JPH048407B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized agrochemical composition, and more specifically, to stabilizing a composition by preventing different types of agrochemical active substances from decomposing due to chemical reactions with each other, thereby reducing their medicinal efficacy. In general, the composition of pesticides includes those that are expected to have a single medicinal effect through a single pesticide active substance, and those that are expected to have a single medicinal effect by combining two or more types of pesticide active substances. Some are expected to have a wide range of excellent medicinal effects, while others are aimed at labor-saving simultaneous control. In particular, mixtures containing two or more pesticide active substances are currently widely used in the field of agrochemicals, but these mixtures take a long time from manufacture to use. During this time, different types of pesticide active substances may undergo chemical reactions with each other and decompose, resulting in no longer exhibiting biological activity or sometimes causing chemical damage. For example, 5-methyl-1,2,4-triazolo(3,4-b)benzothiazole (hereinafter abbreviated as TC), a fungicide that exhibits excellent control effects on rice blast, etc., and rice blast, planthopper, etc. etc., with an insecticidal organophosphoric acid compound such as O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate (hereinafter abbreviated as MEP). However, when attempting to exert the combined biological activity of both compounds, both components undergo a chemical reaction with each other and decompose, resulting in no longer exhibiting effective biological activity.
Moreover, even if isopropyl acid phosphate, fatty acids, etc., which are conventionally known as stabilizers for organic phosphoric acid compounds, are added, no stabilizing effect can be obtained. For this reason, various efforts have been made to suppress the decomposition of mixed agricultural chemicals containing TC and organic phosphoric acid compounds [for example, methods that add phosphoric acids as a stabilizer (JP-A-10102-1983); One that forms a cyclodextrin clathrate compound (Japanese Patent Laid-Open No. 56-75496), one that forms an acid addition salt of TC (Japanese Patent Laid-Open No. 56-75413), one that adsorbs TC on an adsorbent (Japanese Patent Laid-Open No. 56-75413). -77208), etc.], but none of these methods can be said to be sufficient in terms of stabilizing effect, industrial manufacturing method, utilization rate of the active ingredient after pesticide application, etc. The present inventor has conducted various studies on the stabilization of mixed pesticides, paying attention to the current situation where it is difficult to put these useful mixed pesticides into practical use, although it is hoped that they will appear. , only oxalic acid or (and) benzenesulfonic acid specifically suppresses the chemical reaction that occurs between TC and organophosphoric acid compounds, hardly decomposing even during long-term storage, and preventing production from factory production. We found that the active ingredients remained sufficiently until it was actually used, and based on these findings, we conducted further studies.
The invention has been completed. That is, the present invention relates to TC or a salt thereof and the general formula [In the formula, X and X' are sulfur atoms or oxygen atoms,
Y is a sulfur atom, oxygen atom or imino group, R' is an alkyl or alkenyl group having 2 or less carbon atoms substituted with lower alkoxycarbonyl, lower alkyl, halogen, hydroxy, phenyl or lower alkylcarbamoyl, 3-methyl- 4
The present invention relates to a stabilized agrochemical composition prepared by mixing an insecticidal organophosphoric acid compound represented by the formula -nitrophenyl group or acetyl group], a solid carrier, and oxalic acid or (and) benzenesulfonic acid. In the above general formula [], lower alkoxy in lower alkoxycarbonyl is, for example, alkoxy having 1 to 3 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, etc., and lower alkyl in lower alkyl and lower alkylcarbamoyl is, For example, methyl, ethyl,
A linear or branched alkyl having 1 to 3 carbon atoms such as propyl and isopropyl is used, and as the halogen, for example, fluorine, chlorine, bromine, etc. are used. As the alkyl group having 2 or less carbon atoms, methyl or ethyl is used, and as the alkenyl group having 2 or less carbon atoms, a vinyl group is used. is one of the active ingredients of the agrochemical composition of the present invention.
