titanate, vanadic acid oxygen isopropyl ester, zirconium-n-propylate, 1,4-diazabicyclo [2.2.2] octane etc.
When thermosetting resin is carbamate resins, can use any in polyalcohol or the PIC, and preferably as first liquid component, use polyalcohol as first liquid component and use PIC as second liquid component.When using hardening catalyst, hardening catalyst can be joined in any in first liquid component and second liquid component, and preferably join in first liquid component.
When thermosetting resin was urea resin, any in first liquid component and second liquid component was polyamines or water, and another kind is a PIC.
PIC comprises above-mentioned PIC, and polyamines comprises diethylenetriamines, trien etc.
When thermosetting resin is urea resin, can uses any in polyamines, water or the PIC, and preferably use polyamines as first liquid component and use PIC as second liquid component as first liquid component.When making water, use PIC as first liquid component and make water usually as second liquid component as liquid component.
When thermosetting resin was carbamate-urea resin, a kind of in first liquid component and second liquid component was the mixture of polyalcohol and polyamines, and another kind is a PIC.The preferred mixture that uses polyalcohol and polyamines is as first liquid component, and the use PIC is as second liquid component.
When thermosetting resin was epoxy resin, any in first liquid component and second liquid component was curing agent, and another kind is the compound that contains glycidyl.
Curing agent is polyamines normally, and the compound that contains the condensating glycerine base generally includes polyglycidyl ether, poly epihydric alcohol amine etc.
Polyamines comprises diethylenetriamines, trien, m-xylylenediamine, different Buddhist diketone diamines, the two propylamine of methyl-imino, menthanediamine, m-phenylene diamine (MPD), tetramethyl triaminotriphenyl methane NH2, diamino diphenyl sulfone, diaminourea diethyl diphenyl methane, the polyamines of polyamide sex change, the polyamines of ketone sex change, the polyamines of epoxy sex change, the polyamines of thiocarbamide sex change, the polyamines of Mannich sex change, the polyamines of Michael addition sex change etc., and the compound that contains glycidyl comprises polyglycidyl ether, as bisphenol-A class polyglycidyl ether, Bisphenol F class polyglycidyl ether, hydrogenated bisphenol A class polyglycidyl ether, naphthalene class polyglycidyl ether, brominated bisphenol category-A polyglycidyl ether, bisphenol S class polyglycidyl ether, bisphenol AF class polyglycidyl ether, biphenyl class polyglycidyl ether, Fluolein class polyglycidyl ether, phenol novolaks class polyglycidyl ether, o-Hydroxytoluene Novolac class polyglycidyl ether, DPP novolaks class polyglycidyl ether, trihydroxy benzene methylmethane class polyglycidyl ether and four phenoxy group ethane (tetraphenylolethane) class polyglycidyl ethers; With poly epihydric alcohol amine, as four glycidyl group diaminodiphenyl-methane birds of the same feather flock together glycidyl amine, hydantoins poly epihydric alcohol amine, 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3-, phenyl amines poly epihydric alcohol amine, toluidines birds of the same feather flock together glycidyl amine, triglycidyl group isocyanates poly epihydric alcohol amine and amino phenols poly epihydric alcohol amine.
Preferred use polyamines is as first liquid component and use polyglycidyl ether or poly epihydric alcohol amine as second liquid component.
The present invention also provides a kind of method that is used to produce composition pesticide, and described method comprises the step that Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin; To add step wherein subsequently as second liquid component of the raw material that is used for thermosetting resin; And make first liquid component and the reaction of second liquid component to generate the step of thermosetting resin.
In production method of the present invention, the viscosity of first liquid component and second liquid component is generally equal to or less than 2000mPas.
When thermosetting resin is carbamate resins, the viscosity of polyalcohol is equal to or less than 1000mPas, more preferably be equal to or less than 800mPas (Brookfield viscometer, 25 ℃, 12rpm), and the viscosity of PIC is equal to or less than 300mPas, more preferably is equal to or less than 200mPas (Brookfield viscometer, 25 ℃, 12rpm).
