JP2014111571A - Agrochemical granule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agrochemical granule containing a compound represented by the following formula (I), free from the problem of the decomposition of the compound represented by the following formula (I), the agrochemical granule suitable for an application to a nursery box for paddy rice seedling.SOLUTION: An agrochemical granule contains a compound represented by formula (I), where R, R, R, R, R, R, R, R, Xand Xeach represent definitions described in the specifications, calcium carbonate, alpha starch or polyvinyl alcohol, wherein the agrochemical granule contains the calcium carbonate in an amount of 80 wt.% or more.

Description

  The present invention relates to an agrochemical granule.

  In the cultivation of paddy rice, by applying the agrochemical formulation to the seedling box in advance, the agrochemical active ingredient contained in the agrochemical formulation is also applied to the paddy field at the same time as transplanting the seedlings grown in the seedling box to the paddy field, When the efficacy of the pesticidal active ingredient can be expressed even after transplantation, it becomes an efficient control method, and many pesticidal formulations for application to the control method have been developed.

〔式中、
Ｒ¹は水素原子又はメチル基を表し、
Ｒ²は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ³は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ⁴は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ⁵は水素原子、Ｃ１−Ｃ４アルキル基又はＣ１−Ｃ４アルキルアミノ基を表し、
Ｒ⁶は水素原子又はメチル基を表し、
Ｒ⁷はメチル基又はエチル基を表し、
Ｒ⁸はアミノ基、Ｃ１−Ｃ４アルキルアミノ基又はジ（Ｃ１−Ｃ４アルキル）アミノ基を表し、
Ｘ¹及びＸ²はいずれも水素原子を表すか、又は、Ｘ¹及びＸ²が一緒になり単結合を表す。〕
で示される化合物が殺虫化合物として知られている（例えば、特許文献１及び特許文献２参照）。
また、前記式（Ｉ）で示される化合物と、チアジニル等の植物病害防除活性化合物とを含有する農薬粒剤組成物を水稲育苗箱に施用することも知られている（例えば、特許文献３参照）。 On the other hand, the following formula (I)

[Where,
R ¹ represents a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ³ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁴ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁵ represents a hydrogen atom, a C1-C4 alkyl group or a C1-C4 alkylamino group,
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ represents a methyl group or an ethyl group,
R ⁸ represents an amino group, a C1-C4 alkylamino group or a di (C1-C4 alkyl) amino group,
X ¹ and X ² both represent a hydrogen atom, or X ¹ and X ² together represent a single bond. ]
Is known as an insecticidal compound (see, for example, Patent Document 1 and Patent Document 2).
It is also known to apply an agrochemical granule composition containing the compound represented by the formula (I) and a plant disease control active compound such as thiazinyl to a paddy rice seedling box (for example, see Patent Document 3). ).

International Publication No. 93/09126 International Publication No. 97/00265 JP 2011-157352 A

In a conventional granule containing the compound represented by the formula (I) (hereinafter sometimes referred to as the present compound A), for example, the present compound A is decomposed during storage or transportation at a high temperature. There are things to do.
An object of the present invention is to provide an agrochemical granule containing the present compound A that does not have a problem of decomposition of the present compound A, and suitable for use in paddy rice seedling boxes.

〔式中、
Ｒ¹は水素原子又はメチル基を表し、
Ｒ²は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ³は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ⁴は水素原子、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４ハロアルキル基又は（Ｃ１−Ｃ４アルキル）カルボニル基を表し、
Ｒ⁵は水素原子、Ｃ１−Ｃ４アルキル基又はＣ１−Ｃ４アルキルアミノ基を表し、
Ｒ⁶は水素原子又はメチル基を表し、
Ｒ⁷はメチル基又はエチル基を表し、
Ｒ⁸はアミノ基、Ｃ１−Ｃ４アルキルアミノ基又はジ（Ｃ１−Ｃ４アルキル）アミノ基を表し、
Ｘ¹及びＸ²はいずれも水素原子を表すか、又は、Ｘ¹及びＸ²が一緒になり単結合を表す。〕
で示される化合物と、炭酸カルシウムと、アルファー澱粉またはポリビニルアルコールとを含有する農薬粒剤であって、前記炭酸カルシウムを８０重量パーセント以上含有する農薬粒剤。
〔２〕 農薬活性成分を含有する農薬含有粉体が熱硬化性樹脂で被覆されてなり、平均粒子径が１０〜２００μmである被覆粒状農薬と、前記式（Ｉ）で示される化合物と、炭酸カルシウムと、アルファー澱粉またはポリビニルアルコールとを含有する〔１〕に記載の農薬粒剤。
〔３〕 前記式（Ｉ）で示される化合物が、スピノシンＡ、スピノシンＤ、スピネトラムＪ及びスピネトラムＬからなる群より選ばれる１種以上の化合物である〔１〕または〔２〕に記載の農薬粒剤。
〔４〕 前記式（Ｉ）で示される化合物が、スピネトラムである〔１〕または〔２〕に記載の農薬粒剤。 The present inventor has studied the present invention to find an agrochemical granule containing the present compound A that is free from degradation problems of the present compound A and suitable for use in paddy rice seedling boxes. In addition, in the agricultural chemical granules containing alpha starch or polyvinyl alcohol, it was found that the decomposition of the present compound A during storage can be suppressed by setting the calcium carbonate content to 80 weight percent or more.
That is, the present invention is as follows [1] to [4].
[1] Formula (I)

