JPS6121522B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention suppresses chemical reactions between the active ingredients and a decrease in efficacy in a stabilized agrochemical composition, more specifically, in an agrochemical composition containing two or more types of active ingredients. This is related to stabilization. When using agricultural chemicals, it is often done by mixing two or more active ingredients with different mechanisms of action to compensate for the weaknesses of each and bring out the strengths of each. By the way, when these types of agricultural chemicals are prepared in advance in factories and made into products, some of the active ingredients may react with each other during storage and transportation, resulting in undesirable situations such as decreased efficacy or increased toxicity. There is something inviting. For example, 5-methyl-1,2,4-triazolo(3,4-b)benzothiazole (hereinafter referred to as tricyclazole) is an excellent fungicide used to control rice blast; When used in combination with organophosphate compounds, in many cases both components react with each other and turn into different compounds that do not exhibit biological activity, making it difficult to put agricultural chemicals based on mixtures of these compounds into practical use. It was hot. The reaction that occurs between these components has not yet been clarified, but when a mixture of these is analyzed after being left for several months, tricyclazole and organic phosphate compounds are hardly detected. On the other hand, the addition of stabilizers to inhibit the decomposition of pesticides containing single active ingredients is already practiced. For example, higher fatty acids, phosphoric acid, isopropyl acid phosphate, or surfactants are added to organic phosphate insecticides, and amine compounds or paraformaldehyde are added to dithiocarbamate fungicides. Alternatively, it is known to stabilize carbamate insecticides by adding phosphoric acid to them. However, these methods all prevent the compound present as a single active ingredient from being decomposed by heat, light, or the contact action of coexisting substances, and in the case of tricyclazole and organophosphate compounds, As such, the situation is completely different from the case of preventing a decrease in efficacy due to the reaction of two types of compounds, so the former stabilizing means cannot simply be applied to the latter. Therefore, it is desirable to obtain a stabilizer capable of suppressing the chemical reaction between the active ingredients and stabilizing the agrochemical composition containing two or more active ingredients without reducing the efficacy of each active ingredient. This has become an important issue in the field. As a result of extensive research into the formulation of agricultural chemicals containing a combination of tricyclazole and organophosphate compounds as active ingredients, the present inventors found that, unexpectedly, if phosphoric acids were added to the formulation, the active ingredients would interact. The inventors have found that the reaction between the two is suppressed, that it can withstand long-term storage, and that it does not cause any problems in terms of drug damage or toxicity.Based on this knowledge, the present invention has been completed. That is, the present invention is characterized in that 10 to 1000 parts by weight of phosphoric acids are added as a stabilizer per 100 parts by weight of tricyclazole to a pesticide containing a combination of tricyclazole and an organic phosphate compound as an active ingredient. A stabilized agrochemical composition is provided. In the composition of the present invention, examples of the organic phosphate compound used in combination with tricyclazole include the following.

【table】

【table】

[Table] In addition, organic phosphorus compounds such as those shown below, which have a chemical structure similar to that of organic phosphate esters, can also be used.