Usually by first liquid component is joined in the container, under drying condition, in container, roll simultaneously Powdered agricultural chemicals, carry out step that Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin, wherein Powdered agricultural chemicals is not scattered in the liquid medium.This step is preferably carried out at 10 to 80 ℃ usually at 0 to 100 ℃.For the viewpoint of safety, this step is preferably carried out under nitrogen atmosphere.As the method that rolls Powdered agricultural chemicals in container, that mentions has: for example a) wherein make the dish-type that accommodates Powdered agricultural chemicals or cylinder type container around tilting or the method for horizontal rotational shaft; B) wherein in accommodating the container of Powdered agricultural chemicals, settle the roughly the same stirring vane of the diameter of bottom of size and container and make the method for its rotation; And c) wherein in accommodating the container of Powdered agricultural chemicals, rolls the method for Powdered agricultural chemicals by air flow.
To add wherein later step also at 0 to 100 ℃ as second liquid component of the raw material that is used for thermosetting resin, preferably carry out at 10 to 80 ℃.For the viewpoint of safety, this step is preferably carried out under nitrogen atmosphere.Based on 1 equivalent, first liquid component, to be generally 0.9 to 1.05 equivalent, the ratio of preferred 0.95 to 1.00 equivalent is used second liquid component.
If thermosetting resin is that the polyurethane resin and first liquid component are polyalcohols, second liquid component is a PIC so, and advantageously suitably regulate the amount of PIC, make that PIC is 0.8 to 1.1 equivalent with respect to 1 equivalent based on the polyalcohol of hydroxyl (OH) based on the amount of NCO (NCO), be preferably 0.9 to 1.1 equivalent, more preferably 0.95 to 1.05 equivalent.
Make the reaction of first liquid component and second liquid component with the step of processing thermosetting resin also usually at 0 to 100 ℃, preferably carry out at 40 to 80 ℃.For the viewpoint of safety, this step is preferably carried out under nitrogen atmosphere.In this step, preferably mix, give shearing force by rotating vane to Powdered agricultural chemicals simultaneously.More special having of mentioning: by with 50 to 3000m/ minutes, preferred 100 to 2000m/ minutes, the more preferably blade of 200 to 1000m/ minutes speed (according to the speed of blade inlet edge) rotation, the method for stirring powder powder agricultural chemicals.Usually stir until unhardened thermosetting resin and harden fully, and the pesticide granule that obtains does not show viscosity.Can be according to the kind of thermosetting resin and the temperature change mixing time of process.
In the pesticide granule that obtains as mentioned above, in addition where necessary, first liquid component and second liquid component are added simultaneously or successively, and make these component reaction to generate thermosetting resin, and this step carried out once or repeat several times to increase the thickness of the clad of making by thermosetting resin, and promote the phase inter coagulation of particle, thereby can postpone emitting of active component.That is, can regulate the speed of emitting of active component according to purpose.
Based on the Powdered agricultural chemicals of 100 weight portions, the addition of uncured thermosetting resin, promptly the total amount of first liquid component and second liquid component is generally 5 to 150 weight portions, is preferably 10 to 100 weight portions, more preferably 25 to 80 weight portions.
As the concrete container that uses in production method of the present invention, that mentions has: the NEWGRAMACHINE that is produced by SeishinKigyo K.K. shows in container along the device of its peripheral circular motion as particle wherein; And the HIGH SPEEDMIXER and the HIGH FLEX GRAR that produce by Fukae Powtec K.K., as being equipped with the slow-speed of revolution agitator in blender and the device of the high rotating speed cutter mill on the side, wherein the raw material that will pack into by the effect of two blades mixes at short notice, disperses and shears.In addition, that mentions has: the HIGH SPEED MIXER that produces by Freund Sangyo K.K., the VERTICALGRANULATOR that produces by Powrex K.K., the NEW SPEED MILL that produces by Okada Seiko K.K., and as the device that shows identical function.
In addition, can also use the device of in JP 9-75703A, describing.
In production method of the present invention, need not to use solvent such as water etc., so drying process etc. is optional, so can easily produce the pesticide granule that contains the pesticide activity component that is in the controllable release mode.
