JPH019A - Stabilized insecticidal and fungicidal pesticide compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to 4,6-dimethyl-2-(1-(o-tolyl)
- A stabilized agricultural chemical composition characterized in that boron oxide and/or a complex of boron oxide is blended into a mixed preparation containing 1-ethylidenehydrazinocopyrimidine or a salt thereof and an organic phosphorus compound. be.

BACKGROUND ART In general, pesticides are composed of a single pesticide active substance that is expected to have a single medicinal effect, and two or more pesticide active substances that are mixed to achieve each single active substance. Some are expected to have a wider range of excellent medicinal effects than others, while others are intended to simultaneously control various pests and diseases in a labor-saving manner.

In particular, mixtures containing two or more pesticide active substances are currently widely used in the field of agricultural chemicals, but these mixtures take a long time to be used after they are manufactured. During this time, it may decompose and show no biological activity, and sometimes it may not cause any phytotoxicity.

4,6-dimethyl-2-(1-(o-tolyl)-1-ethylidenehydrazinocopyrimidine (hereinafter sometimes abbreviated as Compound M) represented by the formula is a compound that can be used to treat rice blast fungi and sesame leaf blight. It is known to be an excellent agricultural fungicide that exhibits strong antibacterial activity against a wide range of plant pathogenic bacteria, such as phytopathogens. , for example, 0,0-tmethyl-〇-(3-methyl-4
-nitrophenyl) phosphorothionate (hereinafter sometimes abbreviated as MEP) and several other organic phosphorus compounds are commonly used.

However, an agrochemical mixture containing the above compound M and an organic phosphorus compound such as MEP, exhibits an anti-blast blight effect, an anti-sesame leaf blight effect, and a control effect against Japanese planthoppers, stink bugs, etc. to a practical degree. is still unknown.

Furthermore, in a pesticide mixture containing Compound M and an organic phosphorus compound, it is not known what effect the Compound M and the organic phosphorus compound have on each other, particularly on their respective stability.

Problems to be Solved by the Invention There is a strong desire to develop a mixture of Compound M, which has an outstanding blast effect, and an insecticidal organophosphorus compound such as MEP, which has the biological activity of both compounds. ing.

However, the present inventors have found that when Compound M and an organic phosphorus compound are mixed, both active ingredients are significantly decomposed, and such a mixture no longer exhibits biological activity after long-term storage. In particular, the decomposition of organic phosphoric acid compounds over time is large. For example, as shown in Reference Example 1 below, compound M
and MEP, when no stabilizer is added, after storage at 40°C for 30 days, compound M is 31.6%,
MEP is degraded to 94.7%.

Moreover, isopropyl acid phosphate, fatty acids, etc. have long been known as stabilizers for organic phosphorus compounds, but even if these ordinary stabilizers for organic phosphorus compounds are added to the mixture, there is no stabilizing effect. cannot be obtained. (Refer to Reference Examples 2.4 to 13 below) Furthermore, when a strong acid such as a sulfonic acid is added, the decomposition of the organic phosphorus compound is suppressed, but on the contrary Compound M decomposes and loses its effectiveness (Reference Examples below). (See Example 3).

An object of the present invention is to provide a highly stable mixture in which decomposition of both active ingredients is suppressed as much as possible in an agrochemical composition containing Compound M and an organic phosphorus compound.

Means for Solving the Problems The inventors of the present invention solved the above problems and conducted various studies to obtain a stable mixture of compound M and an organic phosphorus compound. They discovered that the decomposition of organic phosphorus compounds can be specifically inhibited by blending the organic phosphorus compound with compound M without decomposing it, and after further studies, the present invention was completed.

That is, the present invention relates to a stable agricultural chemical composition containing Compound M or a salt thereof, an organic phosphorus compound, and boron oxide and/or a boron oxide complex.

In the agrochemical composition of the present invention, Compound M, which is an active ingredient exhibiting a medicinal effect against rice blast, etc., may be used as such, or may be used in the form of hydrochloric acid, sulfuric acid, or nitric acid.

It may also be used as a salt with an inorganic acid such as phosphoric acid, or an organic acid such as acetic acid, citric acid, or tartaric acid. Compound M and its salt are
For example, it can be produced by the method described in the above-mentioned Japanese Patent Publication No. 61-21551.

A wide variety of organic phosphorus compounds can be used in the present invention, including the following compounds that are commonly used as insecticides.