[Table] These organic phosphate compounds are used in an amount ranging from 50 to 1000 parts by weight per 100 parts by weight of tricyclazole. Next, in the present invention, the phosphoric acid added as a stabilizer is represented by the general formula (HPO ₃ ) _o or H _o+2 P _o O _3o+1 (n in the formula is a positive integer) Examples of such compounds include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and polyphosphoric acid which is a mixture of these and linear condensed phosphoric acid. These phosphoric acids are added in amounts ranging from 10 to 1000 parts by weight per 100 parts by weight of tricyclazole. In addition to tricyclazole, organic phosphate esters, and phosphoric acids, the agricultural chemical composition of the present invention contains auxiliary additive components commonly used in ordinary agricultural chemicals, such as fillers such as clay and white carbon, lignin sulfonates, and alkylbenzene sulfones. surfactants such as acid salts, polyoxyethylene alkylaryl ethers, and alkylnaphthalene sulfonic acids;
A binder such as polyvinyl alcohol or carboxymethyl cellulose, a dispersion stabilizer such as ethylene glycol or glycerin, etc. can be contained. In addition, insecticides, fungicides, herbicides, etc. other than the active ingredients of the present invention can be further blended. In order to prepare the agrochemical composition of the present invention, predetermined essential components and auxiliary additive components added as desired are mixed uniformly, and this is formulated into a powder, granule, wettable powder, sol, etc. good. It has been known to suppress the reaction by adding a third substance to two types of compounds that tend to react with each other. However, it is not known that the active ingredients of agricultural chemicals can be stabilized by such means. In the case of pesticides, there are no stabilizers that enable long-term storage, and even if they were, they would be special, making them very expensive, causing phytotoxicity to plants and toxicity to animals, and This is because it involves negative aspects such as adverse effects on desired physical and chemical properties. In the present invention, by using phosphoric acids as a stabilizer, we have succeeded in obtaining an excellent stabilizing effect without the above-mentioned difficulties. Next, the present invention will be explained in more detail with reference to Examples and Test Examples. Example 1 (powder) 1 part by weight of tricyclazole, 2 parts by weight of MEP, 4 parts by weight of white carbon, and 88 parts by weight of mineral clay fine powder
Parts by weight were mixed and pulverized to prepare a pesticide. Next, 5 parts by weight of polyphosphoric acid was added as a stabilizer to this mixture and mixed in the same manner as in Example 1. For comparison, 5 parts by weight of fine powder clay was added instead of polyphosphoric acid (Comparative Example 1-1).
A product containing 5 parts by weight of isopropyl acid phosphate (Comparative Example 1-2) and a product containing 5 parts by weight of tall oil fatty acid (Comparative Example 1-3) were prepared. Example 2 (hydrating powder) 20 parts by weight of tricyclazole, dimethylvinphos
40 parts by weight of sodium lauryl sulfate, 3 parts by weight of calcium lignosulfonate, 5 parts by weight of orthophosphoric acid, 5 parts by weight of white carbon, and 24 parts by weight of fine mineral clay were weighed and mixed to make a diet-o.
- Finely pulverized with a Jet-o-mizer to make a mixed wettable powder. For comparison, a sample having the same composition was prepared except that orthophosphoric acid was replaced with finely divided clay (Comparative Example 2). Example 3 (powder) 1 part by weight of tricyclazole, 2 parts by weight of CVMP,
5 parts by weight of pyrophosphoric acid, 4 parts by weight of white carbon, and 88 parts by weight of fine mineral clay were weighed and mixed, and the mixture was pulverized using an impact pulverizer to obtain a mixed powder. For comparison, a sample with the same composition was prepared except that pyrophosphoric acid was replaced with finely divided clay (Comparative Example 3). Example 4 (granules) 2 parts by weight of tricyclazole raw material finely pulverized with a diet-o-mizer, 10 parts by weight of EDDP, 2 parts by weight of sodium alkylbenzenesulfonate, 2 parts by weight of polyphosphoric acid, 2 parts by weight of sodium ligninsulfonate, polyvinyl Weigh and mix 1 part by weight of alcohol, 10 parts by weight of white carbon, and 71 parts by weight of fine mineral clay, pulverize with an impact pulverizer, add water, knead, granulate with a pelleter, dry, and classify. It was made into a mixed granule. For comparison, a product with the same composition except that polyphosphoric acid was replaced with fine powder clay was prepared (Comparative Example 4). Example 5 (Sol) 10 parts by weight of the tricyclazole raw material finely pulverized with a diet-o-mizer, 20 parts by weight of IBP, 5 parts by weight of a mixture of polyoxyethylene stylphenyl ether and sodium alkylnaphthalene sulfonate, sodium lignin sulfonate. 2 parts by weight, 1 part by weight of tetrapolyphosphoric acid, 10 parts by weight of ethylene glycol