Pesticide granule of the present invention can be directly injected to will controlled insect go up will protected plant or soil in, or dilute with water, and add auxiliary agent such as surfactant etc. where necessary obtaining suspension, and spray suspension.
Embodiment
To further describe the present invention by the following example, but the invention is not restricted to these embodiment.
In following production example, use HIGH SPEED MIXER device (the LFS-GS-1J type is produced by Fukae Powtec K.K.).
HIGH SPEED MIXER device is an agitating device, and it has: the horizontal circle dish-type container part that has opening on top; Paddle, described stirring vane is around the vertical line rotation of conduct by the axle of the bottom centre of horizontal circle dish-type container part; With the chopping blade, described chopping blade shroud makes the horizontal line rotation for the axle of the side of passing described container part, wherein said container part has the volume of about 2L and the internal diameter of about 18cm, and stirring vane is made up of three blades, described three blades have the radius that is about 9cm and are connected on the bottom surface, make that three blades can be along the bottom surface and the inwall rotation of container part.The chopping blade has two pairs of twin blades, and described twin blade has on the radius and the rotary side wall surface that is connected to container part of 2cm, not contact with stirring vane with the bottom surface of this container part.
Reference example 1 (preparation of Powdered agricultural chemicals 1)
With the 5-chloro-N-(1 of 45.5 weight portions as pesticide activity component, 3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1,3-dimethyl pyrazole-4-formamide (common first names: furan pyrrole bacterium amine (furametpyr)) and 9 weight portion TOKUSEAL GU-N (by Tokuyama Soda Co., Ltd. the amorphous silica hydrate of Sheng Chaning) and 45.5 weight portions mix equably as the bentonite FUJI (producing) of thinner by Hojun K.K., and by cintrifugal disintegrator mixture is all pulverized, to obtain the Powdered agricultural chemicals 1 that average grain diameter is 5.0 μ m (measuring by the MASTERSIZER 2000 that is produced by MALVERN).
Reference example 2 (preparation of Powdered agricultural chemicals 2)
With 65 weight portions as (E)-N-(6-chloro-3-the pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines of pesticide activity component (common first names: Nitenpyram) and 35 weight portions mix equably as the SHOKOZAN Clay S (kaolinton: produce) of thinner by Shokozan Kogyosho K.K., and by cintrifugal disintegrator mixture is all pulverized, to obtain the Powdered agricultural chemicals 2 that average grain diameter is 1 6.0 μ m (measuring by the MASTERSIZER 2000 that is produced by MALVERN).
Reference example 3 (preparation of polyalcohol premix 1)
54.1 weight portion SUMIFEN TM (by the side chain PPG of Sumika Bayer Urethane K.K. production) and 45.9 weight portion SUMIFEN 1600U (by the straight-chain polyether polyalcohol of Sumika Bayer UrethaneK.K. production) are mixed equably to obtain polyalcohol premix 1.The viscosity of polyalcohol premix 1 is 393 mPa (Brookfield viscometer, 25 ℃, 12rpm, Rotor No.1).
Reference example 4 (preparation of polyalcohol premix 2)
41.3 weight portion SUMIFEN TM (by the side chain PPG of Sumika Bayer Urethane K.K. production) and 58.7 weight portion SUMIFEN 1600U (by the straight-chain polyether polyalcohol of Sumika Bayer UrethaneK.K. production) are mixed equably to obtain polyalcohol premix 2.The viscosity of polyalcohol premix 2 is 282mPa (Brookfield viscometer, 25 ℃, 12rpm, Rotor No.1).Reference example 5 (preparation of polyalcohol premix 3)
31.2 weight portion SUMIFEN TM (by the side chain PPG of Sumika Bayer Urethane K.K. production) and 68.8 weight portion SUMIFEN 1600U (by the straight-chain polyether polyalcohol of Sumika Bayer UrethaneK.K. production) are mixed equably to obtain polyalcohol premix 3.The viscosity of polyalcohol premix 3 is 277mPa (Brookfield viscometer, 25 ℃, 12rpm, Rotor No.1).Reference example 6 (preparation of polyalcohol premix 4)
With 19.9 weight portions 1,2-ethylidene glycol (by Nippon Shokubai Co., Ltd. produces) and 80.1 weight portion SUMIFEN 1600U (by the straight-chain polyether polyalcohol of Sumika Bayer Urethane K.K. production) mix equably to obtain polyalcohol premix 4.The viscosity of polyalcohol premix 4 is 176mPa (Brookfield viscometer, 25 ℃, 12rpm, Rotor No.1).
