JP2012193142A - Method for producing coated composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a coated composition which has excellent sustained releasability of a bioactive constituent.SOLUTION: The method for producing a coated composition in which a powdered material containing a bioactive constituent is coated with a thermosetting resin includes a step of, in a mixing machine which has a tank and an impeller for mixing rotating along the bottom face of the tank, and in which the minimum interval between the bottom face of the tank and the impeller is ≥100 μm, mixing the powdered material and the raw material for a thermosetting resin. By using the method, the coated composition in which the sustained releasability or the like of the bioactive constituent is improved can be obtained.

Description

  The present invention relates to a method for producing a coating composition containing a bioactive component and coated with a thermosetting resin.

In Patent Document 1, a thermosetting resin raw material and a pesticide are added to a mixer (stirring device) having a container part, an agitator blade attached to the bottom surface of the container part, and a chopper blade attached to the side wall surface of the container part. It is described that it is possible to produce a coated granular agricultural chemical composition in which a powdered agricultural chemical is coated with a thermosetting resin.
In such a mixer, there is a gap (sometimes referred to as clearance) between the bottom surface of the container portion and the agitator blade, and if this gap is large, the stirring efficiency is reduced or the bottom of the container portion is attached. Kimono increases. Therefore, from the viewpoints of stirring operation, recovery efficiency of the target object, etc., the gap between the container bottom surface and the agitator blade in such a mixer is usually set to be as narrow as possible.

JP2007-119442

The present inventors have studied to increase the coating amount by adding more coating resin raw material in order to further improve the sustained release property of the pesticidal active ingredient contained in the coated pesticidal composition. However, even if the amount of the coating resin material is increased, the sustained release of the agrochemical active ingredient corresponding to the increased amount cannot be improved, and more coating resin materials may be required. There has been a demand for a method for producing a coated agricultural chemical composition having a higher coating efficiency of a conductive resin.
An object of the present invention is to provide a method for producing a coated agrochemical composition having a higher coating efficiency of a thermosetting resin.

  As a result of intensive studies to find out a method for producing a coated agricultural chemical composition that solves the above-mentioned problems, the present inventors have found that the bottom surface of the container part of the mixer used in the production process and the stirring blade (agitator blade provided in the container part) It was found that the thermosetting resin can be efficiently coated on the pesticidal pesticide by setting the gap with the above to a certain interval or more.

The present invention is as follows.
[1] A powdery substance containing a biologically active component in a mixer having a rotating blade at the bottom of the tank and the tank, and having a minimum distance between the bottom surface of the tank and the rotating blade of 100 μm or more, and Having a step of mixing the thermosetting resin raw material,
A method for producing a coating composition in which the powder is coated with a thermosetting resin.
[2] The method according to item [1], wherein the minimum distance between the tank and the rotary blade is 400 to 1600 μm.
[3] The method according to any one of [1] or [2] above, wherein the volume median diameter of the coating composition is 10 to 200 μm.
[4] The production method according to any one of the above items [1] to [3], wherein the bioactive component is clothianidin.
[5] The method according to any one of the above items [1] to [4], wherein the thermosetting resin is a urethane resin.
[6] Adjusting the minimum distance between the bottom surface of the tank and the rotary blade of the mixer having a rotary blade at the bottom of the tank and the tank to 100 μm or more, and
The manufacturing method of the coating composition with which this powdery material was coat | covered with the thermosetting resin which has the process of mixing the powdery material containing a bioactive component, and a thermosetting resin raw material in this mixer.
[7]
The coating composition manufactured with the manufacturing method of any one of said item [1]-[6] (it is hereafter described as this coating composition).

By the manufacturing method of this invention, the coating composition coat | covered with the thermosetting resin can be manufactured more efficiently. In the production method of the present invention, the thermosetting resin raw material is effectively used for producing a resin that coats the bioactive component-containing powdered material more effectively without waste.
Since the utilization efficiency of the thermosetting resin raw material is higher in the production method of the present invention, more thermosetting resin is coated with the powdered agricultural chemical even if the same amount of the thermosetting resin raw material is used, The coating can be thicker. As a result, the obtained coated agrochemical composition can release the pesticidal active ingredient over a longer period of time and has higher stability against external factors such as light. On the other hand, in order to obtain a coated agrochemical composition having the same sustained release effect as before, the use amount of the thermosetting resin raw material can be further reduced by using the production method of the present invention.
Thus, by the production method of the present invention, it is possible to obtain a coating composition in which the sustained release property of the bioactive ingredient and the stability against external factors are further improved using the same amount of thermosetting resin raw material as before. In addition, it is possible to obtain a coating composition having a sustained release property of the biologically active ingredient equivalent to the conventional one and stability against external factors by using a smaller amount of the thermosetting resin raw material. The production method of the present invention is a highly productive method.