[Where,
R ¹ represents a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ³ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁴ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁵ represents a hydrogen atom, a C1-C4 alkyl group or a C1-C4 alkylamino group,
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ represents a methyl group or an ethyl group,
R ⁸ represents an amino group, a C1-C4 alkylamino group or a di (C1-C4 alkyl) amino group,
X ¹ and X ² both represent a hydrogen atom, or X ¹ and X ² together represent a single bond. ]
A pesticidal granule containing a compound represented by the formula: calcium carbonate and alpha starch or polyvinyl alcohol, the pesticidal granule containing 80% by weight or more of the calcium carbonate.
[2] A coated agrochemical comprising an agrochemical-containing powder containing an agrochemical active ingredient and coated with a thermosetting resin and having an average particle size of 10 to 200 μm, a compound represented by the formula (I), and carbonic acid The agrochemical granule according to [1], containing calcium and alpha starch or polyvinyl alcohol.
[3] The agrochemical grain according to [1] or [2], wherein the compound represented by the formula (I) is one or more compounds selected from the group consisting of spinosyn A, spinosyn D, spinetram J and spinetram L Agent.
[4] The agrochemical granule according to [1] or [2], wherein the compound represented by the formula (I) is spinetoram.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an agrochemical granule for treating paddy rice seedling boxes that does not have a problem of decomposition of the contained compound A.

  The present compound A is, for example, a compound described in JP-A-2009-132670, WO 93/09126 and WO 97/00265, and can be produced by the method described in the document. . Content of this compound A with respect to the agrochemical granule (henceforth this invention granule) of this invention is 0.1 to 5 weight% normally, Preferably it is 0.2 to 2 weight%.

式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｘ¹及びＸ²は〔表１〕に記載の組合せを表す。 As this compound A, the following compounds are mentioned, for example.
A compound represented by the following formula (I);

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X ¹ and X ² represent the combinations described in [Table 1].

Among the compounds A, in [Table 1], the compound described in No. 1 is spinosyn A, the compound described in No. 4 is spinosyn D, and the compound described in No. 23 is described in spinetoram J, No. 24. Is a compound known as spinetoram L.
In addition, as a general name spinosad, a mixture of the compound described in No. 1 (spinosine A) and the compound described in No. 4 (spinosine D) is known as an active ingredient of agricultural chemicals. A mixture of the compound described in .23 (Spinetram J) and the compound described in No. 24 (Spinetram L) is known as an active ingredient of agricultural chemicals, and these can also be used in the present invention.

The calcium carbonate used for the granule of the present invention (hereinafter sometimes referred to as the present calcium carbonate) will be described. Calcium carbonate is roughly classified into two types, heavy calcium carbonate and precipitated calcium carbonate, depending on its production method, and any calcium carbonate may be used in the granule of the present invention.
Heavy calcium carbonate, also called natural calcium carbonate, is produced by mechanically crushing and classifying natural raw materials mainly composed of CaCO ₃ such as limestone, shells and chalk (dry or wet).
Precipitated calcium carbonate, also called synthetic calcium carbonate, dissolves quick lime obtained by calcining limestone in water and turns it into lime milk, or carbon dioxide gas method by blowing carbon dioxide, or soda calcium chloride or lime milk in water Manufactured by a soluble salt reaction method by reacting with ash.

  The granule of the present invention contains the calcium carbonate usually in an amount of 80 to 99% by weight, preferably 85 to 98% by weight, based on the total weight of the granule of the present invention.

The granule of the present invention contains alpha starch or polyvinyl alcohol as a binder. By using alpha starch or polyvinyl alcohol, it becomes an agrochemical granule that is non-disintegrating when contacted with water (hereinafter, sometimes referred to as an underwater non-disintegrating agrochemical granule).
In the present invention, the alpha starch refers to heating an aqueous suspension of ordinary starch (beta starch), making it alkaline, or adding salts to form a viscous transparent or translucent starch paste. It refers to a powder that is easily swelled and / or dissolved in cold water, obtained by immediately drying the paste using a spray dryer or the like. Examples of the commercially available alpha starch include amylox No. 1A (manufactured by Nippon Corn Starch Co., Ltd.).
In the present invention, the non-disintegrating agrochemical granule in water means an agrochemical granule having a disintegration time in water of 24 hours or more. More specifically, the method for measuring the disintegration time in water is as follows. First, put 50 mL of hard water 3 times in a glass petri dish with a diameter of 9 cm, and let it stand so that the five test granules are almost uniform. To do. And the disintegration time in water can be calculated | required by measuring the time until a test granule stops an original form immediately after injection | pouring.

  The granule of the present invention contains alpha starch or polyvinyl alcohol in an amount of usually 0.5 to 10 percent by weight, preferably 1 to 5 percent by weight based on the total weight of the granule of the present invention.