TC can also be used as a salt with an organic or inorganic acid. Examples of acids that can be used include:
Inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, hydrobromic acid, tartaric acid, malic acid, citric acid, mandelic acid, acetic acid,
Trifluoroacetic acid, acrylic acid, bromoacetic acid, chloroacetic acid, formic acid, cyclohexane-1,1-dicarboxylic acid, oxalic acid, maleic acid, fumaric acid, malonic acid, benzenesulfonic acid, O-aminobenzenesulfonic acid, p-toluene Organic acids such as sulfonic acid and methanesulfonic acid are used. These acids and
Acid addition salts with TC can be prepared by reacting with the desired acid using a conventional method in a suitable solvent such as water, an organic solvent such as an alcohol such as methanol or ethanol, and then distilling off the solvent. They are separated by, for example, In the insecticidal organophosphoric acid compound represented by the general formula [], X is a sulfur atom, X' is oxygen, Y is a sulfur atom or oxygen atom, and R' is the number of carbon atoms substituted with two lower alkoxycarbonyls. Compounds exhibiting up to 2 alkyl groups or 3-methyl-4-nitrophenyl groups are preferred. As the insecticidal organic phosphoric acid compound represented by the general formula [], specifically, for example, the following are used. Compound Abbreviation (1) O,O-dimethyl-O-(3-methyl-4-
Nitrophenyl) phosphorothioate
(MEP) (2) S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethylphosphorothionate
(Marathon) (3) 2,2-dichlorovinyl O,O-dimethyl phosphate (DDVP) (4) O,O-dimethyl 2,2,2-trichloro-
1-Hydroxyethylphosphonate
(DEP) (5) O,S-dimethyl-N-acetylphosphoroamidothiolate (acephenate) (6) 1-Methyl-2-methylcarbamoylvinyl O,O-dimethylphosphate
(alphaate) (7) S-[α-(ethoxycarbonyl)benzyl]
O,O-dimethyl phosphorothionate
(Elsan) (8) S-(N-methylcarbamoylmethyl)O,
O-dimethyl phosphorothiorothionate
(Dimethoate) These insecticidal organic phosphoric acid compounds are appropriately used in a weight ratio of 2:1 to 1:5, preferably 1:1 to 1:2, relative to TC or its salt. Next, the weight ratio of oxalic acid or benzenesulfonic acid used in the present invention to TC or its salt is 5:
It is mixed in the range of 1 to 1:10, but the weight ratio is 2:
The preferred range is 1 to 1:4. Solid carriers include vegetable powders (such as soybean flour, tobacco flour, wheat flour, and wood flour), mineral powders (such as clays such as kaolin, bentonite, and acid clay, and talcs such as talc powder and waxite powder). , diatomaceous earth,
silica such as mica powder), calcium carbonate,
Sulfur powder, activated carbon, etc. may also be used, and one or a mixture of two or more of these may be used. The agrochemical composition of the present invention can be made into a solid dosage form such as a powder, a wettable powder, or a granule using a commonly known method. The content of TC or its salt and insecticidal organophosphoric acid compound is 0.5 to 5% in the case of powder.
It may be used in a range of 5 to 15% in the case of wettable powders and 1 to 10% in the case of granules. Of course, antioxidants (e.g. dibutylhydroxytoluene, 4,
4'-thiobis-6-t-butyl-3-methylphenol, etc.), dispersants (e.g., ethylene glycol, glycerin, etc.), surfactants (e.g., lignin sulfonate, alkylbenzene sulfonate, polyoxyethylene alkyl (aryl ether, alkylnaphthalene sulfonate, etc.), binders (eg, polyvinyl alcohol, carboxymethyl cellulose, etc.), flow aids (eg, white carbon, etc.), synergists, etc. can be used as appropriate. Active ingredients other than the TC or its salt and the insecticidal organic phosphoric acid compound of the present invention include known insecticides (e.g., 2-sec-butyl-N-methylcarbamate, O-sec-butylphenyl methylcarbamate, etc.) and fungicides. (For example 4, 5, 6, 7
-Tetrachlorophthalide, Blastocide S-benzylaminobenzene sulfonate, validamycin A, etc.) can also be further blended. Next, Examples, Reference Examples, and Test Examples will be described to further explain the present invention in detail. Example 1 1 part by weight of TC, 2 parts by weight of MEP, 2 parts by weight of oxalic acid, and 95 parts by weight 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 A powder was obtained in the same manner as in Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 1 part by weight of benzenesulfonic acid, and part by weight of clay. Example 3 1 part by weight of TC, 2 parts by weight of MEP, 2-sec-butylphenyl-N-methylcarbamate (BPMC)
A powder was obtained in the same manner as in Example 1 using 2 parts by weight, 2 parts by weight of oxalic acid, and 93 parts by weight of clay. Example 4 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of oxalic acid, 5 parts by weight of alpha starch, and 87 parts by weight of clay are weighed and mixed in a kneader, then water is poured and kneaded well. This is granulated using a granulator and dried using a fluidized bed dryer to obtain granules. Example 5 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of benzenesulfonic acid, 5 parts by weight of alpha starch, 2 parts by weight of clay