The mixer used in the method of the present invention (hereinafter referred to as the present mixer) is a device having a tank (container) and a rotating blade (agitator blade) for mixing at the bottom of the tank.
Such a tank is a cylindrical container whose bottom is generally circular or substantially circular, and has a cylindrical shape or a substantially cylindrical shape.
Such a rotary blade is composed of a single blade or a plurality of blades. A rotary blade is installed in the bottom part in a tank so that it may rotate along a tank bottom face and a side wall. Usually, a rotation axis is provided at the center of the tank bottom surface in a direction perpendicular to the tank bottom surface, and a rotary blade is attached to the rotation shaft at the center thereof. The rotation surface of the rotary blade faces the bottom of the tank, and the tip of the rotary blade rotates along the side wall of the tank. The size of the rotary blade is such that it does not hinder the rotation in the tank, and the diameter of the rotary surface of the rotary blade is usually the same as the diameter of the bottom surface of the tank.

  If necessary, the mixer may be provided with blades rotating around a horizontal axis protruding from the side surface of the tank.

The tank bottom surface in the present invention refers to the surface inside the tank where the rotary blades are installed. Usually, the bottom surface has a circular shape and has a gap with the rotary blade.
In the production method of the present invention, the minimum gap between the bottom surface of the mixer and the rotary blade is adjusted to 100 μm or more. The minimum distance between the bottom surface of the tank and the rotary blade in the present invention indicates the minimum distance (thickness) of the gap between the bottom surface of the tank and the rotary blade.

The minimum distance between the bottom surface of the tank and the rotary blade in the present invention is measured and determined by the following procedure.
1) Insert a clearance gauge from the tank side into the gap between the tank bottom and the rotating blade, and slide it toward the rotating shaft to which the rotating blade is attached. The thickness of the clearance gauge that can reach the rotating shaft is defined as the size of the clearance.
2) When the rotary blade is composed of a plurality of blades, the operation of 1) is performed on all the blades.
3) Rotate the rotating blades (180 / number of rotating blades) ° and perform the same operations as 1) and 2).
4) Among the gap sizes obtained in 1) to 3), the smallest one is set as the minimum gap.
In this invention, the minimum space | interval of the bottom face of a tank and a rotary blade is 100 micrometers or more. The upper limit of the minimum interval may be an extent that does not cause a problem in the stirring operation and the amount of residue, but is usually 3000 μm or less. The minimum distance is preferably in the range of 400 to 1600 μm.

  Examples of the mixer used in the production method of the present invention include, for example, a high-speed mixer manufactured by Fukae Powtech Co., Ltd., a high flex glal, a vertical granulator manufactured by Powrec Co., Ltd., a granumist manufactured by Freund Sangyo Co., Ltd. Examples include commercial products such as a high-speed stirring granulator and an apparatus described in JP-A-9-75703.

In the present invention, the biologically active ingredient is used in the agricultural field, horticultural field, and / or the epidemiological field like the agricultural chemical active ingredient. For example, the insecticidal compound, the insect growth regulating compound, the bactericidal compound, the herbicidal compound, Examples include plant growth regulating compounds. The biologically active ingredient in the present invention is solid at 20 ° C, preferably solid at 50 ° C.
Examples of such biologically active ingredients include the following compounds.