  The granule of the present invention is a coated granular pesticide (hereinafter referred to as the present coated granular pesticide) having an average particle size of 10 to 200 μm, which is obtained by coating a pesticide-containing powder containing an agrochemical active ingredient with a thermosetting resin. It is preferable to further contain. The present coated granular pesticide is a coated granular pesticide having sustained release performance in which a pesticide-containing powder is hardened with a thermosetting resin and coated.

Such a coated granular pesticide can be produced, for example, by the method described in JP-A-2007-119442.
Specifically, this coated granular pesticide is produced, for example, as follows. That is, the production method (hereinafter sometimes referred to as the present coated granular pesticide production method) is:
(1) A step of mixing the agrochemical-containing powder and a first liquid raw material that is a raw material of the thermosetting resin (hereinafter, sometimes referred to as step (1)),
(2) A step of adding a second liquid raw material to be a raw material of the thermosetting resin to the mixture obtained in the previous step (hereinafter, sometimes referred to as step (2)),
(3) A step of obtaining a thermosetting resin solidified product of an agrochemical-containing powder by reacting the first liquid raw material and the second liquid raw material to produce a thermosetting resin (hereinafter, step (3) and May be noted), and
(4) A first liquid raw material and a second liquid raw material, which are raw materials for the thermosetting resin, are added simultaneously or sequentially to the thermosetting resin solidified product of the agrochemical-containing powder obtained in the previous step, and the first liquid raw material is added. And the second liquid raw material are reacted to coat the thermosetting resin solidified product of the agrochemical-containing powder with a thermosetting resin (hereinafter sometimes referred to as step (4)).
including.

In the present invention, the average particle size of the agricultural chemical-containing powder (hereinafter sometimes referred to as the present agricultural chemical powder) is usually 1 to 100 μm, preferably 1 to 30 μm. Is usually 10 to 200 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm.
In the present invention, the present pesticidal powder may be a powdery pesticidal active ingredient alone, but is usually a composition containing an pesticidal active ingredient and a diluted powder, preferably substantially an agrochemical active ingredient and a diluted powder. It is a composition which consists of.
In the present invention, the average particle diameter means a volume median diameter. The volume median diameter can be measured by, for example, a laser diffraction particle size measuring instrument such as MASTERSIZER2000 manufactured by MALVERN.

Examples of the pesticidal active ingredient contained in the present coated granular pesticide include an insecticidal compound, a bactericidal compound, a herbicidal compound, and a plant growth regulating compound. Such an agrochemical active ingredient has a water solubility of 100 ppm or more at 20 ° C., and is an agrochemical active ingredient that is solid at 20 ° C. As the agrochemical active ingredient used in the present invention, it is preferable to use an agrochemical active ingredient that is solid even at 50 ° C.
Examples of such agrochemical active ingredients include the following compounds.

  Examples of insecticidal compounds include propoxer, isoprocarb, XMC, pirimicarb, carbofuran, mesomil, acephate, trichlorfone, dimethylvinphos, cyromazine, imidacloprid, acetamiprid, clothianidin, nitenpyram, thiamethoxam, dinotefuran, thiaclopridio citrum salt, , Flonicamid, MIPC, thiosultap Na salt.

  As the pesticidal active ingredient contained in the present coated granular pesticide, among the above insecticidal compounds, the use of neonicotinoid compounds is preferred. Examples of such neonicotinoid compounds include imidacloprid, thiacloprid, clothianidin, thiamethoxam, nitenpyram, dinotefuran, and acetamiprid, and clothianidin is more preferable.

  Examples of the bactericidal compound include metalaxyl, furametopir, trifluzamide, pyrimethanil, kasugamycin, polyoxin, validamycin, metminostrobin, tricyclazole, pyroxylone, probenazole, ferrimzone, and microbutanyl.

  As herbicidal compounds, for example, metribuzin, fluometuron, 2,4-D, dicamba, mecoprop, primsulfuron methyl, imazosulfuron, sulfosulfuron, imazapyr, imazetapir, bispyrivac Na salt, acifluorfen Na salt, sulfentrazone, Mention may be made of paraquat, triflusulfuronmethyl, glufosinate ammunium salt, glyphosate, bentazone, propanyl and tebuthiuron.

  Examples of the plant growth regulating compound include maleic hydrazide, etephone, gibberellic acid, and mepicut chloride.

When the pesticidal powder contains a diluted powder, the amount of the pesticidal active ingredient is usually 1 to 95 weight percent, preferably 10 to 90 weight percent based on the total weight of the pesticidal powder. The amount is usually 5 to 99 weight percent, preferably 10 to 90 weight percent.
The diluted powder is a powdery solid carrier usually used for agricultural chemical powders, and the average particle size of the diluted powder is usually 1 to 100 μm. 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, zeolite, tuff, vermiculite, laponite, pumice, diatomaceous earth, acid clay, activated white And the like.
The present pesticidal powder is obtained by mixing and pulverizing a pesticidal active ingredient and, if necessary, a diluted powder. This agrochemical powder can also be obtained by mixing each component pulverized in advance.

