JPH0127041B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a highly stable agricultural and horticultural fungicidal composition containing methyl 1-(n-butylcarbamoyl)benzimidazol-2-ylcarbamate (hereinafter referred to as benomyl) as a fungicidal active ingredient. be. Benomyl is known to have excellent bactericidal properties (Special Publication No. 45-25720) and is used as a fungicide in the field of agriculture and horticulture, but it has problems with storage stability and its active ingredients deteriorate over time. It had the disadvantage that it decomposed (Special Publication No. 47-31618) or that its physical properties deteriorated over time. For example, in the case of wettable powders, when the powder is poured into water and stirred, the powder is not completely dispersed or suspended in the water, and an increase in undispersed particles is observed, which causes them to settle to the bottom of the water. These can cause problems when dispersing formulations, and it is desired to develop formulations with good stability that prevent quality deterioration over time. In order to formulate benomyl, which tends to deteriorate in quality over time, many studies have been conducted in the past to prevent deterioration over time. However, its component stabilizing effect is insufficient,
In addition, almost no effect was observed in preventing deterioration of physical properties. In addition, the present inventors previously proposed a method of adding metal oxides for the purpose of stabilizing benomyl (Japanese Patent Application Laid-Open No. 1989-99505), but according to this method, benomyl could be almost stabilized. Although this is possible, its effect on physical deterioration is insufficient. This invention was made in order to solve the problems of the conventional products as described above, and by containing dry process white carbon, it prevents deterioration of the components and physical properties and provides a stable agricultural and horticultural product. The purpose of the present invention is to provide a disinfectant composition for disinfection. This invention is an agricultural and horticultural fungicidal composition characterized by containing methyl 1-(n-butylcarbamoyl) bezimidazol-2-ylcarbamate and dry process white carbon. The benomyl used in the present invention has the formula: It is indicated by. In addition, dry process white carbon is white carbon (fine particle silicic acid) produced by a dry process, and includes the following types. Manufactured by thermal decomposition (pyrolysis method, gas phase method) of silicon halide. …As in equation (2),
Silicon halide vapor such as silicon tetrachloride, hydrogen, and oxygen (air) are mixed and combusted in a fixed ratio to produce fine particles of silicic acid and by-product hydrochloric acid at a flame temperature of 1000 to 1200°C, and both are separated by cooling. The gaseous hydrochloric acid is removed from the silicic acid using hot air. SiCl ₄ +H ₂ +O ₂ →SiO ₂・nH ₂ O + HCl…(2) Produced by thermal decomposition of silicic acid-containing materials. ...As shown in equation (3), when silicic acid-containing materials with high silicic acid content, such as silica stone, silica sand, and white clay, are heated and reduced at approximately 2000°C using an electric arc in the presence of a carbon source such as coke and anthracite, The vaporized silicon monoxide is oxidized again by air and collected as fine particles of silicic acid. SiO ₂ +C+O ₂ →SiO ₂・nH ₂ O+CO ₂ …(3) Manufactured by thermal decomposition of organosilicon compounds. ...As in (4), various silicate esters,
Organic silicate compounds such as ethyl silicate are thermally decomposed and fine particles of silicic acid are collected. R.SiO.AC+O ₂ →SiO _{2.nH 2} O (4) Among the above dry process white carbons, those are particularly preferred. Further, it is also possible to use other materials than those exemplified above. These may be used alone or in combination. Dry process white carbon has extremely high purity of silicon oxide compared to wet process white carbon (white carbon manufactured by wet process).
It has characteristics such as extremely low adsorption of moisture. Wet white carbon has traditionally been used as a diluent in the formulation of agricultural chemicals, but as shown in the test examples below, it has no stabilizing effect on benomyl, and therefore cannot be used as a stabilizer in the present invention. Can not. The blending ratio of dry process white carbon to benomyl is 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight of dry process white carbon to 1 part by weight of benomyl.