  Insecticidal compounds and insect growth-regulating compounds include pyrethroid compounds such as deltamethrin, tralomethrin, acrinathrin, tetramethrin, and tefluthrin; Carbamate compounds; organic phosphorus compounds such as acephate, trichlorfone, tetrachlorvinphos, dimethylvinphos, pyridafenthion, azinephosethyl, azinephosmethyl; diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, flucycloxuron, cyromazine , Diafenthiuron, Hexithiazox, Novallon, Teflubenzuron, Riflumuron, 4-chloro-2- (2-chloro-2-methylpropyl) -5- (6-iodo-3-pyridylmethoxy) pyridazin-3 (2H) -one, 1- (2,6-difluorobenzoyl) -3- [2-Fluoro-4- (trifluoromethyl) phenyl] urea, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl] urea, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazon-4-one, 1- Urea compounds such as (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1,2,2-tetrafluoroethoxy) phenyl] urea; imidacloprid, aceta Chloronicotyl compounds such as pride, clothianidin, nitenpyram, thiamethoxam, dinotefuran, thiacloprid; spinosins such as spinosad; diamide compounds such as fulvendiamide, chlorantraniliprole, cyantraniliprole; phenylpyrazole compounds such as fipronil, ethiprole, spiro Tetramic, spiromesifen, spirodiclofen and other tetramic acid compounds, cartap, buprofezin, thiocyclam, bensultap, phenazaquin, fenpyroximate, pyridaben, hydramethylnon, chlorfenapyr, fenproximate, pymetrozine, pyrimidifene, tebufenozide, tebufenpyrad, Triazamate, Indoxacarb, Sulfluramide, Milbemecti , Avermectin, boric acid, paradichlorobenzene.

  Bactericidal compounds include benzimidazole compounds such as benomyl, carbendazim, thiabendazole, and thiophanate methyl; phenyl carbamate compounds such as dietofencarb; dicarboximide compounds such as procimidone, iprodione, and vinclozolin; Azole compounds such as cyproconazole, flusilazole, and triazimephone; acylalanine compounds such as metalaxyl; carboxyamide compounds such as furametopil, mepronil, flutolanil, and trifluzamide; organophosphorus compounds such as tolcrofosmethyl, focetylaluminum, and pyrazophos; pyrimesanil , Mepanipyrim, cyprodinil and other anilinopyrimidine compounds; Cyanopyrrole compounds such as sonyl and fenpiclonyl; antibiotics such as blasticidin S, kasugamycin, polyoxin, and validamycin; methoxyacrylate compounds such as azoxystrobin, cresoxime methyl, and SSF-126; chlorothalonil, manzeb, captan, phorpet, tricyclazole , Pyroxylone, Probenazole, Fusaride, Simoxanyl, Dimethomorph, CGA245704, Famoxadone, Oxolinic acid, Fluazinam, Ferimzone, Diclocimet, Clobenazone, Isovaredione, Tetrachloroisophthalonitrile, Thiophthalimidooxybisphenoxyarsine, 3-Iodo-2- Propylbutyl carbamate, parahydroxybenzoate, sodium dehydroacetate Potassium sorbate, orysastrobin, isotianil, triazinyl, is thiuram and the like.

  Herbicidal compounds include: triazine compounds such as atrazine and metribudine; urea compounds such as fluometuron and isoproturon; hydroxybenzonitrile compounds such as bromoxynyl and ioxynil; 2,6-dinitroaniline compounds such as pendimesalin and trifluralin Compound; Allyloxyalkanoic acid compounds such as 2,4-D, dicamba, fluroxypyr, and mecoprop; Bensulfuron methyl, Metulfuron methyl, Nicosulfuron, Primsulfuron methyl, Cyclosulfamlone, Imazosulfuron, Propyrisulfuron, Sulphonylurea compounds such as sulfosulfuron; imidazolinone compounds such as imazapyr, imazaquin, and imazetapill; bispyribac Na salt, bisthiobac Na salt, acifluorfen Na , Sulfentrazone, paraquat, flumeturum, triflusulfuron methyl, phenoxaprop-p-ethyl, diflufenican, norflurazon, isoxaflutol, glufosinate amnium salt, glyphosate, bentazone, mefenacet, propanil, flutamide , Full microlac pentyl, flumioxazin, bromobutide and the like.

  Examples of plant growth regulating compounds include maleic hydrazide, chlormecut, etephone, gibberellin, mepicut chloride, thiazuron, inavenfide, paclobutrazol, uniconazole.