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 sometimes referred to as a first liquid component and a second liquid component). It can be manufactured by the present coated granular pesticide manufacturing method. In addition, as a thermosetting resin in this coated granular agrochemical, a urethane resin is preferable.

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 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 polyisocyanate (polymeric MDI) obtained by phosgenating a polyamine through 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.
As the curing agent, polyamine is usually used. Examples of polyamines include diethylenetriamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, methyliminobispropylamine, mensendiamine, metaphenylenediamine, diaminophenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, polyamide-modified polyamine, and ketone. Examples include modified polyamines, epoxy modified polyamines, thiourea modified polyamines, Mannich modified polyamines, and Michael addition modified polyamines.
Examples of the compound having a glycidyl group include polyglycidyl ether and polyglycidylamine. Examples of the polyglycidyl ether 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. Ether, bisphenol AF type polyglycidyl ether, biphenyl type polyglycidyl ether, fluorin type polyglycidyl ether, phenol novolac type polyglycidyl ether, o-cresol novolac type polyglycidyl ether, DPP novolac type polyglycidyl ether, trishydroxyphenylmethane type Examples include polyglycidyl ether and tetraphenylolethane type polyglycidyl ether. Examples of the polyglycidylamine include tetraglycidyldiaminodiphenylmethane type polyglycidylamine, hydantoin type polyglycidylamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, aniline type polyglycidylamine, and toluidine type polyglycidyl. Examples include amines, triglycidyl isocyanurate type polyglycidyl amines, and aminophenol type polyglycidyl amines.

  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).

Next, the four steps of the method for producing a coated granular pesticide will be described.
In the step (1), the first liquid component is usually added to the container while the agricultural chemical powder is rolled in the container under dry conditions in which the agricultural chemical powder is not dispersed in the liquid medium. In this step, the agrochemical powder and the first liquid component are mixed to obtain a mixture of the agrochemical powder and the first liquid component. By rolling the mixture of the pesticidal powder and the first liquid component in a container for an appropriate time, the individual particles in the pesticidal powder are covered with the first liquid component.
Step (1) is usually performed at 0 to 100 ° C, preferably 20 to 90 ° C. From the viewpoint of safety, implementation in a nitrogen atmosphere is preferable.

In the step (1), as a method of rolling the agrochemical powder in a container under dry conditions, for example, the following methods are used.
a) A method of rotating a bread-shaped or drum-shaped container containing the pesticide powder around an oblique or horizontal axis;
b) In a container containing the agrochemical powder, a stirring blade having the same size as the diameter of the bottom surface of the container is installed and rotated;
c) A method of applying an air flow to the pesticide powder in a container containing the pesticide powder.
In the step (1), when the first liquid component is added to the pesticidal powder in a rolling state, the first liquid component is spread on the surface of the individual particles of the pesticidal powder. The individual particles of the agrochemical powder are covered with the first liquid component. Furthermore, by continuing the rolling state, the first liquid component is usually distributed almost uniformly on the surface of all particles of the agricultural chemical powder.
In step (1), the first liquid component having a low viscosity (for example, 1000 mPa · s (25 ° C. or less)) is used in order to uniformly coat all the particles of the agricultural chemical powder with the first liquid component. It is preferable.

In step (2), the second liquid component is added to the container while rolling the mixture obtained in the previous step (1), that is, the mixture of the agrochemical powder and the first liquid component in the container. This is a step of obtaining a mixture of the agrochemical powder, the first liquid component, and the second liquid component.
Step (2) is usually performed at the same temperature as step (1), that is, 0 to 100 ° C., preferably 20 to 90 ° C. From the viewpoint of safety, implementation in a nitrogen atmosphere is preferable.

The second liquid component added in the step (2) is a reactive functional group in the second liquid component with respect to an equivalent amount of the reactive functional group in the first liquid component added in the previous step (1). Is generally used in an amount such that it is 0.9 to 1.05, preferably 0.95 to 1.00.
When the thermosetting resin is a urethane resin and the first liquid component is a polyol, the second liquid component is a polyisocyanate, but the equivalent of the hydroxyl group (OH) in the polyol used in the previous step (1). On the other hand, the isocyanate group (NCO) equivalent in the polyisocyanate added in the step (2) is 0.8 to 1.1, preferably 0.9 to 1.1, more preferably 0.95 to 1.05. The amount of polyisocyanate is adjusted appropriately so that
In the step (2), it is preferable to use a second liquid component having a low viscosity (for example, 300 mPa · s (25 ° C. or less)).