2 parts by weight. The agricultural and horticultural disinfectant composition of the present invention contains calcium oxide (CaO), barium oxide (BaO), aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ), and ditrioxide in addition to benomyl and dry process white carbon. It may contain one or more compounds selected from boron (B ₂ O ₃ ) and zinc oxide (hereinafter referred to as metal oxides, etc.), thereby increasing the stabilizing effect of benomyl. The proportion of these metal oxides, etc. used is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, per 1 part by weight of benomyl. The agricultural and horticultural fungicidal composition of the present invention can be produced by mixing or pulverizing benomyl, dry process white carbon, and, if necessary, the metal oxides, etc., by a known method. Metal oxides etc. can be mixed into the formulation, but
It is also possible to encapsulate one or more of them in air-permeable sachets and then encapsulate them in the packaging of the agricultural and horticultural sterilizing composition of the present invention. At the time of formulation, if necessary, auxiliary agents such as diluents, surfactants, and fixing agents commonly used in agricultural and horticultural chemicals may be added to form a formulation such as a wettable powder. Examples of the diluent include fine mineral powders such as clay, talc, bentonite, and diatomaceous earth. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene styrylphenyl ether, as well as alkylaryl sulfonates and alkyl sulfates. Examples include ionic surfactants such as ester salts, fatty acid salts, lignin sulfonates, alkylbenzene sulfonates, naphthalene sulfonates, and alkylamine salts. Examples of the fixing agent include solid paraffin, vinyl acetate resin, and natural oils and fats. In addition to the above-mentioned compounds, in the present invention, other stabilizers made of natural or synthetic substances, fungicides, insecticides, herbicides, plant growth promoters, etc. may be used as necessary to the extent that they do not inhibit the effects of the present invention. regulator, synergist,
Attractants, repellents, fertilizers, fragrances, coloring agents, physical property improvers, etc. may be added. Specific examples of other fungicides and insecticides that can be blended include copper-based fungicides such as cupric hydroxide and copper 8-quinolinol, or zinc ethylenebis(dithiocarbamate), ethylenebis( organic sulfur fungicides such as manganese dithiocarbamate), zinc-maneb complex compound, zinc dimethyldithiocarbamate, dimethyl 4,4′-o-phenylenebis(3-thioallophanoate) and bis(dimethylthiocarbamoyl)disulfide, or , N-(parafluorophenyl)-2,3-dichloromaleimide, 4,5,6,7-tetrachlorophthalide, N-(trichloromethylthio)-4-
Organochlorine disinfectants such as cyclohexene-1,2-dicarboximide and tetrachloroisophthalonitrile, or S-benzyl thiophosphate = O,O-diisopropyl and O-ethyl dithiophosphate = S,S'-diphenyl, etc. organophosphorus fungicides, or benzanilide fungicides such as 2-methyl-3'-isopropoxy-benzanilide and 3'-isopropoxy-2-trifluoromethylbenzanilide, or Blastcy Antibiotics such as Zin S, polyoxin and kasugamycin, or O,O-dimethyl thiophosphate=O-4-nitro-m-tolyl, O,O-diethyl thiophosphate=O
-2-isopropyl-4-methyl-6-pyrimidinyl, S-2-methoxy-5-oxo-1,3,4-thiadiazolin-4-ylmethyl dithiophosphate, O,O-dimethyl thiophosphate =O-4-methylthio-m-tolyl, thiophosphoric acid, O,O-dimethyl=O-3,5,6-trichloro-2-pyridyl, O,O-diethyl thiophosphate=O-3,5,6- Trichloro-2-pyridyl, S-[α-(ethoxycarbonyl)benzyl] dithiophosphate=O,O-dimethyl, 2- phosphoric acid
Chloro-1-(2,4-dichlorophenyl)vinyl dimethyl and 2-chloro-1- phosphate
Organophosphorus insecticides such as (2,4,5-trichlorophenyl)vinyl dimethyl, or 3-chloro-N-ethoxy-2,6-benzoate
Organochlorine insecticides such as dimethoxybenzimidic anhydride and chlormethanesulfonamide, or 1-naphthyl methylcarbamate, m-tolyl methylcarbamate and o methylcarbamate
Examples include carbamate insecticides such as -sec-butylphenyl. As explained above, since the agricultural and horticultural fungicidal composition of the present invention contains benomyl and dry process white carbon, it has extremely high storage stability, and decomposition of benomyl and deterioration of physical properties are small. Therefore, the formulation of the agricultural and horticultural fungicidal composition of the present invention exhibits high bactericidal activity even after long-term storage, and maintains good physicochemical properties desired during spraying. Furthermore, the agricultural and horticultural fungicidal composition of the present invention is not toxic to humans or livestock, and has little phytotoxicity to plants. Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Note that all parts in each example indicate parts by weight. Further, the white carbon used in each example and the white carbon that can be used are shown in Table 1. In Table 1, "dry method" indicates dry white carbon, "wet method" indicates wet white carbon, and "manufacturing method" indicates the method for producing the white carbon.