In the present invention, a powdery substance containing a biologically active ingredient (hereinafter referred to as the present powdery substance) usually has an average particle diameter (volume median diameter) of 1 to 100 μm, preferably 1 to 30 μm. The average particle diameter (volume median diameter) and the average particle diameter (volume median diameter) of other components described later can be measured with a laser diffraction particle size measuring instrument such as MASTERSIZER2000 manufactured by MALVERN.
Although this powdery material may contain only a powdery biologically active ingredient as a component, it is usually a powdery composition containing a biologically active ingredient and a diluent.

When the present powdery substance contains a diluent, the amount of the bioactive ingredient is usually 1 to 95% by weight, preferably 10 to 90% by weight, based on the total weight of the present powdery substance. Usually 5 to 99% by weight, preferably 10 to 90% by weight.
The average particle diameter (volume median diameter) of the diluent is usually in the range of 1 to 100 μm.
Such a diluent is a powdery solid carrier usually used in agricultural chemical powders. Examples of such powdery solid carriers include kaolin minerals (kaolinite, dickite, nacrite, halosite, etc.), serpentine (chrysotile, lizarite, anticorite, amesite, etc.), montmorillonite minerals (sodium montmorillonite, calcium montmorillonite, Magnesium montmorillonite), smectite (saponite, hectorite, soconite, hydelite, etc.), pyrophyllite, talc, wax, mica (muscovite, fengite, sericite, illite, etc.), silica (cristobalite, quartz, etc.), Double-chain clay minerals (palygorskite, sepiolite, etc.), sulfate minerals such as gypsum, dolomite, calcium carbonate, gypsum, zeolite, tuff, vermiculite, laponite, pumice, diatomaceous earth, acid white , It includes activated clay.
The powdery product may further contain an agrochemical auxiliary such as a surfactant, a stabilizer, a colorant, and a fragrance.

  Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid ester, Polyoxypropylene glycol mono fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block polymer , Polyoxyethylene fatty acid amide, alkylolamide, polyoxyethylene alkyl Nonionic surfactant such as amine; alkylamine hydrochloride such as dodecylamine hydrochloride, alkyl such as dodecyltrimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylisoquinolinium salt, dialkylmorpholinium salt Cationic surfactants such as quaternary ammonium salts, benzethonium chloride and polyalkylvinylpyridinium salts; fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, lauroyl sarcosine sodium, N- Amino acid condensates of higher fatty acids such as sodium lauroyl glutamate, higher fatty acid esters such as higher alkyl sulfonates and laurate sulfonates Dialkylsulfosuccinates such as honates, dioctylsulfosuccinates, higher fatty acid amidesulfonates such as oleic acid amidesulfonic acid, alkylarylsulfonates such as sodium dodecylbenzenesulfonate, diisopropylnaphthalenesulfonate, alkylaryl Formalin condensates of sulfonates, higher alcohol sulfates such as pentadecane-2-sulfate, polyoxyethylene alkyl phosphates such as dipolyoxyethylene dodecyl ether phosphate, styrene-maleate copolymers, etc. Anionic surfactant; N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, 1- ( 2- And amphoteric surfactants such as carboxyethyl) pyrimidinium betaine and lecithin.

Stabilizers include, for example, epoxidized vegetable oils such as phenol antioxidants, amine antioxidants, phosphoric antioxidants, sulfur antioxidants, UV absorbers, epoxidized soybean oil, epoxidized linseed oil, and epoxidized rapeseed oil , Isopropyl acid phosphate, liquid paraffin, ethylene glycol and the like.
Examples of the colorant include rhodamines such as rhodamine B and solar rhodamine, and dyes such as yellow No. 4, blue No. 1, red No. 2, and the like.
As the fragrance, for example, ester fragrance such as ethyl acetoacetate, ethyl enanthate, ethyl cinnamate, isoamyl acetate, organic acid fragrance such as caproic acid, cinnamic acid, alcohol fragrance such as cinnamon alcohol, geraniol, citral, decyl alcohol, Examples include aldehydes such as vanillin, piperonal and perylaldehyde, ketone fragrances such as maltol and methyl β-naphthyl ketone, and menthol.
This powder is obtained by mixing and crushing a biologically active ingredient, a diluent if necessary, and an agrochemical adjuvant if necessary. This powdery product can also be obtained by mixing each component previously pulverized into powder.

