JP4540685B2 - Stabilized pesticide formulation - Google Patents

Description

  The present invention relates to a stabilized agricultural chemical formulation comprising a guanidine derivative having an excellent insecticidal action, an organic phosphorus-based agricultural chemical active ingredient, and a compound having a polyoxyethylene group.

As agricultural and horticultural insecticides having a pest control ability, guanidine derivatives have been synthesized and those having excellent medicinal effects have been produced. For example, guanidine derivatives described in JP-A-3-157308 are excellent in controlling pests against important rice pests such as green moth, rice weevil, planthoppers, field crops such as aphids, thrips, and Coleoptera. It is an agricultural and horticultural insecticide having a capability, and it has been found that it becomes a useful agricultural and horticultural preparation usually used such as powder, granule, wettable powder, water solvent, flowable and the like.
Furthermore, a mixed preparation of the guanidine derivative and one or more pesticidal active ingredients is a very useful preparation having excellent medicinal effects in a wider range and capable of saving labor simultaneously. In particular, it is described in JP-A-4-112805 that the mixture of the guanidine derivative and the organophosphorus agrochemical active ingredient exhibits a synergistic effect as compared with the case where a single active ingredient is used. ing.

However, in the mixed preparation of the guanidine derivative and the organophosphorus agrochemical active ingredient, the decomposition of each active ingredient is promoted by the action of the active ingredients, so the degree of decomposition becomes extremely large compared to the case of each single preparation, Therefore, long-term storage is difficult, and insecticidal and bactericidal activities cannot be fully exhibited.
Accordingly, there is a demand for the development of a stable agrochemical formulation that suppresses the degradation of guanidine derivatives and organophosphorus agrochemical active ingredients.

〔式中、Ｒ¹は置換されていてもよい同素または複素環基を、ｎは０または１を、Ｒ²は水素または置換されていてもよい炭化水素基を、Ｒ³は第一、第二または第三アミノ基を、Ｘは電子吸引基を示す。〕で表されるグアニジン誘導体（Ｉ）またはその塩と有機燐系農薬活性成分とを有効成分とする混合剤に、ポリオキシエチレン基を有する化合物を含有させることによって、有効成分の分解が抑制され、安定性が向上することを知見した。本発明者らは、この知見に基づいて、さらに研究を重ねた結果、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have obtained a formula

[Wherein, R ¹ represents an optionally substituted homologous or heterocyclic group, n represents 0 or 1, R ² represents hydrogen or an optionally substituted hydrocarbon group, R ³ represents a first group, A secondary or tertiary amino group and X represents an electron withdrawing group. When the compound having a polyoxyethylene group is contained in a mixture containing the guanidine derivative (I) represented by the formula (I) or a salt thereof and an organophosphorus agrochemical active ingredient as active ingredients, decomposition of the active ingredient is suppressed. It was found that the stability was improved. Based on this finding, the present inventors have further studied and completed the present invention.

〔式中、Ｒ¹は置換されていてもよい同素または複素環基を、ｎは０または１を、Ｒ²は水素または置換されていてもよい炭化水素基を、Ｒ³は第一、第二または第三アミノ基を、Ｘは電子吸引基を示す。〕で表されるグアニジン誘導体（Ｉ）またはその塩、［２］有機燐系農薬活性成分および［３］ポリオキシエチレン基を有する化合物を含有してなる安定化された農薬製剤、
（２）グアニジン誘導体(Ｉ)が、式

で表される化合物である第（１）項記載の農薬製剤、
（３）さらに抗酸化剤および／またはエポキシ基を有する化合物を含有する第（１）項記載の農薬製剤、
（４）ポリオキシエチレン基を有する化合物が、ポリエチレングリコール類、ポリオキシエチレンポリオキシプロピレン共重合物、ポリオキシエチレンアルキルエーテル類あるいはそのリン酸又は硫酸エステル塩類、ポリオキシエチレンアルキルアリールエーテル類あるいはそのリン酸又は硫酸エステル類、ポリオキシエチレン脂肪酸エステル類およびポリオキシエチレンソルビタン脂肪酸エステル類から選ばれる１種以上である第（１）項記載の農薬製剤、
（５）抗酸化剤が、フェノール系抗酸化剤、アミン系抗酸化剤、チオジプロピオン酸誘導体系抗酸化剤および燐系抗酸化剤から選ばれる１種以上である第（３）項記載の農薬製剤、および
（６）エポキシ基を有する化合物が、エポキシ化植物油、環状脂肪族化合物およびグリシジル化合物から選ばれる１種以上である第（３）項記載の農薬製剤に関する。 That is, the present invention
(1) Formula [1]

[Wherein, R ¹ represents an optionally substituted homologous or heterocyclic group, n represents 0 or 1, R ² represents hydrogen or an optionally substituted hydrocarbon group, R ³ represents a first group, A secondary or tertiary amino group and X represents an electron withdrawing group. A stabilized pesticidal formulation comprising a guanidine derivative (I) or a salt thereof, [2] an organophosphorus pesticide active ingredient, and [3] a compound having a polyoxyethylene group,
(2) The guanidine derivative (I) has the formula