Production example 1
The Powdered agricultural chemicals 1 of 100 weight portions is encased in the container of above-mentioned HIGH SPEED MIXER device, and makes stirring vane (rotating speed: 1800rpm) with chopping blade (rotating speed: 2000rpm) rotation.In this device,, and mainly strong shearing force is applied on the Powdered agricultural chemicals by shredding blade by whole agitator stirring powder powder agricultural chemicals under the state of rolling.Then, with the container heating, and add 1.55 weight portion polyalcohol premixs 1, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.Observe polyalcohol premix 1 and be penetrated into sight in the Powdered agricultural chemicals.After three minutes, add 0.95 weight portion PIC { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer UrethaneK.K. production), viscosity: 130mPa (25 ℃) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After just adding, the thickening phenomenon is confirmed, and viscosity reduces afterwards, and observes the sclerosis (with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins) of polyurethane resin.
In addition, after 5 minutes, with 1) add 1.55 weight portion polyalcohol premixs 1,2) continue to stir and mixed 3 minutes, 3) add 0.95 weight portion PIC and 4) continue to stir and the operation that mixed 5 minutes repeats 3 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 4 times of 10 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 10 weight portions), obtain pesticide granule of the present invention.
Production example 2 to 6
According to production example 1 in identical process, by adding the carbamate resins raw material, obtain pesticide granule of the present invention with the amount that is added to 2.5 weight portions, the interpolation frequency described in the table 1 at every turn.
Table 1
| Powdered agricultural chemicals 1 (weight portion) | Each resin raw material that adds ( *) addition (weight portion) | The interpolation frequency of resin raw material ( *) | The total addition level of resin raw material (weight portion) | |
| Production example 1 | 100 | 2.5 | 4 times | 10 |
| Production example 2 | 100 | 2.5 | 8 times | 20 |
| Production example 3 | 100 | 2.5 | 12 times | 30 |
| Production example 4 | 100 | 2.5 | 16 times | 40 |
| Production example 5 | 100 | 2.5 | 20 times | 50 |
| Production example 6 | 100 | 2.5 | 22 times | 55 |
(
*) resin raw material refers to the carbamate resins raw material, and its amount is polyalcohol premix and PIC sum.
Experimental example 1
1) measurement of average grain diameter
Measure the volume median diameter of the pesticide granule of the present invention that in production example 1 to 6, obtains by the MASTERSIZER 2000 that produces by MALVERN.The results are shown in the table 2.
2) elution test
The pesticide granule of the present invention that obtains with Powdered agricultural chemicals 1 with in production example 1 to 6 is with according to 5-chloro-N=(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1,3-dimethyl pyrazole-4-formamide is that the amount of 5mg is packed in the 100mL helix tube, and the 200g ion exchange water is added wherein, and mixture was kept 24 hours in 25 ℃ thermostatic chamber.Afterwards, filter out solid constituent, and measure the 5-chloro-N-(1 that is eluted in the water by filter, 3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1, the amount of 3-dimethyl pyrazole-4-formamide, and calculate the ratio (eluting rate) that is eluted in the water.The results are shown in the table 2.
Table 2
| Volume median diameter (μ m) | Eluting rate (%) | ||
| After 1 day | After 3 days | ||
| Powdered agricultural chemicals 1 | 5.0 | 85 | 100 |
| Production example 1 | 34.7 | 80 | 90 |
| Production example 2 | 36.9 | 74 | 88 |
| Production example 3 | 40.9 | 45 | 80 |
| Production example 4 | 43.1 | 41 | 73 |
| Production example 5 | 44.8 | 39 | 69 |
| Production example 6 | 45.0 | 36 | 56 |
Production example 7
The Powdered agricultural chemicals 2 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.In this device, by all being in the agitator stirring powder powder agricultural chemicals the state of rolling under, and mainly strong shearing force is applied on the Powdered agricultural chemicals by shredding blade.Then, with the container heating, and add 1.55 weight portion polyalcohol premixs 1, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.Observe polyalcohol premix 1 and be penetrated into sight in the Powdered agricultural chemicals.After three minutes, add 0.95 weight portion PIC { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika BayerUrethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After just adding, the thickening phenomenon is confirmed, and viscosity reduces afterwards, and observes the sclerosis (with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins) of polyurethane resin.