In the present invention, examples of the thermosetting resin include urethane resin, urea resin, urethane-urea resin, and epoxy resin.
The thermosetting resin is generally obtained by reacting two kinds of liquid raw materials (hereinafter referred to as a first liquid component and a second liquid component), and the present coating composition is made of a thermosetting resin. Depending on the type, it can be produced by the following method.

When the thermosetting resin is a urethane resin, one of the first liquid component and the second liquid component is a polyol and the other is a polyisocyanate.
Examples of the polyol include condensed polyester polyol, polyether polyol, poly (meth) acrylic acid polyol, lactone polyester polyol, and polycarbonate polyol. The condensed polyester polyol is usually obtained by a condensation reaction between a polyol and a dibasic acid. The polyether polyol is usually obtained by addition polymerization of propylene oxide or ethylene oxide to a polyhydric alcohol or the like. Poly (meth) acrylic acid polyol is usually obtained by condensation reaction of poly (meth) acrylic acid and polyol, condensation reaction of (meth) acrylic acid and polyol, or polymerization reaction of (meth) acrylic acid ester monomer. It is done. The lactone polyester polyol is obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol as an initiator. Polycarbonate polyol is usually obtained by reaction of glycol and carbonate.

  As the polyol used in the present invention, a mixture of a branched polyol and a linear polyol is preferable. In the polyol mixture, the number of hydroxyl groups present in the polyol is preferably 60% or less derived from the linear polyol. The branched polyol is a polyol having 3 or more hydroxyl groups in the molecule, and a polyol having 3 hydroxyl groups in the molecule is preferable. A linear polyol is a polyol having two hydroxyl groups in the molecule, and usually has hydroxyl groups at both ends of the molecule.

  As the linear polyol, a mixture of a linear polyol having an OH equivalent of 100 or less and a linear polyol having an OH equivalent of 100 or more is preferable. In the outer mixture, the number of hydroxyl groups present in the polyol is preferably 60% or less derived from a linear polyol having an OH equivalent of 100 or more. Examples of the linear polyol having an OH equivalent of 100 or less include ethylene glycol, propylene glycol, and trimethylene glycol.

  As polyisocyanate used in the present invention, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), Examples include trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate. In addition, it can replace with said polyisocyanate and can also use these modified bodies and oligomers, as long as it has fluidity | liquidity. Examples of modified products include adduct modified products, biuret modified products, isocyanurate modified products, block modified products, prepolymer modified products, and dimerized modified products. A polymethylene polyphenyl isocyanate (polymeric MDI) obtained by phosgenating a polyamine via condensation of aniline and formalin is preferable in terms of easy reaction control and low workability and excellent workability.

A urethane resin is produced | generated by making a polyol and polyisocyanate react, for example at 40-100 degreeC. At that time, a catalyst such as an organic metal or an amine is added as necessary.
Examples of the catalyst in this case include dibutyltin diacetate, dibutyltin dichloride, dibutyltin dilaurate, dibutylthiostannic acid, stannous octylate, and di-n-octyltin dilaurate; triethylenediamine, N-methylmorpholine N, N-dimethyldidodecylamine, N-dodecylmorpholine, N, N-dimethylcyclohexylamine, N-ethylmorpholine, dimethylethanolamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo (5,4 0) Undecene-7, isopropyl titanate, tetrabutyl titanate, oxyisopropyl vanadate, n-propyl zirconate, and 1,4-diazabicyclo [2,2,2] octane.

When the thermosetting resin is a urea resin, one of the first liquid component and the second liquid component is a polyamine and the other is a polyisocyanate.
Examples of the polyisocyanate include the aforementioned polyisocyanates.
Examples of the polyamine include diethylenetriamine and triethylenetetraamine.

When the thermosetting resin is a urethane-urea resin, one of the first liquid component and the second liquid component is a polyol and a polyamine, and the other is a polyisocyanate.
Examples of the polyol, polyamine, and polyisocyanate include those described above.