The agrochemical formulation according to item (1), which is a compound represented by:
(3) The agrochemical formulation according to item (1), further comprising an antioxidant and / or a compound having an epoxy group,
(4) Polyoxyethylene group-containing compounds are polyethylene glycols, polyoxyethylene polyoxypropylene copolymers, polyoxyethylene alkyl ethers or phosphoric acid or sulfate esters thereof, polyoxyethylene alkyl aryl ethers or the like Agrochemical formulation according to item (1), which is at least one selected from phosphoric acid or sulfuric acid esters, polyoxyethylene fatty acid esters and polyoxyethylene sorbitan fatty acid esters,
(5) The antioxidant according to item (3), wherein the antioxidant is at least one selected from a phenolic antioxidant, an amine antioxidant, a thiodipropionic acid derivative antioxidant and a phosphorus antioxidant. The agrochemical formulation and (6) the agrochemical formulation according to (3), wherein the compound having an epoxy group is one or more selected from epoxidized vegetable oils, cycloaliphatic compounds and glycidyl compounds.

  The agrochemical preparation containing the compound having a polyoxyethylene group of the present invention is excellent in storage stability because the decomposition of the guanidine derivative (I) or a salt thereof and the organophosphorus agrochemical active ingredient is excellent, and thus it can be stored for a long time. In addition, it can be advantageously used as an excellent agrochemical preparation that can sufficiently exhibit insecticidal and bactericidal activities.

The guanidine derivative (I) used in the agrochemical formulation of the present invention produces a stereoisomer of a cis-form [Z-form (zusammen)] and a trans-form [E-form (entgegen)] with respect to the X configuration, and R ² is hydrogen. When it is an atom and R ³ is a primary or secondary amino group, a tautomer is theoretically generated, and any of these isomers is included in the guanidine derivative (I) or a salt thereof of the present invention. It is.
In the above formula (I), R ¹ represents an optionally substituted homologous or heterocyclic group. The allotrope or heterocyclic group represented by R ¹ is a cyclic group containing only the same atom or a cyclic group containing two or more different atoms, and means a cyclic hydrocarbon group or a heterocyclic group.
Examples of the cyclic hydrocarbon group represented by R ¹ include C _3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, such as cyclopropenyl, 1-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, C _3-8 cycloalkenyl groups such as 1,4-cyclohexadienyl, such as phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthryl, 1-, 2-, 3-, 4- or 9 -C _6-14 aryl groups such as phenanthryl, 1-, 2-, 4-, 5- or 6-azurenyl are used.
A preferable cyclic hydrocarbon group is, for example, an aromatic group such as a C _6-14 aryl group such as phenyl.

As the heterocyclic group represented by R ¹ , for example, a 5- to 8-membered ring containing 1 to 5 heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom or a condensed ring thereof is used. Specific examples thereof include, for example, 2- or 3-thienyl, 2- or 3-furyl, tetrahydro-3-furanyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 5- (1,2,4-oxadiazolyl), 1,3,4-oxadiazolyl, 3- or 5- (1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- or 5- (1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxide- 2-, 3- or 4-pi Jyl, 2-, 4- or 5-pyrimidinyl, N-oxide-2-, 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofuryl, benzothiazolyl, Benzoxazolyl, triazinyl, oxotriazinyl, tetrazolo [1,5-b] pyridazinyl, triazolo [4,5-b] pyridazinyl, oxoimidazolinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, Thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperazinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, 1,8-naphthyridinyl Pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, and phenoxazinyl is used.
Preferred examples of the heterocyclic group include 5- or 6-membered nitrogen-containing heterocyclic groups such as 2-, 3- or 4-pyridyl, 2-, 4- or 5-thiazolyl.

These allotropes or heterocyclic groups represented by R ¹ may have 1 to 5 (preferably 1 to 3, more preferably 1) substituents which are the same or different. Examples of such substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like. C _1-15 alkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, C _3-10 cycloalkyl such as cyclohexyl, for example vinyl, allyl, 2-methylallyl, 2-butenyl, 3-butenyl, 3-octenyl, etc. C _{2- 10} alkenyl, for example C _2-10 alkynyl such as ethynyl, 2-propynyl, 3-hexynyl, etc., C _3-10 cycloalkenyl such as cyclopropenyl, cyclopentenyl, cyclohexenyl, etc., C _6-10 aryl such as phenyl, naphthyl, etc. For example, benzyl, phenyl ester C _7-10 aralkyl such as Le, nitro, hydroxyl, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, for example, methoxycarbonyl, C _1-4 alkoxy such as ethoxy carbonyl - carbonyl, sulfo, such as fluorine, chlorine, bromine, Halogen such as iodine, for example C _1-4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, etc., C _6-10 aryloxy such as phenoxy, such as methylthio, ethylthio, C _1-4 alkylthio such as n-propylthio, isopropylthio, n-butylthio, t-butylthio, etc., C _6-10 arylthio such as phenylthio, C _1-4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, etc., eg phenylsulfinyl etc C _6-10 arylsulfinyl, for example methylsulfonyl, C _1-4 alkylsulfonyl such as ethylsulfonyl, for example C _6-10 arylsulfonyl such as phenylsulfonyl, amino, for example acetylamino, propionylamino C _2-6 acylamino amino or the like, For example, mono- or di-C _1-4 alkylamino such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, etc., C _3-6 cycloalkylamino such as cyclohexylamino, etc. C _6-10 arylamino such as anilino, C _2-4 acyl such as acetyl, C _6-10 aryl-carbonyl such as benzoyl, such as 2- or 3-thienyl, 2- or 3-furyl, 3 -, 4- or 5-pyrazolyl, 2-, 4- or 5-thiazo 1,3-, 4- or 5-isothiazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-imidazolyl, 1,2,3- or 1 Oxygen, sulfur such as 1,2,4-triazolyl, 1H or 2H-tetrazolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-pyrimidinyl, 3- or 4-pyridanidyl, quinolyl, isoquinolyl, indolyl And a 5- or 6-membered heterocyclic group containing 1 to 4 heteroatoms selected from nitrogen or a condensed ring group thereof.