(i) o,o-dimethyl-〇-(3-methyl-4-nitrophenyl)phosphorothionate (MEP) (2)S
-(α-(Ethoxycarbonyl)benzyl]0.0-dimethyl phosphorothiolothionate (PAP) (3) 0.0-dimethyl-〇-methylthio m-tolyl phosphorothionate (MPP) (4) 0 -Ethyl-8,S-diphenylphosphorodithiolate (EDDP) (5) O-2-diethylamino-4-methyl-6=pyrimidinyl-0,0-dimethylphosphorothioate (pirimiphos methyl) (6) S-1 ,2-bis(ethquincarbonyl)ethyl 09O-tumethylphosphorodithiolate (Marathon) (7)S-2-ethylsulfinyl-1-methylethyldimethylphosphorothiolate (ESP)(8)S-(
N-formyl-N-methylcarbamoyl-methyl)dimethylphosphorothiolothionate (formothione) (9)S-(2-ethylthioethyl)dimethylphosphorothiolothionate (thiometone) (IQ)S-((2-methoxy -5-oxo-1,3゜4-thiadiazolin-4-yl)methylcotmethylphosphorothiothionate (DMTP) (11)2,2-dichlorovinyldimethylphosphate (DDVP) (120E)-1-methyl- 2-(Methylcarbamoyl)vinyldimethylphosphate (monocrotovos) (13) I, 2-dibromo-2,2-dichloroethyldimethylphosphate (BrlP) (14) 2-chloro-1-(2,4,5- Trichlorophenyl)-vinyl dimethyl phosphate (CVMP) (15) 2-chloro-1-(2,4-dichlorophenyl)-vinyl dimethyl phosphate (dimethylvinphos) (16) 0.S-dimethyl N-acetylphosphoroamide thio (acephate) (17) Dimethyl 2,2.2-trichloro-1-hydroxyethylphosphonate (DEP) As an organic phosphorus compound, it is advantageously applied to a dimethyl phosphoric acid compound having a particular partial structure. When a 0.0-dimethylphosphorothioate compound or a 0,0-dimethylphosphorothiorothionate compound having a partial structure of The MEPs mentioned above can therefore be significantly stabilized by the body.

Particularly suitable are PAP, MPP and the like. However, the organic phosphorus compounds applicable to the present invention are not limited to those listed above.

These organic phosphorus compounds have a weight ratio of about 2 to compound M.
The boron oxide complex used in the present invention is, for example, B t Os.
Al t O3, B t O3-T i O, etc. are used, but are not particularly limited thereto.

These boron oxides or boron oxide complexes are compound M
or a weight ratio of about 20:1 to 1:
The weight ratio is about 10:1 to 1:1.
4 is a preferred range.

The agrochemical composition of the present invention can be produced by pulverizing and mixing by a known method. During production, powders are prepared by mixing with diluents and carriers commonly used for agricultural chemicals and using known methods.

It can be in a solid dosage form such as a wettable powder, an emulsion, or a single granule. Solid carriers or diluents include vegetable powders (eg, soybean flour, tobacco flour, wheat flour).

(wood powder, etc.), mineral powders (e.g., clays such as kaolin, bentonite, acid clay, etc., talcs, such as talc powder, waxite powder, etc.), diatomaceous earth (e.g., silicas, such as radiolite, mica powder, etc.), carbonic acid Calcium, sulfur powder, activated carbon, etc. are also used, and these ti or a mixture of two or more types can be used.

In such formulations antioxidants (e.g. dibutylhydroxytoluene, 4,4'-thiobis-6-t
-butyl-3-medylphenol, etc.).

Dispersants (e.g. ethylene glycol, glycerin, etc.)
, surfactants (e.g. lignin sulfonates).

alkylbenzene sulfonate, polyoxyethylene alkylaryl ether, alkylnaphthalene sulfonate, etc.), flow aids (e.g., white carbon, etc.),
Preservatives, military agents, etc. can be added as appropriate. In the case of a powder, it is also possible to make it a driftless (DL) powder by further adding an additive (eg, liquid paraffin) that has the effect of reducing scattering and floating. Furthermore, in the agricultural chemical composition of the present invention, in addition to 4,6-dimethyl-2-(1-(o-)lyl)-1-ethylidenehydrazino]pyriminone or a salt thereof and an organic phosphorus compound, if necessary, , other pesticide active ingredients can be blended. Such agrochemical active ingredients include known insecticides (for example, 2-5ec-7'tylphenyl-N-methylcarbamate (BPMC).

fenobucarb), cartap, bensultap, etc.).