In addition, after 5 minutes, with 1) add 1.55 weight portion polyalcohol premixs 1,2) continue to stir and mixed 3 minutes, 3) add 0.95 weight portion PIC and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 20 times that to use total amount be 50 weight portions with respect to the Powdered agricultural chemicals 2 of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
Production example 8 to 11
According to step identical in production example 7, obtain pesticide granule of the present invention by adding the carbamate resins raw material with the amount that is added to 2.5 weight portions, the interpolation frequency described in the table 3 at every turn.
Table 3
| Powdered granula 2 (weight portion) | Each resin raw material that adds ( *) addition (weight portion) | Resin raw material ( *) the interpolation frequency | Resin raw material ( *) total addition level (weight portion) | |
| Production example 7 | 100 | 2.5 | 20 times | 50 |
| Production example 8 | 100 | 2.5 | 24 times | 60 |
| Production example 9 | 100 | 2.5 | 28 times | 70 |
| Production example 10 | 100 | 2.5 | 32 times | 80 |
| Production example 11 | 100 | 2.5 | 40 times | 100 |
(
*) resin raw material refers to the carbamate resins raw material, and its amount is polyalcohol premix and PIC sum.
Experimental example 2
1) measurement of average grain diameter
Measure the volume median diameter of the pesticide granule of the present invention that in production example 7 to 11, obtains by the MASTERSIZER 2000 that produces by MALVERN.The results are shown in the table 4.
2) elution test
The pesticide granule of the present invention that obtains with Powdered agricultural chemicals with in production example 7 to 11 is being that the amount of 5mg is packed in the 100mL helix tube according to (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines, and the 100g ion exchange water is added wherein, and mixture was kept 24 hours in 25 ℃ thermostatic chamber.Afterwards, filter solid constituent, and measure the amount that is eluted to (E)-N-(6-chloro-3-the pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines in the water, and calculate the ratio (eluting rate) that is eluted in the water by filter.The results are shown in the table 4.
Table 4
| Volume median diameter (μ m) | Eluting rate (%) | ||
| After 1 day | After 3 days | ||
| Powder agricultural chemicals 2 | 16.0 | 100 | 100 |
| Production example 7 | 53.3 | 86 | 90 |
| Production example 8 | 52.3 | 77 | 84 |
| Production example 9 | 57.4 | 23 | 51 |
| Production example 10 | 57.9 | 12 | 23 |
| Production example 11 | 61.5 | 3 | 5 |
Production example 12
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 850rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.Then, with the container heating, and add 1.55 weight portion polyalcohol premixs 1, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 0.95 weight portion PIC { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer Urethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins).
In addition, after 5 minutes, with 1) add 1.55 weight portion polyalcohol premixs 1,2) continue to stir and mixed 3 minutes, 3) add 0.95 weight portion PIC and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 20 times of 50 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
The pesticide granule that obtains has the bigger average grain diameter of pesticide granule of the present invention that obtains than in production example 5.
Production example 13
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: rotation 2000 rpm) of this device.Then, with the mixer heating, and add 1.65 weight portion polyalcohol premixs 2, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 0.85 weight portion PIC { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer Urethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins).
In addition, after 5 minutes, with 1) add 1.65 weight portion polyalcohol premixs 2,2) continue to stir and mixed 3 minutes, 3) add 0.85 weight portion PIC and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 20 times of 50 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
Compare with the pesticide granule of the present invention that obtains in production example 5, the pesticide granule that obtains provides 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1, the wash-out faster of 3-dimethyl pyrazole-4-formamide.