These substituents are, for example, C _6-10 aryl, C _7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10 In the case of arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 arylamino, heterocyclic group and the like, further halogen, hydroxyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s- butyl, t-C _1-4 alkyl and butyl, such as vinyl, allyl, C _2-4 alkenyl such as 2-methylallyl, such as ethynyl, C _2-4 alkynyl, C _6-10 aryl 2-propynyl, and the like , C _1-4 alkoxy, phenoxy, C _1-4 alkylthio, phenylthio and the like, may be substituted. In addition, the substituent of the homologous or heterocyclic group is C _1-15 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, In the case of C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino, C _6-10 arylamino and the like, halogen as described above, 1 to 5 groups may be substituted with a hydroxyl group, C _1-4 alkoxy, C _1-4 alkylthio or the like.
A preferred example of R ¹ is a 5- or 6-membered nitrogen-containing heterocyclic group such as pyridyl or thiazolyl optionally substituted with 1 to 2 halogen atoms. n represents 0 or 1, but is preferably 1.

Represented by R ² Examples of the hydrocarbon group in the "optionally substituted hydrocarbon group", the alkyl group of C _1-15 previously described for R ^1, the cycloalkyl group of C _3-10, a C _2-10 An alkenyl group, a C _2-10 alkynyl group, a C _3-10 cycloalkenyl group, a _6-10 aryl group, a C _7-10 aralkyl group and the like are used.
As the substituent in the "optionally substituted hydrocarbon group" represented by R ^2, those such as the same as those described above as the substituent of homocyclic or heterocyclic group represented by R ¹ are used .
Preferable examples of R ² include hydrogen, for example, C _1-4 alkyl groups such as methyl, ethyl, propyl and the like.

〔式中、Ｒ⁴及びＲ⁵は、同一または相異なり、水素または置換されていてもよい炭化水素基を、あるいはＲ⁴及びＲ⁵は一緒になって隣接した窒素と共に環状アミノ基を示す。〕で表わされる基等が用いられる。
ここにおいて、第一アミノ基とは例えば上記式で言えばＲ⁴及びＲ⁵が水素である無置換アミノ基を、第二アミノ基とはＲ⁴かＲ⁵のいずれかが水素であるモノ置換アミノ基を、第三アミノ基とはＲ⁴とＲ⁵のどちらも水素でないジ置換アミノ基を意味する。
Ｒ⁴及びＲ⁵で示される「置換されていてもよい炭化水素基」としては、例えば上記Ｒ²で述べたものと同一のもの等が用いられる。
また、Ｒ⁴及びＲ⁵が一緒になって隣接窒素と共に示す環状アミノ基としては、例えばアジリジノ，アゼチジノ，ピロリジノ，モルホリノ，チオモルホリノ基等が用いられる。
Ｒ³の好ましい例としては、例えば無置換アミノ基、例えばメチルアミノ，エチルアミノ，プロピルアミノ等のモノ−Ｃ_1-4アルキルアミノ基、例えばジメチルアミノ，エチルメチルアミノ等のジ−Ｃ_1-4アルキルアミノ基、例えばホルムアミド，Ｎ−メチルホルムアミド，アセトアミド等のＣ_1-4アシルアミノ基等が挙げられる。 R ³ represents a primary, secondary or tertiary amino group, examples of which include, for example, the formula

[Wherein, R ⁴ and R ⁵ are the same or different and represent hydrogen or an optionally substituted hydrocarbon group, or R ⁴ and R ⁵ together represent a cyclic amino group together with the adjacent nitrogen. And the like are used.
Here, the primary amino group is, for example, an unsubstituted amino group in which R ⁴ and R ⁵ are hydrogen in the above formula, and the secondary amino group is a mono-substituted group in which either R ⁴ or R ⁵ is hydrogen. An amino group and a tertiary amino group mean a disubstituted amino group in which neither R ⁴ nor R ⁵ is hydrogen.
As the “optionally substituted hydrocarbon group” represented by R ⁴ and R ⁵ , for example, the same groups as those described above for R ² can be used.
As the cyclic amino group together with the adjacent nitrogen R ⁴ and R ⁵ together, for example aziridino, azetidino, pyrrolidino, morpholino, thiomorpholino and the like are used.
Preferable examples of R ³ include, for example, an unsubstituted amino group, for example, a mono-C _1-4 alkylamino group such as methylamino, ethylamino, propylamino and the like, for example, a di-C _1-4 such as dimethylamino, ethylmethylamino and the like. Examples include alkylamino groups such as C _1-4 acylamino groups such as formamide, N-methylformamide, and acetamide.