In the step (3), the first liquid component and the second liquid component are reacted with each other while applying a shearing force to the mixture obtained in the previous step (2) using a rotating blade or the like. This is a step of generating a thermosetting resin.
Step (3) is usually carried out at 0 to 100 ° C, preferably 20 to 95 ° C, more preferably 40 to 90 ° C. It is easy to operate at the same temperature as in step (1) and step (2). This step is also preferably performed in a nitrogen atmosphere from the viewpoint of safety.
Depending on the operating temperature in step (3), the type of thermosetting resin, the presence or absence of a curing catalyst, the time required for the uncured thermosetting resin to cure varies. When the curing rate of the thermosetting resin is sufficiently high, the first liquid component and the second liquid in the step (3) are substantially added before the addition of all the second liquid component in the step (2). A reaction with the liquid component starts and a part of the thermosetting resin is generated. In such a case, in the step (2), the mixture of the agrochemical powder and the first liquid component is rolled in a container, and further the shear force is applied to the mixture with a rotating blade or the like, It is preferable to add two liquid components.

  In the step (3), as a method of giving shearing force to the mixture of the agrochemical powder, the first liquid component, and the second liquid component with a rotating blade, specifically, the tip portion of the blade is The blade rotating in the range of 50 to 3000 m / min, preferably 100 to 2000 m / min, more preferably 200 to 1000 m / min, is used for the agrochemical powder, the first liquid component, and the second liquid component. The method of making it contact with a mixture is mentioned. At this time, the operation of applying the shearing force is performed until the time when the thermosetting resin does not exhibit tackiness, and the entire mixture of the agrochemical powder, the first liquid component, and the second liquid component is almost even. It is preferable to appropriately adjust the amount of the pesticide powder charged in the container, the number of rotating blade pairs, and the like so that a shearing force is applied.

  Step (3) is usually performed until the uncured thermosetting resin is completely cured and the resulting thermosetting resin solidified product of the agrochemical powder does not exhibit tackiness. This time varies depending on the properties of the thermosetting resin and the operating temperature.

  In this coated granular agrochemical production method, in addition to the above steps (1) to (3), step (4) is further performed once or a plurality of times. In the step (4), the first liquid component and the second liquid component are added simultaneously or sequentially to the thermosetting resin solidified product of the agricultural chemical powder obtained as described above, and the first liquid component and This is a step of reacting the second liquid component to coat the thermosetting resin solidified product of the agrochemical powder with the thermosetting resin. The step (4) is to thicken the thermosetting resin film. Thus, the release of the pesticidal active ingredient can be further delayed. That is, the release rate of the pesticidal active ingredient can be adjusted according to the purpose.

  The total amount of the first liquid component and the second liquid component, that is, the amount of the uncured thermosetting resin added in one operation of the step (1) and the step (2) or the step (4). Can be changed depending on the type of thermosetting resin, operating temperature, conditions of equipment used, etc., but usually 0.3 to 15 parts by weight, preferably 100 parts by weight of the present agricultural chemical powder. Is 0.5 to 10 parts by weight, and may or may not be changed in step (1) and step (2) or step (4).

As a specific container that can be used in this coated granular pesticide manufacturing method, as a device that causes the particles to make a circular motion along the outer periphery of the container, there is a Negura machine manufactured by Seishin Corporation. A high-speed mixer and high-flex glal manufactured by Earth Technica Co., Ltd. can be used to mix, disperse and shear the input material in a short time by the action of both blades. . Furthermore, as a device having the same performance, there can be mentioned a granumist manufactured by Freund Sangyo Co., Ltd. and a vertical granulator manufactured by Pou Lec Co., Ltd.
For example, a device described in JP-A-9-75703 can be specifically mentioned.

  In this coated granular agricultural chemical, the amount of the thermosetting resin is usually 10 to 300 parts by weight, preferably 20 to 200 parts by weight, and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the present agricultural chemical powder. .

  The coated granular pesticide may contain a flow aid for the purpose of improving its fluidity and preventing caking of the coated granular pesticide. As the flow aid, the aforementioned diluted powder is used.

  The granule of the present invention contains the coated granular agricultural chemical usually in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the granule of the present invention.

  The granule of the present invention is further a formulation aid such as a surfactant, a binder, a solid carrier, a stabilizer, a colorant, and a fragrance, and an agrochemical active ingredient contained in the compound A and the coated granular pesticide. The agrochemical active ingredient (hereinafter, may be referred to as the present compound B) may be contained.

Examples of such surfactants 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 fatty acid ester, polyoxyethylene castor oil derivative, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block polymer , Polyoxyethylene fatty acid amide, alkylol amide, polyoxyethylene amide Nonionic surfactants such as kilamine; fatty acid sodium, sodium polyoxyalkylene alkyl ether carboxylate, alkyl sulfonate, fatty acid ester sulfonic acid, dialkyl sulfosuccinate, fatty acid amide sulfonate, alkyl aryl sulfonate, alkyl aryl Examples include anionic surfactants such as formalin condensates of sulfonates, higher alcohol sulfates, and polyoxyalkylene alkyl phosphates.
When this invention granule contains surfactant, the total content is 0.1 to 5 weight% normally, Preferably it is 0.5 to 2 weight%.