Production example 14
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.Then, with the mixer heating, and add 1.71 weight portion polyalcohol premixs 3, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 0.79 weight portion PIC { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer Urethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins).
In addition, after 5 minutes, with 1) add 1.71 weight portion polyalcohol premixs 3,2) continue to stir and mixed 3 minutes, 3) add 0.79 weight portion PIC and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 20 times of 50 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
Compare with the pesticide granule of the present invention that obtains in production example 5, the pesticide granule that obtains provides 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1, the wash-out faster of 3-dimethyl pyrazole-4-formamide.
Production example 15
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.Then, with the mixer heating, and add 3.10 weight portion polyalcohol premixs 1, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 1.90 weight portion PICs { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer Urethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 5.0 weight portion polyurethane resins).
In addition, after 5 minutes, with 1) add 3.10 weight portion polyalcohol premixs 1,2) continue to stir and mixed 3 minutes, 3) add 1.90 weight portion PICs and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, thereby the temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 10 times of 50 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 5.0 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
Compare with the pesticide granule of the present invention that obtains in production example 5, the pesticide granule that obtains provides 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1, the slower wash-out of 3-dimethyl pyrazole-4-formamide.
Production example 16
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.Then, with the mixer heating, and add 1.20 weight portion polyalcohol premixs 4, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 1.30 weight portion PICs { SUMIDUL 44V10 (by the polymethylene polyphenyl base PIC of Sumika Bayer Urethane K.K. production) }, the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion polyurethane resins).
In addition, after 5 minutes, with 1) add 1.20 weight portion polyalcohol premixs 4,2) continue to stir and mixed 3 minutes, 3) add 1.30 weight portion PICs and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is polyurethane resin raw material (the interpolation frequency of carbamate resins raw material: 20 times of 50 weight portions with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each carbamate resins raw material that adds: 2.5 weight portions; The total addition level of carbamate resins raw material: 50 weight portions), obtain pesticide granule of the present invention.
Production example 17
The Powdered agricultural chemicals 1 of 100 weight portions is packed in the container of above-mentioned HIGH SPEED MIXER device, and make the stirring vane (rotating speed: 1800rpm) and chopping blade (rotating speed: 2000rpm) rotation of this device.Then, with the mixer heating, and add 0.83 weight portion polyamine mixture (the E206W curing agent is produced viscosity: 400mPa (25 ℃) by Konishi K.K.), the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.After three minutes, add 1.67 weight portion polyglycidyl ethers (E206W master's reagent is produced Bisphenol F class epoxy master reagent, viscosity: 500mPa (25 ℃) by Konishi K.K.), the temperature with Powdered agricultural chemicals remains on 75 ± 5 ℃ simultaneously.(with respect to the Powdered agricultural chemicals of 100 weight portions, corresponding to 2.5 weight portion epoxy resin).
In addition, after 5 minutes, with 1) add 0.83 weight portion E206W curing agent, 2) continue to stir and mixed 3 minutes, 3) add 1.67 weight portion E206W master reagent and 4) continue to stir and the operation that mixed 5 minutes repeats 19 times, continue simultaneously to stir, temperature in the HIGH SPEED MIXER device is remained on 75 ± 5 ℃, afterwards, allow the mixture cooling to obtain pesticide granule of the present invention.
Therefore, using total amount is 50 parts by weight of epoxy resin raw materials (the interpolation frequencies of epoxy resin raw material: 20 times with respect to the Powdered agricultural chemicals of 100 weight portions; The addition of each epoxy resin raw material that adds: 2.5 weight portions; The total addition level of epoxy resin raw material: 50 weight portions), obtain pesticide granule of the present invention.
Industrial usability
Pesticide granule of the present invention can make pesticide activity component obtain controlled release. Production method of the present invention can provide the composition pesticide that contains the pesticide activity component that is in the controlled release form easily.
Claims (17)
1. the pesticide granule of a coating, described pesticide granule obtains by Powdered agricultural chemicals is assembled.
2. pesticide granule according to claim 1, wherein said thermosetting resin are carbamate resins, urea resin or epoxy resin.