Examples of the electron withdrawing group represented by X include cyano, nitro, alkoxycarbonyl (eg, C _1-4 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, etc.), hydroxycarbonyl, C _6-10 aryl-oxycarbonyl (eg, , Phenoxycarbonyl, etc.), heterocyclic oxycarbonyl (the above-mentioned are used as the heterocyclic group, for example, pyridyloxycarbonyl, thienyloxycarbonyl, etc.), for example, halogen (Cl, Br, etc.) Good C _1-4 alkylsulfonyl (eg, methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.), sulfamoyl, di-C _1-4 alkoxyphosphoryl (eg, diethoxyphosphoryl, etc.), such as halogen (Cl, Br, F, etc.) Etc.) C _1-4 acyl _optionally substituted by (eg, a) Cetyl, trichloroacetyl, trifluoroacetyl, etc.), C _6-10 aryl-carbonyl (eg, benzoyl, etc.), carbamoyl, C _1-4 alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl, etc.) and the like are used.
Preferred electron withdrawing groups include, for example, nitro, trifluoroacetyl, and cyano.

〔式中、Ｒ^1bはピリジル基、ハロゲノピリジル基またはハロゲノチアゾリル基を示し、Ｒ^2c，Ｒ^4a，Ｒ^5aは同一または相異なり、水素、メチル基、エチル基、 ホルミル基またはアセチル基を示す。〕で表わされる化合物(Ｉ^b)またはその塩等が挙げられる。
式(Ｉ^b)で表わされる化合物(Ｉ^b)において、Ｒ^1bは例えば３−ピリジル基を、例えば６−クロロ−３−ピリジル、６−ブロモ−３−ピリジル、５−ブロモ−３−ピリジル等のハロゲノピリジル基を、または２−クロロ−５−チアゾリル、２−ブロモ−５−チアゾリル等のハロゲノチアゾリル基を示す。 Preferred examples of the guanidine derivative (I) or a salt thereof include, for example,

[In the formula, R ^1b represents a pyridyl group, a halogenopyridyl group or a halogenothiazolyl group, and R ^2c , R ^4a and R ^5a are the same or different and represent hydrogen, a methyl group, an ethyl group, a formyl group or an acetyl group. Show. ] Compound (I ^b ) represented by the formula:
In the compound (I ^b ) represented by the formula (I ^b ), R ^1b represents, for example, a 3-pyridyl group such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 5-bromo-3-pyridyl, etc. Or a halogenothiazolyl group such as 2-chloro-5-thiazolyl or 2-bromo-5-thiazolyl.

  The most preferred guanidine derivative (I) includes a compound represented by the above formula (II). Among these compounds, (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (hereinafter abbreviated as compound (IIa)) is preferable.

Examples of the salt of the guanidine derivative (I) include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, and perchloric acid, such as formic acid, acetic acid, tartaric acid, malic acid, citric acid, and sulphur. Salts with organic acids such as acid, succinic acid, benzoic acid, picric acid, p-toluenesulfonic acid are used.
The guanidine derivative (I) or a salt thereof and a production method thereof are described, for example, in JP-A-3-157308.
One or more guanidine derivatives (I) or salts thereof in the agricultural chemical preparation of the present invention can be used.
The content of the guanidine derivative (I) or a salt thereof in the agricultural chemical preparation of the present invention is usually about 0.01 to 90% by weight, preferably about 0.05 to 50% by weight, based on the whole preparation.

Examples of the organophosphorus pesticide active ingredient used in the agrochemical formulation of the present invention include, for example, cyanophos (CYAP), fenthion (MPP), fenitrothion (MEP), diclofenthion (ECP), pyrimifosmethyl, etrimphos, diazinon, quinalphos, isoxathione, pyridafenthion. , Chlorpyrifosmethyl, Chlorpyrifos, Oxydeprofos (ESP), Bamidethione, Profenofos, Marathion (Marathon), Fentoate (PAP), Dimethoate, Formothione, Thiomethone, Disulfoton (Ethylthiomethone), Hosalon, Phosmet (PMP), Methidathion (DMTP), Prothiophos, Sulprofos, Pyracrofos, Dichlorvos (DDVP), Monocrotofos, Nared (BRP), Tetrachlorvinho (CVMP), dimethylvinphos, chlorfenvinphos (CVP), propaphos, acephate, isofenphos, dioxabenzophos (salithione), trichlorfone (DEP), EPN, an organic phosphorus insecticide such as ethion, iprobenphos (IBP), One or more organic phosphorus fungicides such as edifenphos (EDDP), tolcrofosmethyl, pyrazophos, fosetyl and the like are used.
The content of the organophosphorus agrochemical active ingredient in the agrochemical formulation of the present invention is usually about 0.1 to 90% by weight, preferably about 0.5 to 80% by weight.