【table】

[Table] Example 1 (Wettable powder) Benomyl: 50 parts, Aerosil-130: 5 parts, sodium dodecylbenzenesulfonate: 3 parts, calcium ligninsulfonate: 5 parts, clay: 37
After mixing the two parts, it is crushed to make a wettable powder. Example 2 (Wettable powder) Benomyl: 20 parts, tetrachloroisophthalonitrile: 50 parts, Aerosil-200: 3 parts, calcium oxide: 2 parts, sodium dodecylbenzenesulfonate: 3 parts, calcium ligninsulfonate:
After mixing 5 parts and 17 parts of clay, the mixture is ground and used as a wettable powder. Example 3 (Wettable powder) Benomyl: 20 parts, bis(dimethylthiocarbamoyl) disulfide: 20 parts, furanzyl-251:
5 parts of diboron trioxide: 3 parts, sodium dodecylbenzenesulfonate: 2 parts, sodium naphthalenesulfonate: 3 parts, and clay: 47 parts, and the mixture is ground to obtain a wettable powder. Example 4 (Wettable powder) Benomyl: 20 parts, N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide: 50 parts, Turnip-O-Sil M-5: 1 part, zinc oxide: 3 parts, sodium lauryl sulfate: 3 parts,
Polyoxyethylene nonyl phenyl ether: 2
1 part, diatomaceous earth: After mixing 21 parts, crush it and use it as a wettable powder. Example 5 (Wettable powder) Benomyl: 20 parts, 2-methyl-3'-isopropoxy-benzanilide: 60 parts, Aerosil R-
972: 4 parts, aluminum oxide: 1 part, polyoxyethylene styryl phenyl ether: 3 parts, sodium naphthalene sulfonate: 4 parts, clay:
After mixing 8 parts, the mixture is ground and used as a wettable powder. Example 6 (Wettable powder) Benomyl: 50 parts, Aerosil-130: 5 parts, diboron trioxide: 3 parts, sodium dodecylbenzenesulfonate: 3 parts, calcium ligninsulfonate: 5 parts, clay: 34 parts. After mixing, the mixture is crushed to form a wettable powder. Next, a test example regarding the effect of preventing decomposition and the effect of preventing physical deterioration of benomyl in the formulation of the above example will be shown. Test Example 1 Additive (white carbon) according to Example 1
The preparations prepared with different types of were placed in a 40℃ thermostat.
After storage for 30 and 60 days, Benomyl was analyzed and its physical properties were measured to examine its decomposition prevention effect and physical deterioration prevention effect. Analysis of benomyl was performed by extracting benomyl from each preparation with chloroform, then separating it using high performance liquid chromatography.
Quantification was performed using an ultraviolet absorption detector. Physical properties were measured by counting the number of undispersed particles. The results are shown in Table 2. The method for calculating the decomposition rate and the method for measuring the physical properties of benomyl are as follows. Benomyl decomposition rate Decomposition rate (%) = Benomyl content immediately after production (%) -
Benomyl content after storage (%) / Benomyl content immediately after production (%) x 100 Undispersed particle measurement method Take 50g of the wettable powder in a beaker, add about 100ml of water to moisten it, and stir lightly. suspension 32
Transfer to mesh sieve. After washing the residue on the sieve with a small amount of water, calculate the number of particles that did not pass through the sieve, and define this as undecomposed particles.

[Table] Test Example 2 Table 3 shows the results of testing under the same conditions as Test Example 1 for formulations prepared according to Example 6 with different types of metal oxides.

[Table] Test Example 3 Additive (white carbon) according to Example 1
The preparations prepared with different types of were placed in a thermostat at 50℃.
After storage for 30 and 60 days, benomyl was analyzed and its physical properties were measured, and its decomposition prevention effect and physical deterioration prevention effect were examined. The method for calculating the decomposition rate of benomyl and the method for measuring the physical properties are the same as in Test Example 1. The results are shown in Table 4.

[Table] Test Example 4 Table 5 shows the results of testing under the same conditions as Test Example 3 for formulations prepared according to Example 6 with different types of metal oxides.

[Table] From the above results, the formulation of the agricultural and horticultural fungicidal composition according to the present invention has a lower
It can be seen that there is little decomposition of benomyl, deterioration of physical properties is prevented, and it has extremely excellent stability.

Claims (1)

[Scope of Claims] 1. An agricultural and horticultural fungicidal composition comprising methyl 1-(n-butylcarbamoyl)benzimidazol-2-ylcarbamate and dry process white carbon. 2. The agricultural and horticultural fungicidal composition according to claim 1, wherein the dry process white carbon is fine particle silicic acid produced by thermal decomposition of a silicon halide, a silicic acid-containing substance, or an organosilicon compound. 3. The agricultural and horticultural fungicidal composition according to claim 1 or 2, further comprising one or more compounds selected from calcium oxide, barium oxide, aluminum oxide, silicon dioxide, diboron trioxide, and zinc oxide. .