Parts by weight, 0.1 parts by weight of carboxymethyl cellulose, and 51.9 parts by weight of water were weighed, mixed in a homo mixer, and then wet-pulverized to obtain a mixed sol. For comparison, a product with the same composition was prepared except that tetrapolyphosphoric acid was replaced with finely divided clay (Comparative Example 5). Example 6 (powder) 1 part by weight of tricyclazole, 2 parts by weight of Cartap (insecticidal ingredient), 2 parts by weight of dimethylvinphos, 5 parts by weight of pyrophosphoric acid, 5 parts by weight of white carbon,
85 parts by weight of fine mineral clay were weighed and mixed and pulverized using an impact pulverizer to obtain a mixed powder. In addition, for comparison, a product with the same composition was prepared except that pyrophosphoric acid was replaced with finely divided clay (Comparative Example 6). Example 7 (Powder) 1 part by weight of tricyclazole, 2 parts by weight of propavos, 3 parts by weight of metaphosphoric acid, 3 parts by weight of white carbon, 0.5 part by weight of tall oil fatty acid, and 90.5 parts by weight of mineral fine powder clay (DL clay) were weighed and mixed. The mixture was pulverized using an impact pulverizer to obtain a mixed DL powder. In addition, for comparison, a product having the same composition was prepared except that metaphosphoric acid fine powder clay was used (Comparative Example 7). Example 8 (Powder) 1 part by weight of tricyclazole, 3 parts by weight of diazinon, 1 part by weight of tripolyphosphoric acid, 3 parts by weight of white carbon, and 92 parts by weight of fine mineral clay were weighed and mixed and pulverized using an impact crusher to form a mixed powder. did. In addition, for comparison, a product having the same composition was prepared except that tripolyphosphoric acid was replaced with fine powder clay (Comparative Example 8). Example 9 (powder) 1 part by weight of tricyclazole, 2 parts by weight of MPP, 3 parts by weight of tetrapolyphosphoric acid, 3 parts by weight of white carbon, and 91 parts by weight of fine mineral clay were weighed and mixed,
It was pulverized into a mixed powder using an impact pulverizer. For comparison, a product with the same composition was prepared except that tetrapolyphosphoric acid was replaced with fine powder clay (Comparative Example 9). Example 10 (Powder) 1 part by weight of tricyclazole, 2 parts by weight of PAP, 10 parts by weight of tripolyphosphoric acid, 5 parts by weight of white carbon, and 82 parts by weight of fine mineral clay were weighed and mixed and pulverized using an impact pulverizer to form a mixed powder. did. For comparison, a product with the same composition was prepared except that tripolyphosphoric acid was replaced with finely powdered clay (Comparative Example 10). Example 11 (Powder) 2 parts by weight of tricyclazole, 15 parts by weight of IBP, 3 parts by weight of polyphosphoric acid, 1 part by weight of sodium alkylbenzenesulfonate, 3 parts by weight of sodium ligninsulfonate, and 10 parts by weight of white carbon were uniformly mixed and subjected to an impact method. After finely pulverizing with a pulverizer,
Water was added, kneaded, granulated, dried, and classified to obtain mixed granules. For comparison, a product with the same composition except that polyphosphoric acid was replaced with fine powder clay was prepared (Comparative Example 11). Test Example 1 Formulations of Examples 1 to 11 and Comparative Examples 1 to 11,
After putting 30g of each into sample pins and sealing them, 49
It was stored in a thermostat kept at ℃. After 30 days, tricyclazole and organic phosphate compounds were analyzed by gas chromatography, and in addition to this, in Example 6 and Comparative Example 6, cartap was analyzed. The decomposition rate was calculated from the analysis values of each component before storage in the incubator and the analysis values after storage at 40°C for 30 days. The test results are shown in column A of the following table. Test Example 2 Formulations of Examples 1 to 11 and Comparative Examples 1 to 11,
After putting 30g of each into sample pins and sealing them,
After leaving it in a room without temperature control for 12 months, tricyclazole and organic phosphate compounds were analyzed using gas chromatography. Then, the decomposition rate was calculated from the analysis values of each component immediately after production and the analysis values after standing at room temperature for 12 months. The test results are shown in column B of the following table.

【table】

[Table] As is clear from the results, the composition of the present invention shows significantly less decomposition of tricyclazole than the composition without the addition of a stabilizer.

Claims (1)

[Claims] 1 5-methyl-1,2,4-triazolo (3,
4-b) 5-methyl-1,2,
4-triazolo(3,4-b)benzothiazole
A stabilized agricultural chemical composition characterized in that 10 to 1000 parts by weight of phosphoric acids are added per 100 parts by weight. 2. The composition according to claim 1, wherein the phosphoric acid is orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, or various polyphosphoric acids.