When the thermosetting resin is an epoxy resin, one of the first liquid component and the second liquid component is a compound having a curing agent and the other having a glycidyl group.
Examples of the curing agent include diethylenetriamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, methyliminobispropylamine, mensendiamine, metaphenylenediamine, diaminophenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, polyamide-modified polyamine, Examples include ketone-modified polyamines, epoxy-modified polyamines, thiourea-modified polyamines, Mannich-modified polyamines, and Michael addition-modified polyamine polyamines.
Examples of the compound having a glycidyl group include polyglycidyl ether and polyglycidylamine. Polyglycidyl ethers include bisphenol A type polyglycidyl ether, bisphenol F type polyglycidyl ether, hydrogenated bisphenol A type polyglycidyl ether, naphthalene type polyglycidyl ether, brominated bisphenol A type polyglycidyl ether, bisphenol S type polyglycidyl ether Bisphenol AF polyglycidyl ether, biphenyl polyglycidyl ether, fluorein polyglycidyl ether, phenol novolac polyglycidyl ether, o-cresol novolac polyglycidyl ether, DPP novolac polyglycidyl ether, trishydroxyphenylmethane poly Examples thereof include glycidyl ether and tetraphenylolethane type polyglycidyl ether. Examples of polyglycidylamine include tetraglycidyldiaminodiphenylmethane type polyglycidylamine, hydantoin type polyglycidylamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, aniline type polyglycidylamine, and toluidine type polyglycidylamine. , Triglycidyl isocyanurate type polyglycidylamine, aminophenol type polyglycidylamine and the like.

  When the thermosetting resin is a urethane resin, the viscosity of the polyol as one raw material is preferably 1000 mPa · s or less, more preferably 800 mPa · s or less (B-type viscometer, 25 ° C., 12 rotations), and the other The viscosity of the polyisocyanate as a raw material is preferably 300 mPa · s or less, more preferably 200 mPa · s or less (B-type viscometer, 25 ° C., 12 rotations).

In the present invention, the present coating composition is obtained by solidifying a present powdery product with a thermosetting resin.
Specifically, the present coating composition can be produced, for example, by the following method.
A step of mixing the present powder and the first liquid component which is a raw material of the thermosetting resin, a step of adding a second liquid component which is a raw material of the thermosetting resin to the first liquid component, A step of obtaining a thermosetting resin solidified product of the present powdery product by reacting with the second liquid component to produce a thermosetting resin, and further to the thermosetting resin solidified product of the obtained present powdery product. The present coating composition is prepared by a production method including a step of adding a first liquid component and a second liquid component simultaneously or sequentially and reacting them to coat a thermosetting resin solidified powder with a thermosetting resin. Can be manufactured.
These processes are performed in the tank of this mixer.

  In the above step, the step of adding the first liquid component and the second liquid component simultaneously or sequentially and reacting them to produce a thermosetting resin is repeated once or a plurality of times.

  This step is usually performed at 0 to 100 ° C, preferably 20 to 90 ° C. This step is preferably performed in a nitrogen atmosphere from the viewpoint of safety.

  In the present coating composition, the amount of the thermosetting resin is usually 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and more preferably 40 to 150 parts by weight with respect to 100 parts by weight of the present powdery product. .

  The average particle diameter (volume median diameter) of the present coating composition is usually 10 to 200 μm, preferably 20 to 150 μm.

The coating composition can be used to produce solid preparations such as powders, granules and tablets by mixing with auxiliary agents such as solid inert carriers, binders and surfactants, and dispersion media such as water and organic solvents. A liquid preparation can be produced by mixing with (solvent) and auxiliary agents such as a surfactant.
The present coating composition, a solid preparation containing the present coating composition and a liquid preparation (hereinafter generally referred to as the present composition) are applied to a place where the biological activity of the bioactive component is required. Examples of the place include a place where a pest to be controlled or an insect or a plant that requires growth control inhabit, or a place where there is a possibility of inhabiting in the future. , Concrete, wood and the like.
The composition may be applied directly to pests to be controlled or insects or plants that require growth control.
As a method of applying the present composition, the present composition is sprayed as it is on the application target place / application target, or a diluted solution of the present composition obtained by diluting the present composition with water or the like is sprayed. And a method of premixing the present composition or a diluted solution of the present composition with a concrete raw material when applied to concrete.