In addition to the guanidine derivative (I) or a salt thereof and an organophosphorus agrochemical active ingredient, the agrochemical preparation of the present invention may further contain an agrochemical active ingredient such as one or more insecticides and fungicides.
Specifically, insecticides include carbaryl (NAC), metorcarb (MTMC), isoprocarb (MIPC), propoxyl (PHC), xylylcarb (MPMC), XMC, bendiocarb, pyrimicarb, mesomil, oxamyl, thiodicarb, etc. Synthetic pyrethroid insecticides such as carbamate insecticides, resmethrin, permethrin, cypermethrin, cyfluthrin, phenpropatoline, cycloprotorin, fulvalinate, flucitrinate, cyhalothrin, fenvalerate, etofenprox, acrinatrin, Nereistoxin insecticides such as thiocyclam and bensultap, chloronicotyl insecticides such as nitenpyram, silafluophene, diflubenzuron, teflubenzuron, chlorf Azuron, insect growth inhibitors such as buprofezin, hexythiazox, cyhexatin (fenbutatin oxide), pyridaben, include acaricides such as clofentezine.
In addition, as fungicides, sulfur fungicides such as dilam and thiuram, polyhaloalkylthio fungicides such as captan, organochlorine fungicides such as chlorothalonil (TPN) and fusalide, thiophanate methyl, benomyl, carbendazole, thiabendazole, and dietofencarb Benzimidazole fungicides, dicarboximide fungicides such as iprodione, vinclozolin, procymidone, fluorimide, carboxamide fungicides such as oxycarboxyl, mepronil, flutolanil, pencyclon, acylalanine fungicides such as metalaxyl, oxadixil, triadimephone, N-heterocyclic ergosterol biosynthesis inhibitors such as hexaconazole and triphorin, blasticidin S, kasugamycin, polyoxin, validamycin A, milde Antibiotic agents such as neomycin, quintozene (PCNB), hydroxy isoxazole, soil fungicides such as dazomet, dimethirimol, Jikuromejin, Anirajin (triazine), ferimzone, probenazole, isoprothiolane, tricyclazole, pyroquilon, etc. oxolinic acid.
When the guanidine derivative (I) or a salt thereof and an organophosphorus agrochemical active ingredient are further incorporated with another agrochemical active ingredient, the total amount of the agrochemical active ingredient is usually about 0.5 to 95% by weight based on the whole preparation. , Preferably about 1.0 to 50% by weight, more preferably about 1.5 to 20% by weight.

Examples of the compound having a polyoxyethylene group used in the agricultural chemical preparation of the present invention include polyethylene glycols, polyoxyethylene polyoxypropylene copolymers, such as polyoxyethylene such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. Alkyl ethers or phosphoric acid or sulfuric acid ester salts thereof, for example, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether or phosphoric acid or sulfuric acid esters thereof such as polyoxyethylene oleic acid Esters, polyoxyethylene fatty acid esters such as polyoxyethylene distearate, such as polyoxyethylene sorbitan monostearate 1 or more can be mentioned, such as carboxymethyl sorbitan fatty acid esters.
The content of the compound having a polyoxyethylene group in the agricultural chemical preparation of the present invention is usually about 0.01 to 30% by weight, preferably about 0.05 to 15% by weight, based on the whole preparation.

If desired, the agrochemical formulation of the present invention may further contain an antioxidant and / or a compound having an epoxy group.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a thiodipropion derivative-based antioxidant, and a phosphorus-based antioxidant. Specifically, for example, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), 2,6-dibutyl-4-ethylphenol, 2,6-di-tert-butylphenol, stearyl-β- (3,5- Dibutylhydroxyphenyl) propionate, 4,4′-methylenebis- (2,6-di-tert-butylphenol), 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylenebis -(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4-tert-butylcatechol, 2,4-dimethyl-6-tert-butylphenol, Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Irganox 1010), , 4,6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene (Ionox 330), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane (Topanol CA), nordihydroguaiaretic acid (NDGA), dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate (RA-1093), DL-tocopherol, propyl gallate Phenolic compounds such as Antioxidant Hoechst TMOZ, such as α-naphthylamine, diphenylamine, 2,2,4-trimethyldihydroquinoline, phenyl-β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, phenyl-α-naphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenyl Nylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N, N′-bis (1-methylheptyl) -p-phenylenediamine, N, N′-diphenylethylenediamine, p-isopropoxydiphenylamine, Amine systems such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, aldol-α-naphthylamine, such as dilauryl thiodipropionate (DLTP), distearyl thiodipropionate (DSTP), Dimyristylthiodipropionate, 2- (3,5-di-tert-butyl-4-hydroxyanilino) -4,6-dioctylthiotriazine (RA-565), 4,4′-thiobis- (3- Methyl-6-tert-butylphenol) (Y-SR), 2,2'-thiobis- (4-methyl-6-tert-butylphenol), di Thiodipropion derivative systems such as cudididithiophosphate and trilauryltrithiophosphate such as triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris (nonylphenyl) phosphite, SANKO-220, SANKO-DC In addition, one or more of phosphorus-based materials such as erythorbic acid, sodium erythorbate, and isopropyl citrate are used. The content of these compounds in the agricultural chemical preparation of the present invention is usually about 0.01 to 50% by weight, preferably about 0.05 to 20% by weight, based on the whole preparation.