Granules were obtained in the same manner as in Example 4 using 87 parts by weight. Example 6 TC5 parts by weight, MEP5 parts by weight, white carbon
Weigh out 10 parts by weight, 10 parts by weight of oxalic acid, 5 parts by weight of sodium lauryl sulfate, 2 parts by weight of sodium ligninsulfonate, and 63 parts by weight of clay, and mix them in a Raikai machine. Mix the entire amount again using a flash mixer to obtain a wettable powder. Example 7 A powder was obtained in the same manner as in Example 1 using 1 part by weight of TC, 2 parts by weight of Marathon, 2 parts by weight of oxalic acid, and 95 parts by weight of clay. Example 8 1 part by weight of TC hydrochloride (synthesized according to the method described in JP-A-56-75413), 2 parts by weight of MEP, 2 parts by weight of oxalic acid
Weigh out 95 parts by weight of clay and mix in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder. Example 9 A powder was obtained in the same manner as in Example 8 using 1 part by weight of TC, 2 parts by weight of MEP, 1 part by weight of oxalic acid, 1 part by weight of benzenesulfonic acid, and 95 parts by weight of clay. Reference example 1 Weigh 1 part by weight of TC, 2 parts by weight of MEP, and 97 parts by weight of clay, and mix them in a Raikai machine. Mix the entire amount again with a flash mixer to obtain a powder. Reference Example 2 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 1 part by weight of 85% phosphoric acid, and 96 parts by weight of clay. Reference Example 3 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 1 part by weight of PAP (isopropyl acid phosphate), and 96 parts by weight of clay. Reference Example 4 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 3 parts by weight of metaphosphoric acid, and 94 parts by weight of clay. Reference Example 5 Weigh out 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of alpha starch, and 92 parts by weight of clay, mix in a kneader, then pour water and knead well. This is granulated using a granulator and dried using a fluidized bed dryer to obtain granules. Reference example 6 TC5 parts by weight, MEP5 parts by weight, white carbon
10 parts by weight, 5 parts by weight of sodium lauryl sulfate, 2 parts by weight of sodium ligninsulfonate, Clay 73
Weigh out the weight parts and mix in a Raikai machine. Mix the entire amount again using a flash mixer to obtain a wettable powder. Reference Example 7 A powder was obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of Marathon, and 97 parts by weight of clay. Reference Example 8 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of acetic acid, and 92 parts by weight of clay. Reference Example 9 A powder was obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of formic acid, and 92 parts by weight of clay. Reference Example 10 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of malonic acid, and 92 parts by weight of clay. Reference Example 11 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 5 parts by weight of maleic acid, and 92 parts by weight of clay. Reference Example 12 A powder is obtained in the same manner as in Reference Example 1 using 1 part by weight of TC, 2 parts by weight of MEP, 2 parts by weight of p-toluenesulfonic acid, and 95 parts by weight of clay. Test Example 20 g of each of the preparations obtained in Examples 1 to 9 and Reference Examples 1 to 12 was placed in a sample bottle, sealed tightly, and stored at 40°C for 30 days. Further, 20 g of each preparation was placed in separate sample bottles, tightly capped, and stored at room temperature for one year. Immediately after the expiration of the period, samples were taken out and the content of TC, MEP, or Marathon was measured using high performance liquid chromatography. In addition, the decomposition rate (%) was calculated|required from the following formula. Degradation rate (%) = (1 - Content of active ingredient in sample after storage at constant temperature for a certain period of time/Content of active ingredient in preparation) x 100 The test results are shown in Table 1.

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【table】

Claims (1)

[Claims] 1 5-methyl-1,2,4-triazolo(3,
4-b) Benzothiazole or its salt and general formula [In the formula, X and X' are sulfur atoms or oxygen atoms,
Y is a sulfur atom, oxygen atom or imino group, R' is an alkyl or alkenyl group having 2 or less carbon atoms substituted with lower alkoxycarbonyl, lower alkyl, halogen, hydroxy, phenyl or lower alkylcarbamoyl, 3-methyl- 4
A stabilized agrochemical composition prepared by mixing an insecticidal organophosphoric acid compound represented by the formula - nitrophenyl group or acetyl group], a solid carrier, and oxalic acid or (and) benzenesulfonic acid.