Preparation of powdered pesticide 1 (powder) 70.0 parts by weight of (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (general Name: clothianidin) and 30.0 parts by weight of Katsuyama Clay S (manufactured by Katsumiyama Mining) are uniformly mixed, and pulverized using a turbo mill (T-400 manufactured by Turbo Mill Industry Co., Ltd.). Powdered pesticide (hereinafter referred to as powdery) with a volume median diameter of 9.9 μm (MASTERSIZER2000 manufactured by MALVERN) containing 1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (Referred to as pesticide 1).

-Preparation of polyol premix 1 46.3 parts by weight of Sumifene TM (branched polyether polyol made by Sumika Bayer Urethane), 52.2 parts by weight of Sumifene 1600U (linear polyether polyol made by Sumika Bayer Urethane), And 1.5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Kayaku Akzo) were uniformly mixed to obtain a liquid mixture (hereinafter referred to as polyol premix 1). The viscosity of the polyol premix 1 was 322 m · Pa (B-type viscometer, 25 ° C., 12 revolutions, rotor No. 1).

Production Example 1
・ Preparation of coated pesticide 1 High-speed mixer device (FS-GS-200 type, manufactured by Fukae Pautech Co., Ltd .; agitator blade (rotary blade) and round with a vertical line passing through the center of the bottom of the round dish container The height of the agitator blades is set so that the minimum gap between the agitator blades in the container and the bottom surface of the container in the container of the horizontal line passing through the side surface of the dish-shaped container (tank) part is 1100 μm. Adjusted.
After the adjustment, 100 parts by weight of powdered pesticide 1 was charged into the container, and the agitator blade and chopper blade were rotated at a rotation speed of 170 rpm and 2500 rpm, respectively. Next, the container was heated to bring the temperature of the powdered pesticide 1 to 85 ± 3 ° C., and 1.93 parts by weight of the polyol premix 1 was added thereto over 2 minutes while maintaining the temperature. Three minutes later, with the product temperature maintained at 85 ± 3 ° C., 1.07 parts by weight of Sumijoule 44V10 (polymethylene polyphenyl polyisocyanate made by Sumika Bayer Urethane, viscosity 130 m · Pa (25 ° C.)) Was added over 2 minutes. Six minutes later, the following “urethane addition operation” was performed 34 times with the product temperature maintained at 85 ± 3 ° C.

[Urethane addition operation]
Add 1.93 parts by weight of polyol premix 1 over 2 minutes-> wait for 3 minutes-> add 1.07 parts by weight of Sumidre 44V10 over 2 minutes-> wait for 6 minutes.

4.76 parts by weight of calcium carbonate (NS # 2300 manufactured by Nitto Flour Chemical Co., Ltd.) is added to 100 parts by weight of the powder obtained after the urethane addition operation (34 times), and the mixture is stirred for 3 minutes and covered with urethane. The coated agricultural chemical 1 was obtained (volume median diameter: 36 μm).

Production Example 2
-Preparation of coated agricultural chemical 2 The height of the agitator blade was adjusted so that the minimum gap between the agitator blade and the bottom surface in the container of the high speed mixer device (the same device used in Production Example 1) was 1100 μm. .
After the adjustment, 100 parts by weight of powdered pesticide 1 was charged into the container, and the agitator blade and chopper blade were rotated at a rotation speed of 170 rpm and 2500 rpm, respectively. Next, the container was heated to bring the temperature of the powdered pesticide 1 to 80 ± 3 ° C., and 1.93 parts by weight of the polyol premix 1 was added thereto over 2 minutes while maintaining the temperature. Three minutes later, with the product temperature maintained at 80 ± 3 ° C., 1.07 parts by weight of Sumijoule 44V10 (polymethylene polyphenyl polyisocyanate made by Sumika Bayer Urethane, viscosity 130 m · Pa (25 ° C.)) Was added over 2 minutes. Six minutes later, the following “urethane addition operation” was performed 28 times while maintaining the product temperature at 80 ± 3 ° C.

[Urethane addition operation]
Add 1.93 parts by weight of polyol premix 1 over 2 minutes-> wait for 3 minutes-> add 1.07 parts by weight of Sumidre 44V10 over 2 minutes-> wait for 6 minutes.

4.76 parts by weight of calcium carbonate (NS # 2300, manufactured by Nitto Flour Chemical Co., Ltd.) is added to 100 parts by weight of the powder obtained after the urethane addition operation (28 times), and the mixture is stirred for 3 minutes and covered with urethane. A coated pesticide 2 was obtained (volume median diameter: 37 μm).