Examples of such solid carriers include kaolin minerals such as kaolinite, dickanite, nacrite, and hallosite, serpentine such as chrysotile, lizarite, anticorite, and amesite, montmorillonite minerals such as sodium montmorillonite, calcium montmorillonite, and magnesium montmorillonite, and saponite. , Smectite such as hectorite, soconite, and hydelite, pyrophyllite, talc, wax, mica such as muscovite, fengite, sericite, illite, silica such as cristobalite, quartz, hydrous magnesium silicate such as attapulgite, sepiolite, Sulphate minerals such as gypsum, dolomite, zeolite, tuff, vermiculite, laponite, pumice, diatomaceous earth, acid clay, activated clay, etc .; Plant-based carriers such as shicob flour, walnut shell flour, rice husk, wheat flour, wood flour, straw, bran, soybean flour; urea, lactose, sucrose, salt, salt cake, sodium tripolyphosphate, potassium pyrophosphate, ammonium sulfate, etc. A water-soluble carrier is mentioned.
When the granule of the present invention contains a solid carrier, the total content is usually 0.1 to 20 percent by weight, preferably 1 to 10 percent by weight.

  Such stabilizers include, for example, epoxidation of phenol antioxidants, amine antioxidants, phosphoric antioxidants, sulfur antioxidants, UV absorbers, epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, etc. Examples include vegetable oils, isopropyl acid phosphate, liquid paraffin, and ethylene glycol.

  Examples of such colorants include rhodamines such as rhodamine B and solar rhodamine, and dyes such as yellow No. 4, blue No. 1, and red No. 2.

  Examples of such fragrances include ester fragrances such as ethyl acetoacetate, ethyl enanthate, ethyl cinnamate, and isoamyl acetate, organic acid fragrances such as caproic acid and cinnamic acid, and alcohol fragrances such as cinnamon alcohol, geraniol, citral, and decyl alcohol. , Aldehydes such as vanillin, piperonal and perylaldehyde, ketone flavors such as maltol and methyl β-naphthyl ketone, and menthol.

  The present compound B is not particularly limited and includes various conventionally known herbicidal compounds, plant growth regulating compounds, fungicidal compounds, insecticidal compounds, insect growth regulating compounds and the like.

  Examples of insecticidal compounds and insect growth regulating compounds that may be used as the present compound B include pyrethroid compounds such as deltamethrin, tralomethrin, acrinathrin, tetramethrin, tefluthrin, etc .; , Mesomil, phenoxycarb, carnomate compounds such as fenobucarb; acephate, trichlorfone, tetrachlorbinphos, dimethylbinphos, pyridafenthion, pyrimifosmethyl, fenthion, fenitrothion, diadion, quinalphos, isoxathione, pyridafenthion, chlorpyrifosmethyl, bamidthioneate, malathione , Dimethoate, disulfone, monochrome Organic phosphorus compounds such as phos, chlorfenvinphos, propaphos, EPN, pyracrophos, azine phosethyl, azine phosmethyl; diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, flucycloxuron, cyromazine, diafenthiuron , Hexothiazox, Novallon, teflubenzuron, triflumuron, 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) Nyl] urea, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazon-4-one, 1- (2,6-difluoro Urea compounds such as benzoyl) -3- [2-fluoro-4- (1,1,2,2-tetrafluoroethoxy) phenyl] urea; neonicoti such as imidacloprid, acetamiprid, clothianidin, nitenpyram, thiamethoxam, dinotefuran, thiacloprid Noid compounds; Diamide compounds such as fulvendiamide, chlorantraniliprole, cyantraniliprole; Phenylpyrazole compounds such as fipronil and etiprole, Tetramic acid compounds such as spirotetramat, spiromesifene, spirodiclofen, cartap , Buprofezin, thiocyclam, bensultap, phenazaquin, fenpyroximate, pyridaben, hydramethylnon, chlorfenapyr, fenproximate, pymetrozine, pyrimidifene, tebufenozide, tebufenpyrad, triazamate, indoxacarb, sulfuramide, milbemectin, avermectin, benzene It is done.

  Examples of bactericidal compounds that may be used as the present compound B include benzimidazole compounds such as benomyl, carbendazim, thiabendazole, and thiophanate methyl; phenylcarbamate compounds such as dietofencarb; dicarboximide compounds such as procimidone, iprodione, and vinclozoline; diniconazole, prope Azole compounds such as nazole, epoxiconazole, tebuconazole, difenoconazole, cyproconazole, flusilazole, triadimephone; acylalanine compounds such as metalaxyl; carboxyamide compounds such as furametopyl, mepronil, flutolanil, trifluzamide; tolcrofosmethyl, fosetilaluminum Organophosphorus compounds such as pyrazophos; pyrimesanil, mepanipyrim, cyprodinil, etc. Nilinopyrimidine compounds; Cyanopyrrole compounds such as fludioxonil and fenpiclonil; Antibiotics such as blasticidin S, kasugamycin, polyoxin and validamycin; Methoxy acrylate compounds such as azoxystrobin, cresoxime methyl, and SSF-126; Chlorothalonil, manzeb, captan , Folpet, Tricyclazole, Pyroxylone, Probenazole, Fusaride, Simoxanyl, Dimethomorph, CGA245704, Famoxadone, Oxolinic acid, Fluazinam, Ferimzone, Diclocimet, Clotenazone, Isovaradione, Tetrachloroisophthalonitrile, Thiophthalimidooxybisphenoxyarsine, 3 -Iodo-2-propylbutyl carbamate, parahydroxybenzoic acid Esters, sodium dehydroacetate, potassium sorbate, orysastrobin, isotianil, triazinyl, is thiuram and the like.