3. pesticide granule according to claim 1, wherein said thermosetting resin is a carbamate resins.
4. according to claim 1,2 or 3 described pesticide granules, wherein said Powdered agricultural chemicals is the composition that comprises pesticide activity component and thinner.
5. according to claim 1,2 or 3 described pesticide granules, wherein said Powdered agricultural chemicals be comprise 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1,3-dimethyl pyrazole-4-formamide is as the Powdered agricultural chemicals of pesticide activity component.
6. pesticide granule according to claim 5, wherein said Powdered agricultural chemicals be comprise 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1,3-dimethyl pyrazole-4-formamide is as the Powdered agricultural chemicals of pesticide activity component and thinner.
7. according to claim 1,2 or 3 described pesticide granules, wherein said Powdered agricultural chemicals is to comprise the Powdered agricultural chemicals of (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines as pesticide activity component.
8. pesticide granule according to claim 7, wherein said Powdered agricultural chemicals are to comprise the Powdered agricultural chemicals of (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines as pesticide activity component and thinner.
9. method that is used to produce composition pesticide, described method comprise the step that Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin; Add step as second liquid component of the raw material that is used for thermosetting resin; Make the reaction of first liquid component and second liquid component to generate thermosetting resin then.
10. the method that is used to produce composition pesticide according to claim 9, described method comprises the step that Powdered agricultural chemicals is mixed with first liquid component as the raw material that is used for thermosetting resin, add as second liquid component that is used for the raw material of thermosetting resin, thereby by making the reaction of first liquid component and second liquid component to generate the step that thermosetting resin obtains pesticide granule, first liquid component and second liquid component are added in the pesticide granule that obtains simultaneously or successively, make their reactions then to coat the step of described pesticide granule with described thermosetting resin.
11. according to claim 9 or the 10 described methods that are used to produce composition pesticide, wherein said Powdered agricultural chemicals be comprise 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuran-base)-1,3-dimethyl pyrazole-4-formamide is as the Powdered agricultural chemicals of pesticide activity component.
12. according to claim 9 or the 10 described methods that are used to produce composition pesticide, wherein said Powdered agricultural chemicals is to comprise the Powdered agricultural chemicals of (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N '-methyl-2-nitro ethenylidene diamines as pesticide activity component.
13. according to claim 9 or the 10 described methods that are used to produce composition pesticide, wherein said thermosetting resin is carbamate resins, urea resin or epoxy resin.
14. according to claim 9 or the 10 described methods that are used to produce composition pesticide, wherein said thermosetting resin is a carbamate resins.
15. the method that is used to produce composition pesticide according to claim 14, wherein first liquid component is a polyalcohol, and second liquid component is a PIC.
16. according to claim 9 or the 10 described methods that are used to produce composition pesticide, wherein said thermosetting resin is an epoxy resin.
17. the method that is used to produce composition pesticide according to claim 16, wherein first liquid component is a polyamines, and second liquid component is polyglycidyl ether or poly epihydric alcohol amine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005091274 | 2005-03-28 | ||
| JP091274/2005 | 2005-03-28 | ||
| JP286831/2005 | 2005-09-30 |
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| CN2013102366658A Division CN103314960A (en) | 2005-03-28 | 2006-01-27 | Agricultural-chemical composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9750257B2 (en) | 2009-01-30 | 2017-09-05 | Sumitomo Chemical Company, Limited | Coated seed |
| CN111848421A (en) * | 2020-08-19 | 2020-10-30 | 贵州省烟草科学研究院 | Polyether-based pesticide adjuvant and preparation method and application thereof |
-
2006
- 2006-01-27 CN CNA2006800097091A patent/CN101146449A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9750257B2 (en) | 2009-01-30 | 2017-09-05 | Sumitomo Chemical Company, Limited | Coated seed |
| CN111848421A (en) * | 2020-08-19 | 2020-10-30 | 贵州省烟草科学研究院 | Polyether-based pesticide adjuvant and preparation method and application thereof |
| CN111848421B (en) * | 2020-08-19 | 2023-04-28 | 贵州省烟草科学研究院 | Polyether-based pesticide auxiliary agent and preparation method and application thereof |
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