Fungicides (e.g., 4,5,6,7-titrachlorphthalide (fusaride), plasticidin S-benzylaminobenzenesulfonate, 3'-isopropoxy-2-
Methylbenzanilide, validamycin A, tridiclazole, etc.) may be added as appropriate to the extent that they do not impair the effects of the present invention.

For example, compound M that has control and therapeutic effects on rice blast
Fusaride has a preventive effect against rice blast.

MEP with excellent control effect on snails, planthoppers, etc.
A combination of these can provide an agrochemical composition that provides excellent simultaneous pest control. Furthermore, by adding PMC that is effective against planthoppers and leafhoppers to the above combination, a stable agrochemical composition having a broader insecticidal and bactericidal spectrum can be obtained.

In this way, when formulating with carriers and other ingredients, the content of Compound M per 100 parts by weight of the formulation is approximately 10 to 90 for emulsions, wettable powders, etc., and about 10 to 90 for oils, powders, etc. o,ooot to about 50 parts by weight, and for granules, about 0.1 to 50 parts by weight is suitable.

In powder agents, it is often effective to contain it more preferably in an amount of about 0.001 to 20 parts by weight. These content ratios are not necessarily limited.

Note that emulsions, hydrating agents, and the like are preferably further diluted (for example, 50 to 5000 times) with water and the like before being sprayed.

The amount of active ingredients to be used, the combination of mixing with other types of drugs, and the ratio of these ingredients will depend on the growth stage of the target plant,
Although it varies depending on various conditions such as growth status, type of disease, propagation of disease onset, timing and method of application of the drug, generally the active ingredient (total amount of Compound M and organic phosphorus compound) is 1O
The amount may be adjusted to about 1 g to 300 g per area.

In addition, the concentration used is 10 to 11000 of the active ingredient.
pp range, and the methods of use include spraying, dusting, irrigating, or seed dressing. The present invention is not limited in any way by the amount, concentration, or method of use.

EXAMPLES Next, the present invention will be explained in more detail by referring to Examples and Reference Examples, but the present invention is not limited to the following Examples.

Example 1 2 parts of Compound M, 3 parts of MEP, 0.5 parts of tridiclazole, 10 parts of boron oxide, and 84.5 parts of clay are weighed and mixed in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 2 2 parts of compound M, 1 part of MEPB, 1.5 parts of fusaride.

Example 1 using 5 parts of boron oxide and 88.5 parts of clay
Obtain a powder in the same manner as above.

Example 3 2 parts of Compound M, 3 parts of MEP, 0 parts of boron oxide-aluminum oxide composite II, and 85 parts of clay were weighed out and mixed in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 4 2 parts of Compound M, 3 parts of MEP, 10 parts of boron oxide-titanium dioxide complex, and 85 parts of clay were weighed and mixed in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 5 2 parts of compound M, 3 parts of MPP, 5 parts of boron oxide, 9 parts of clay
Weigh out 0 parts and mix in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 6 Compound M 2 parts, PAPS part, boron oxide 5 parts, clay 9
Weigh out 0 parts and mix in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 7 2 parts of compound M, 3 parts of MEP, 1.5 parts of fusaride.

2 parts BPMC, 10 parts boron oxide, 5 parts white carbon
1 part, 0.5 part of isopropyl acid phosphate, and 76 parts of clay were mixed in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Example 8 15 parts of compound M, 10 parts of fusaride, 15 parts of MEP, 1
3 parts MC 10 parts, boron oxide IO part, New Calgen N
V410 (surfactant, Takemoto Oil & Fat Co., Ltd. 0 parts, White Carbon 20 parts, Surfactant 5TP-800 (Kochu Kasei Co., Ltd.) 0.5 parts, Deixsol W-K (Dai-Kogyo Seiyaku Co., Ltd.)
1.5 parts 1 8 parts of Radiolite #200 (manufactured by Showa Kasei) were weighed and mixed in a Raikai machine. Pulverize the entire amount
(screen diameter 1 ma+) to obtain a wettable powder.