  Examples of herbicidal compounds that may be used as the present compound B include, for example, bensulfuron methyl, pyrazosulfuron ethyl, azimusulfuron, sulfosulfuron, imazosulfuron, propyrisulfuron, fenmedifam, ashram, pyributycarb, propachlor, metazachlor, Tenilchlor, simazine, atrazine, propazine, cyanazine, amethrin, simethrin, dimetamethrin, promethrin, isoxaben, diflufenican, diuron, linuron, fluometuron, methyl diemron, isoproturon, isouron, tebuthiuron, metabenzothiazurone, propanil, propanil , Bromobutide, Daimlon, Etobenzanide, Indanophan, Amitrol, Sulfen Razone, fentolazamide, isoxaflutole, chloridazone, norflurazon, pyrithiobac, bromacil, terbacil, metribudine, oxadiclomephone, cinmethyline, flumicrolacpentyl, flumioxazin, fluthiaset methyl, azaphenidin, oxadiazone, oxadiargyl, pentoxazone, fentoxatrol, pyrimotrol Examples include methyl, sodium bispyribac, pyriftalide, indanophan, benzobicyclone, dithiopyr, chlorthiamid, and pretilachlor.

  Examples of the plant growth regulating compound that may be used as the present compound B include maleic hydrazide, chlormecat, etephone, gibberellin, mepicut chloride, thidiazuron, inabenfide, paclobutrazole, uniconazole.

  The granule of the present invention was obtained by kneading the mixture containing the present compound A, the present coated granular pesticide, the present calcium carbonate, and, if necessary, a formulation adjuvant and / or the present compound B with water. It can be produced by granulating the kneaded product, then drying the obtained granulated product, and crushing, sieving, sizing, etc., if necessary. The amount of water added during kneading is usually 3 to 50 parts by weight with respect to 100 parts by weight of the mixture. Examples of the kneader used for kneading include a kneader, a Nauter mixer, and a Redige mixer.

  When the kneaded product is extruded and granulated, it is usually performed using a screen of 0.5 to 2.0 mmφ, preferably 0.7 to 1.5 mmφ. The granulated product after extrusion granulation is usually dried at 30 to 90 ° C, preferably 30 to 80 ° C. The grain length of the granule of the present invention is usually 0.5 to 6.0 mm, preferably 0.7 to 4.0 mm. In addition, the grain length in this invention means the maximum length which a grain can take. As the extrusion granulator, screw type extrusion granulator, roll type extrusion granulator, disc pelleter type extrusion granulator, pellet mill type extrusion granulator, basket type extrusion granulator, blade type extrusion granulator Machine, oscillating extrusion granulator, gear type extrusion granulator, ring die type extrusion granulator and the like.

  The granule of the present invention is a non-disintegrating pesticide granule in water, and is suitable for use in paddy rice seedling box treatment. The paddy rice seedling box is a seedling box having a size of 30 cm × 60 cm (inner diameter: 28 cm × 58 cm) and growing rice seedlings until rice planting (generally for 20 to 40 days). The paddy rice seedling box treatment is a simple control means for spraying granules to a seedling box in order to control pests that occur in the Honda after planting rice.

  Next, the present invention will be described in more detail with reference to production examples, test examples, and the like, but the present invention is not limited to only these examples.

Reference Production Example 1 Preparation of Powdered Pesticide Composition 1 30.0 parts by weight of spinetoram and 70.0 parts by weight of calcium carbonate (for Tankar granules, manufactured by Yakusen Lime Co., Ltd.) are uniformly mixed, and a centrifugal grinder The powdered pesticide composition 1 containing spinetoram having a volume median diameter of 4.19 μm (measured by MASTERSIZER 2000 manufactured by MALVERN) was obtained.

Reference Production Example 2 Preparation of Pesticide-Containing Powder 1 70.0 parts by weight of (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (hereinafter referred to as ) And 30.0 parts by weight of beryl (Clay S, manufactured by Katsumiyama Mining Co., Ltd.) are uniformly mixed, using a dry pulverizer (turbo mill, model: T400, manufactured by Turbo Kogyo Co., Ltd.). Pulverized to obtain an agrochemical-containing powder 1 containing clothianidin having a volume median diameter of 9.9 μm (measured by MASTERSIZER 2000 manufactured by MALVERN).