  Moreover, as a compound which has an epoxy group, an epoxy vegetable oil, a cyclic aliphatic compound, a glycidyl compound, etc. are mentioned. Specifically, epoxidized drying oil (eg, epoxidized linseed oil, epoxidized tung oil, epoxidized eno oil, etc.), epoxidized semi-drying oil (eg, epoxidized soybean oil, epoxidized cottonseed oil, epoxidized sesame oil, Epoxy vegetable oils such as epoxidized rapeseed oil), epoxidized non-drying oil (eg, epoxidized castor oil, epoxidized olive oil, epoxidized camellia oil, epoxidized peanut oil, epoxidized coconut oil), such as cyclohexene oxide, vinyl Cyclohexene dioxide, dicyclopentadiene dioxide, 3,4-epoxycyclohexyl-methyl-3 ′, 4′-epoxycyclohexane carbonate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 ′ -Methylcyclohexane carbonate, bis (2,3-epoxycyclopentyl) Ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxycyclohexane-1,1-dimethanol bis (9,10-epoxystearate), epoxidized fatty acid, epoxy fatty acid alkyl ester Cycloaliphatic compounds such as epoxy glycerides, diepoxy glycerides, triepoxy glycerides, composites of mono-, di- or tri-epoxy glycerides, glycerol glycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, mono-, Di- or tri-glycidyl ether complex, allyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 2,2′-bis (4-hydroxyphenyl) propane diglycidyl ether, 2-ethylhexyl glycidyl ether, 2,2′-bis (4-hydroxyphenyl) butanediglycidyl One or more kinds of glycidyl compounds such as ether, phenol formalin resin (trimer) triglycidyl ether, tetrakis (hydroxyphenyl) ethanetetraglycidyl ether, phenylglycidyl ether, epichlorohydrin, propylene oxide, styrene oxide and the like are used. The content of these compounds in the agricultural chemical preparation of the present invention is usually about 0.01 to 10% by weight, preferably about 0.1 to 10% by weight, based on the whole preparation.

The agrochemical formulation of the present invention can be molded into, for example, powders, granules, wettable powders, aqueous solvents, etc., and is a surfactant, extender, flow aid, anti-caking agent, flocculant, moisture remover. Commonly used agricultural chemical adjuvants such as colorants, binders, fragrances, ultraviolet absorbers, ultraviolet scattering agents, preservatives, and the like can be used.
In the agrochemical formulation of the present invention, the surfactant is usually used for the purpose of a dispersant, a spreading agent, a wetting agent, a penetrating agent, a granulating property improving agent, etc., and is a compound having a polyoxyethylene group shown above. In addition, the following surfactants can be used. Specifically, alkyl sulfate salts such as sodium lauryl sulfate, alkylaryl sulfonates such as sodium alkylnaphthalene sulfonate, lignin sulfonates such as sodium lignin sulfonate, sulfosuccinates such as sodium dioctyl sulfosuccinate, malein Polycarboxylic acid salts such as sodium salts of acid and olefin copolymers, anionic surfactants such as formaldehyde condensates of aromatic sulfonates, sorbitan fatty acid esters such as monooleic acid, glycerin fatty acid esters, sucrose fatty acids Examples thereof include nonionic surfactants such as esters, cationic surfactants such as amine salt types and quaternary ammonium salt types, and amphoteric surfactants such as amino acid types and betaine types. When this surfactant is used, it is generally used in an amount of about 0.01 to 30% by weight, preferably about 0.05 to 20% by weight, based on the whole preparation.

Examples of extenders include vegetable powders such as soybean powder, tobacco powder, wheat flour and wood powder, clay minerals such as clay, bentonite, acid clay, radiolite, talc such as talc powder and wax stone powder, diatomaceous earth, mica One or more kinds of mineral powders such as silica such as powder, lactose, baking soda, urea powder, calcium carbonate, alumina, sulfur powder, activated carbon and the like can be used.
As the flow aid, for example, PAP aid (eg, isopropyl acid phosphate), white carbon, talc, tall oil fatty acid and the like are used as necessary.
As the anti-caking agent, for example, white carbon, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide or the like is used as necessary.
As the flocculant, for example, liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, isobutylene polymer (eg, IP Solvent 2835: registered trademark; manufactured by Idemitsu Petrochemical Co., Ltd.) and the like are used as necessary.
As the water removing agent, for example, anhydrous gypsum, silica gel powder or the like is used as necessary.
As the colorant, for example, cyanine green G (manufactured by Sumitomo Chemical Co., Ltd.) or the like is used as necessary.
As the binder, for example, carboxymethyl cellulose sodium salt, pregelatinized starch, sodium lignin sulfonate, dextrin, polyvinyl alcohol, gum arabic, sodium alginate, polyvinyl pyrrolidone, glucose, sucrose, mannitol, sorbitol and the like are used as necessary. .
As the fragrance, for example, Toxanone L (manufactured by Sanyo Kasei) or the like is used as necessary.
Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2-ethoxy-2′-ethyl oxalic acid bisanilide, and dimethyl-1- (2-hydroxyethyl succinate). ) -4-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate or the like is used as necessary.
As the ultraviolet scattering agent, for example, titanium dioxide or the like is used as necessary.
As the preservative, for example, butyl paraben, potassium sorbate, or the like is used as necessary.