Production Example 3
-Preparation of coated agrochemical 3 The same procedure as in Production Example 2 was carried out except that the height of the agitator blade was adjusted so that the minimum gap between the agitator blade and the bottom surface was 1600 μm. Pesticide 3 was obtained (volume median diameter: 53 μm).

Production Example 4
-Preparation of coated pesticide 4 The same procedure as in Production Example 2 was carried out except that the height of the agitator blade was adjusted so that the minimum gap between the agitator blade and the bottom surface was 400 μm. Pesticide 4 was obtained (volume median diameter: 45 μm).

Comparative production example 1
-Preparation of comparative coated pesticide 1 Except that the height of the agitator blade was adjusted so that the minimum gap between the agitator blade and the bottom surface was 50 μm, the same operation as in Production Example 2 was performed, and the product was coated with urethane. Comparative coated pesticide 1 was obtained (volume median diameter: 41 μm).

Test example 1 (surface atomic concentration measurement)
Using an X-ray photoelectron spectrometer (XPS) JPS-9010MC manufactured by JEOL, about 20 to 30 mg of the coated pesticide obtained in the above production example was formed into 8 mmφ tablets using a tablet molding machine. The obtained tablets were placed on a sample stage, and the spectra of Cl2p, S2p, N1s, Ca2p, O1s, C1s, Si2p, and Al2p were measured with an X-ray source AlKα (10 kV, 25 mA). The peak area of each measured element was determined, and the surface atom concentration was calculated using the JEOL-provided relative sensitivity correction coefficient. The results are shown in Table 1.

比較被覆農薬１に比べて、被覆農薬１〜４はクロチアニジン由来のＣｌ原子、Ｓ原子の表面原子濃度が低く、効率良く被覆されていることが確認された。

Compared with the comparative coated pesticide 1, the coated pesticides 1 to 4 have lower surface atomic concentrations of clothianidin-derived Cl atoms and S atoms, and it was confirmed that they were efficiently coated.

Test example 2 (dissolution test)
450 ml of hard water was added to a 500 ml beaker. A predetermined amount of the coated pesticide obtained in the above production example was added thereto. (The predetermined amount is such that the concentration when clothianidin in the test-coated pesticide is completely eluted is 50 ppm.) Three days after input, the amount of clothianidin in each test solution was measured by the LC-IS method. The elution rate of each clothianidin was calculated using the following formula. During the test period, the water in the beaker was stirred at 100 rpm using a circular stirrer (diameter 25 mm, thickness 15 mm), and the water temperature was controlled to 25 ± 1 ° C.

Dissolution rate (%)
= (Amount of clothianidin in test solution / total amount of clothianidin in test coated pesticide) × 100

The results are shown in Table 2.

比較被覆農薬１に比べて、被覆農薬１〜４はクロチアニジンの溶出率が低く、徐放性能が高い。

Compared with comparative coated agricultural chemical 1, coated agricultural chemicals 1 to 4 have a lower elution rate of clothianidin and higher sustained release performance.

Claims (7)

A powder and a thermosetting material containing a bioactive component in a tank and a mixer having a rotary blade at the bottom of the tank and a minimum distance between the bottom surface of the tank and the rotary blade of 100 μm or more Having a step of mixing resin raw materials,
A method for producing a coating composition in which the powder is coated with a thermosetting resin.   The manufacturing method according to claim 1, wherein the minimum distance between the tank and the rotary blade is 400 to 1600 μm.   The production method according to claim 1, wherein the volume median diameter of the coating composition is 10 to 200 μm.   The method according to any one of claims 1 to 3, wherein the biologically active ingredient is clothianidin.   The method according to any one of claims 1 to 4, wherein the thermosetting resin is a urethane resin. Adjusting the minimum distance between the bottom surface of the tank and the rotary blade of the mixer having a rotary blade at the bottom of the tank and the tank to 100 μm or more, and
The manufacturing method of the coating composition with which this powdery material was coat | covered with the thermosetting resin which has the process of mixing the powdery material containing a bioactive component, and a thermosetting resin raw material in this mixer.   The coating composition manufactured with the manufacturing method of any one of Claims 1-6.