Reference Production Example 3 Preparation of coated granular agricultural chemical 1 46.3 parts by weight of branched polyether polyol (Sumiphen TM, manufactured by Sumika Bayer Urethane Co., Ltd.), 52.2 parts by weight of linear polyether polyol (Sumiphen 1600U, Sumika Bayer Urethane Co., Ltd.) and 1.5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol (made by Kayaku Akzo Co., Ltd.) are uniformly mixed to obtain a liquid mixture of polyol and catalyst. (Hereinafter referred to as polyol premix 1). The viscosity of the polyol premix 1 was 322 mPa · s (B-type viscometer, 25 ° C., 12 revolutions, rotor No. 1).
100 parts by weight of the agrochemical-containing powder 1 is charged in a container of a high-speed mixer device (FS-GS-200 type; round plate type, manufactured by Fukae Pautech Co., Ltd.), and the agitator blades and chopper blades of the device are each rotated at a rotational speed. It was rotated at 170 rpm and 2500 rpm. Next, the container was heated to bring the temperature of the agrochemical-containing powder 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 after that, in a state where the product temperature was maintained at 85 ± 3 ° C., 1.07 parts by weight of polymethylene polyphenyl polyisocyanate (Sumijoule 44V10, manufactured by Sumika Bayer Urethane Co., Ltd., viscosity 130 mPa · s (B A mold viscometer, 25 ° C., 12 revolutions, rotor No. 1)) was added over 2 minutes. Six minutes after that, the following urethane addition operation was performed 22 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 polymethylene polyphenyl polyisocyanate over 2 minutes-> wait for 6 minutes.

To 100 parts by weight of the powder obtained after the urethane addition operation (22 times), 4.76 parts by weight of calcium carbonate (NS # 2300, manufactured by Nitto Flour Chemical Co., Ltd.) was added and stirred for 3 minutes. A coated granular pesticide 1 was obtained (volume median diameter: 40 μm).

Production Example 1 Preparation of Pesticide Granule 1 of the Present Invention Powdered Pesticide Composition 1 2.0 parts by weight, coated granular pesticide 1 3.9 parts by weight, alpha starch (Amylox No. 1A, manufactured by Nippon Corn Starch Co., Ltd.) 5.0 A mixture of 8 parts by weight of calcium carbonate (SS # 80, manufactured by Nitto Flour Chemical Co., Ltd.) and 8.1 parts by weight of wax (Clay S, manufactured by Katsumiyama Mining Co., Ltd.) About 18 parts by weight of water containing 1.0 part by weight (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Co., Ltd.) was added and kneaded. About 1.5 kg of the obtained kneaded material is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, manufactured by Hata Plant), and only for 10 seconds. The granulator was operated. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The present agricultural chemical granule 1 was obtained.

Production Examples 2-5 Preparation of Present Agricultural Chemical Granules 2-5 Using the raw materials listed in Table 2, the same operations as in Production Example 1 were carried out to produce the present agricultural chemical granules 2-5, respectively.

なお、表２におけるポリビニルアルコールとして、株式会社クラレ製のクラレポバールＰＶＡ２１７Ｓを使用した。

In addition, as a polyvinyl alcohol in Table 2, Kuraray Poval PVA217S manufactured by Kuraray Co., Ltd. was used.

Comparative Production Examples 1 and 2 Preparation of Comparative Agrochemical Granules 1 and 2 Using the raw materials shown in Table 3, the same operations as in Production Example 1 were performed to produce comparative agrochemical granules 1 and 2, respectively.

Test Example 1 (Stability test)
Inventive agricultural chemical granules 1, 2, 4, and 5 and comparative agricultural chemical granules 1 and 2 were placed in 100 g aluminum-interior craft bags, respectively, and stored in a 40 ° C. incubator for 3 months. After storage, the agrochemical granule was taken out, spinetoram contained in each agrochemical granule after storage was quantified by a known quantitative method, and the decomposition amount of spinetoram during storage was determined by the following formula (1).

Formula (1) Decomposition amount (g) = Spinetram content per 100 g of pesticide granules before storage (g) −Spinetram content per 100 g of pesticide granules after storage (g)

The results are shown in Table 4.

Claims (4)

Formula (I)

[Where,
R ¹ represents a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ³ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁴ represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a (C1-C4 alkyl) carbonyl group,
R ⁵ represents a hydrogen atom, a C1-C4 alkyl group or a C1-C4 alkylamino group,
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ represents a methyl group or an ethyl group,
R ⁸ represents an amino group, a C1-C4 alkylamino group or a di (C1-C4 alkyl) amino group,
X ¹ and X ² both represent a hydrogen atom, or X ¹ and X ² together represent a single bond. ]
A pesticidal granule containing a compound represented by the formula: calcium carbonate and alpha starch or polyvinyl alcohol, the pesticidal granule containing 80% by weight or more of the calcium carbonate.   An agrochemical-containing powder containing an agrochemical active ingredient is coated with a thermosetting resin, a coated granular agricultural chemical having an average particle diameter of 10 to 200 μm, a compound represented by the formula (I), calcium carbonate, The agrochemical granule of Claim 1 containing alpha starch or polyvinyl alcohol.   The agrochemical granule according to claim 1 or 2, wherein the compound represented by the formula (I) is one or more compounds selected from the group consisting of spinosyn A, spinosyn D, spinetram J and spinetram L.   The agrochemical granule according to claim 1 or 2, wherein the compound represented by the formula (I) is spinetoram.