  When a flow aid is used, it is generally used in an amount of about 0.05 to 20% by weight, preferably about 0.1 to 10% by weight, based on the whole preparation. When an anti-caking agent is used, it is generally used in an amount of about 0.05 to 50% by weight, preferably about 0.1 to 20% by weight, based on the whole preparation. When an aggregating agent is used, it is generally used in an amount of about 0.05 to 20% by weight, preferably about 0.1 to 10% by weight, based on the whole preparation. When a water removing agent is used, it is generally used in the range of about 0.1 to 30% by weight, preferably about 0.5 to 20% by weight, based on the whole preparation. When a colorant is used, it is generally used in an amount of about 0.01 to 2.0% by weight, preferably about 0.01 to 1.0% by weight, based on the entire preparation. When a binder is used, it is generally used in the range of about 0.1 to 10% by weight, preferably about 0.5 to 7% by weight, based on the whole preparation. When a fragrance | flavor is used, it is used in the range of about 0.01-5 weight% normally with respect to the whole preparation, Preferably it is about 0.01-1 weight%. When an ultraviolet absorber is used, it is generally used in an amount of about 0.05 to 20% by weight, preferably about 0.1 to 10% by weight, based on the whole preparation. When an ultraviolet scattering agent is used, it is generally used in an amount of about 0.05 to 90% by weight, preferably about 0.1 to 20% by weight, based on the whole preparation. When a preservative is used, it is generally used in an amount of about 0.01 to 1.5% by weight, preferably about 0.05 to 3% by weight, based on the whole preparation.

  The agrochemical formulation of the present invention can be molded into powders DL, granules, aqueous solvents, wettable powders, and the like according to a general method for producing agrochemical formulations, and powders DL and granules are particularly suitable. For example, in the case of the powder DL, it can be produced by an ordinary method such as mixing each of the above components with an automatic mortar and then pulverizing with a pulverizer such as a hammer mill or an air mill. In the case of granules, the pulverized product can be produced by a usual method such as molding into granules using a compression molding machine such as a roller compactor, an extrusion granulator, or a rolling granulator. .

Examples of cultivation plants to be applied include rice, wheat (eg, wheat, barley), sugar beet, corn, cotton, vegetables (eg, cabbage, Chinese cabbage, radish, cucumber, eggplant, potato, etc.), fruit trees (eg, oranges, Momo, none), tea, tobacco, etc.
Examples of pests to be applied include hemiptera pests (e.g., turtles, blue-knot bugs, hoso-helical bugs, nasi-gumbai, brown planthoppers, white-spotted planthoppers, brown-spotted planthoppers, black-spotted leafhoppers, yellow-spotted leafhoppers, on-site white-tailed bugs, Soybean aphids, fake aphids, radish aphids, peach aphids, cotton aphids, apple aphids, etc. ), Coleoptera pests (e.g., Nephiea weevil, cucumber beetle, kiss) Flea beetle, Colorado potato beetle, turtle beetle, rice beetle, weevil, weevil, etc.), Diptera pests (eg, houseflies, mosquitoes), bovine ab, onion flies, grubs, etc., straight moth pests (eg, Tosama grasshopper, kera), etc. Examples include moths (eg, German cockroaches, black cockroaches, etc.), spider mites (eg, spider mites, citrus spider mites, kanzawa spider mites, miscarid mites, apple spider mites, citrus mites, etc.), nematodes (eg, rice winged nematodes)

The agrochemical formulation of the present invention is a safe and excellent agrochemical with extremely low toxicity. And the agrochemical formulation of this invention can be used by the method similar to the conventional insecticide, a disinfectant, etc., As a result, the effect outstanding compared with the conventional product can be exhibited. For example, when the agrochemical formulation of the present invention is used as an insecticide, for example, aerial spraying, soil spraying, foliage spraying, seedling box spraying, side strip application, seed treatment, mixing on the floor, insect spraying, It can be used by underwater application of paddy fields.
The usage-amount of the agrochemical formulation of this invention can be suitably selected, for example according to the kind of agrochemical active ingredient, the kind of dosage form, a target pest, an application time, an application place, an application method, etc.
For example, in the case of the powder DL, it can be used as it is, and is usually used for paddy fields. As an agrochemical active ingredient, about 1-250g per 10a is used according to the kind, Preferably about 2-200g is used.
In the case of granules, they can be used as they are, and are usually used in paddy fields, fields (eg, fields of tea, wheat, sugar beet, corn, potatoes, cotton, etc.), orchards and the like. As an agrochemical active ingredient, about 1-500g per 10a is used according to the kind, Preferably about 2-300g is used.

  Hereinafter, the present invention will be described more specifically with reference to Examples, Reference Examples and Experimental Examples. Compound (IIa) was produced according to the method described in the examples of JP-A-3-157308 (Patent No. 2546003) (Table 4, Compound No. 19).

Using New Pole PE-64 (polyoxyethylene polyoxypropylene copolymer, manufactured by Sanyo Kasei) as a stabilizer, the ingredients of the following formulation are mixed uniformly, kneaded with an appropriate amount of water, and then screened. After granulation with an extrusion granulator having a diameter of 1.0 mmφ, it was dried to obtain granules.
Compound (IIa) 0.5% by weight
Acephate 5.0
New Pole PE-64 1.0
Dextrin 3.0
100 calcium carbonate for granules

Granules were obtained in the same manner as in Example 1 using Nonipol 85 (polyoxyethylene nonylphenyl ether, manufactured by Sanyo Kasei) as a stabilizer.
Compound (IIa) 0.5% by weight
Acephate 5.0
Nonipole 85 1.0
Dextrin 3.0
100 calcium carbonate for granules

Granules were obtained in the same manner as in Example 1 using PEG1000 (polyethylene glycol, manufactured by Sanyo Chemical Co., Ltd.) as a stabilizer.
Compound (IIa) 0.5% by weight
Acephate 5.0
PEG1000 1.0
Dextrin 3.0
100 calcium carbonate for granules

Granules were obtained in the same manner as in Example 1 using Newpol PE-64 and dibutylhydroxytoluene as stabilizers.
Compound (IIa) 0.5% by weight
Acephate 5.0
New Pole PE-64 1.0
Dextrin 3.0
Dibutylhydroxytoluene 2.0
100 calcium carbonate for granules

Granules were obtained in the same manner as in Example 1 using Newpol PE-64 and Adeka Sizer O-180A (epoxidized linseed oil, manufactured by Asahi Denka Kogyo) as the stabilizer.
Compound (IIa) 0.5% by weight
Acephate 5.0
New Pole PE-64 1.0
Dextrin 3.0
Adeka Sizer O-180A 2.0
100 calcium carbonate for granules

Using New Pole PE-64 as a stabilizer, raw materials having the following formulation were uniformly mixed in a mortar to obtain a powder DL.
Compound (IIa) 0.15% by weight
Fenitrothion 3.0
Ferimzone 2.0
Fusaride 1.5
New Pole PE-64 2.0
IP solvent 0.2
PAP auxiliary 0.05
White carbon 3.0
Clay DL total 100

A powder DL was obtained in the same manner as in Example 6 using Newpol PE-64 and dibutylhydroxytoluene as stabilizers with the following formulation.
Compound (IIa) 0.15% by weight
Fenitrothion 3.0
Ferimzone 2.0
Fusaride 1.5
New Pole PE-64 2.0
IP solvent 0.2
PAP auxiliary 0.05
White carbon 3.0
Dibutylhydroxytoluene 2.0
Clay DL total 100

A powder DL was obtained in the same manner as in Example 6 using Newpol PE-64 and Adekasizer O-180A as stabilizers.
Compound (IIa) 0.15% by weight
Fenitrothion 3.0
Ferimzone 2.0
Fusaride 1.5
New Pole PE-64 2.0
IP solvent 0.2
PAP auxiliary 0.05
White carbon 3.0
Adeka Sizer O-180A 2.0
Clay DL total 100

Comparative Example 1

In Example 1, New Paul PE-64 was replaced with New Calgen EP-60P (sodium dioctyl sulfosuccinate, manufactured by Takemoto Yushi), and granules were obtained in the same manner as in Example 1 with the following formulation.
Compound (IIa) 0.5% by weight
Acephate 5.0
New Calgen EP-60P 1.0
Dextrin 3.0
100 calcium carbonate for granules

Test example 1

表１に示されているように、ポリオキシエチレン基を有する化合物を添加することにより、グアニジン誘導体(Ｉ)またはその塩及び有機燐系農薬活性成分の安定性が向上されることが分かった。 The preparations produced in Examples 1 to 5 and Comparative Example 1 were sealed in a glass bottle and placed in a constant temperature bath at 40 ° C. After 3 months, the content of each pesticidal active ingredient was measured by high performance liquid chromatography, and the residual rate was determined from the following formula.
Residual rate of agricultural chemical active ingredient (%) = (content) / (initial content) × 100
The results are shown in [Table 1].

As shown in Table 1, it was found that by adding a compound having a polyoxyethylene group, the stability of the guanidine derivative (I) or a salt thereof and the organophosphorus agrochemical active ingredient was improved.

  The agrochemical preparation containing the compound having a polyoxyethylene group of the present invention is excellent in storage stability because the decomposition of the guanidine derivative (I) or a salt thereof and the organophosphorus agrochemical active ingredient is excellent, and thus it can be stored for a long time. In addition, it can be advantageously used as an excellent agrochemical preparation that can sufficiently exhibit insecticidal and bactericidal activities.

Claims (8)

(1) Formula (II)

A guanidine derivative (II) represented by the formula:
(2) Stabilized pesticide comprising an organophosphorus pesticide active ingredient, and (3) a compound having a polyoxyethylene group selected from a polyoxyethylene polyoxypropylene copolymer and a polyoxyethylene alkylaryl ether Granules. The agrochemical granule according to claim 1, wherein the compound having a polyoxyethylene group is a polyoxyethylene polyoxypropylene copolymer . The agrochemical granule according to claim 1, wherein the compound having a polyoxyethylene group is polyoxyethylene alkylaryl ether . The agrochemical granule according to any one of claims 1 to 3 , wherein the total content of the guanidine derivative represented by the formula (II) or a salt thereof and the organophosphorus agrochemical active ingredient is 1.5 to 20% by weight. . The agrochemical granule according to any one of claims 1 to 4, wherein the organophosphorus agrochemical active ingredient is at least one selected from the group consisting of acephate and fenitrothion . Furthermore, the agrochemical granule in any one of Claims 1-5 containing the compound which has an antioxidant and / or an epoxy group . The agrochemical granule according to claim 6 , wherein the antioxidant is at least one selected from a phenol-based antioxidant, an amine-based antioxidant, a thiodipropionic acid derivative-based antioxidant, and a phosphorus-based antioxidant . The agrochemical granule according to claim 6 , wherein the compound having an epoxy group is one or more selected from epoxidized vegetable oils, cycloaliphatic compounds and glycidyl compounds .