Example 9 15 parts of compound M, 21 parts of MEP. 15 parts of boron oxide, 20 parts of white carbon, 14 parts of New Calgen NV41O (surfactant, manufactured by Takemoto Yushi), 5TP-80 surfactant
0 (manufactured by Kochu Kasei), 1.5 parts of Deixsol W-K (manufactured by Dai-Kogyo Seiyaku), and 14 parts of Radiolite #200 (manufactured by Showa Kasei) were weighed and mixed in a Raikai machine. The entire amount is pulverized with a pulverizer (screen diameter 1 arm) to obtain a wettable powder.

Reference Example 1 2 parts of Compound M, 95 parts of MEPa, and 95 parts of clay were weighed and mixed in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder.

Reference Example 2 A powder was obtained in the same manner as in Reference Example 1 using 2 parts of Compound M, 3 parts of MEP, 1 part of isopropyl acid phosphate, and 94 parts of clay.

Reference Example 3 2 parts of compound M, 3 parts of MEP, 5 parts of benzenesulfonic acid,
A powder was obtained in the same manner as in Reference Example 1 using 90 parts of clay.

Reference example 4 2 parts of compound M, 3 parts of MEP, 2 parts of linoleic acid, 9 parts of clay
3 parts were treated in the same manner as in Reference Example 1 to obtain a powder.

Reference example 5 Compound M 2 parts, MEP 3 parts, boric acid 10 parts, clay 85
A powder was obtained in the same manner as in Reference Example 1 using

Reference Example 6 2 parts of compound M, 3 parts of MEP, 1 part of manganese(II) borate
A powder was obtained in the same manner as in Reference Example 1 using 0 parts of clay and 85 parts of clay.

Reference example 7 2 parts of Compound M, 3 parts of MEP, 10 parts of titanium dioxide.

A powder was obtained in the same manner as in Reference Example 1 using 85 parts of clay.

Reference Example 8 Compound M2 part, MEPa part, aluminum oxide lO part,
A powder was obtained in the same manner as in Reference Example 1 using 85 parts of clay.

Reference Example 9 A powder was obtained in the same manner as in Reference Example 1 using 2 parts of Compound M, 3 parts of MEP, 10 parts of -nickel oxide, and 85 parts of clay.

Reference Example 1O A powder is obtained in the same manner as in Reference Example 1 using 2 parts of Compound M, 3 parts of MEP, 10 parts of calcium oxide, and 85 parts of clay.

Reference example 11 2 parts of compound M, 3 parts of MEP, 10 parts of bismuth oxide.

A powder was obtained in the same manner as in Reference Example 1 using 85 parts of clay.

Reference Example 12 A powder is obtained in the same manner as in Reference Example 1 using 2 parts of Compound M, 3 parts of PAP, 1 part of isopropyl acid phosphate, and 94 parts of clay.

Reference Example 13 A powder is obtained in the same manner as in Reference Example 1 using 2 parts of Compound M, 3 parts of MFP, 1 part of isopropyl acid phosphate, and 94 parts of clay.

Test Examples Examples 1-9. Reference example! - 20 g of each sample obtained in steps I3 was placed in a sample bottle, sealed tightly, and stored at 40°C for 30 days.

Immediately after the expiration of the period, a sample was taken out and the content of the active ingredient was measured using high performance liquid chromatography. Note that the decomposition rate (%) was determined from the following formula.

Decomposition rate (%) = xto.

The test results are shown in Table 1.

table ! Stability Test Results Effect of the Invention The agrochemical composition using boron oxide or its complex of the present invention as a stabilizer has extremely high stability. Furthermore, as shown in detail in the stability test mentioned above, the decomposition of each agricultural chemical active ingredient was lower in the composition of the present invention than in a composition using a general stabilizer such as isopropyl acid phosphate or linoleic acid. For objects, it is significantly suppressed. Thus,
Even if the agricultural chemical composition of the present invention is used after long-term storage, the decomposition of the organic phosphorus compound is suppressed and maintains a high insecticidal effect, and 4,6-dimethyl-2-(1-(.

-Tolyl)-1-ethylidenehydrazinocopyrimidine is also prevented from being degraded, and the control effects on rice blast and sesame leaf blight are simultaneously exhibited without deterioration.

Claims (1)

[Claims] Contains 4,6-dimethyl-2-[1-(o-tolyl)-1-ethylidenehydrazino]pyrimidine or a salt thereof, an organic phosphorus compound, and boron oxide or a complex of boron oxide A pesticide composition characterized by: