JPH0254801B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to providing a new form of agrochemical formulation. More specifically, the present invention relates to a molded agrochemical product characterized by impregnating a pullulan resin with an agrochemical active ingredient and molding it into a certain shape. Pesticides generally have some degree of toxicity to humans, and some of them are acutely toxic, irritate the skin and eyes, and have a strong odor. It is expected that unexpected accidents will occur if sufficient caution is not taken. Conventionally, when formulating agricultural chemicals, wettable powders and emulsions have been widely adopted and used because of their advantages in increasing the concentration of the agricultural chemical's active ingredients. Wettable powders generate dust during the preparation of the spray solution, which poses unfavorable health and safety problems such as the user inhaling highly acutely toxic pesticide active ingredients, or skin irritation and eye damage. It is also quite possible for emulsions to be accidentally or intentionally swallowed during storage. Currently, the only passive response to these health and safety issues is to write on the label how to use and store the product safely. Therefore, the present inventors conducted intensive research to solve the above problems, and as a result, they considered creating a new dosage form for the agricultural chemical active ingredient other than hydrating powders and emulsions.
The invention has been completed. That is, the present invention impregnates a pullulan-based resin with an agricultural chemical active ingredient and makes it into a molded product.
It is possible to eliminate the generation of dust when the active ingredients of these pesticides are applied without impairing their efficacy as pesticides, and to prevent accidental or intentional ingestion of pesticides during storage, resulting in highly acutely toxic pesticides. This protects pesticide users from the dangers of inhalation and contact with the active ingredients, skin irritation, and eye damage. Furthermore, when actually treating chemicals, when diluting the molded product of the present invention with a predetermined amount of water, if you use a molded product with a certain weight and a certain shape, you can dilute it without having to measure the amount of medicine and water each time. A desired dilution solution can be easily prepared with water according to the multiple. As described above, the molded product of the present application is easy to handle and efficient.
In addition, because it contains pullulan resin, which is a type of water-soluble polymer compound, it has been found that it can prevent the drift of spray particles and also improves the adhesion of active pesticide ingredients to plant surfaces. It was done. The pullulan resin used in the present invention is a linear polymer in which maltotriose, which is a trimer of glucose, is repeatedly bonded to the trimer by α-1,6 bonds, which are different bonds. . Further, the molecular weight of the pullulan-based resin can be arbitrarily produced from several tens of thousands to about 2 million depending on the production conditions, but it is preferably from 10,000 to 1 million, although there is no particular limitation. The pullulan-based resin includes those obtained by modifying such pullulan by etherification, esterification, phosphorylation, oxidation, graft polymerization, etc. The molded products of the present invention are mainly film-like products, sheet-like products, and plate-like products, but they can also be processed and molded into flake-like products, rod-like products, cylindrical products, and the like. When carrying out the present invention, the pullulan resin molded product impregnated with the agrochemical active ingredient may be of various shapes as described above, but the purpose of use is determined to maximize the efficacy of the agrochemical active ingredient. It is necessary to select these shapes depending on the shape. For example, its usage includes (1) diluting a predetermined amount with water;
Examples include (2) pasting it on a seedbed or (3) digging it into the field soil. The agricultural chemical active ingredient used in the present invention is not particularly limited, and may be water-soluble or hydrophobic, and may be used in either solid or liquid form. Typical agricultural chemical active ingredients used in the present invention are listed below. However, the present invention is not limited to these examples. For the active ingredient names of pesticides, common names from the Pesticide Handbook (1981 edition) (Japan Plant Protection Association) were used. Examples of insecticides MPP, MEP, isoxathion, diazinon, pyridafenthione, chlorpyrifosmethyl, vamidothion, marathon, PAP, dimethoate, formothion, thiometone, ethylthiometone, phosalone, DMTP, DDVP, CVMP,
CVP, propafos, acephate, DEP,
NAC, MIPC, BPMC, MPMC, XMC, pyrethroid, kelsen, chlorbenzilate, amitraz, binapacryl, tricyclohexyltin hydroxide, cartap, methomyl, aslerin, fenvalerate, DD, etc. Examples of disinfectants: basic copper sulfate, basic copper chloride, cupric hydroxide,
Oxine copper, zineb, mancozeb, ambam, thiuram, milneb, MAF, TPN, fusaride,
IBP, EDDP, Blasticidin S, Fosdaifene, Kasugamycin, Polyoroxin, Validamycin A, Streptomycin, Hydroxyisoxazole, Captan, Difortan, Forpet, Dichlorofluanid, Anilazine, Thiophanatomethyl, Benomyl, Probenazole, Isoprothiolane, Iprodione, Fluorimide, vinclozolin, procymidone, etc. Examples of herbicides 2, 4-PA, MCP, MCPB, phenothiol, naproanilide, CNP, chromethoxynil,
bifuenotux, bentiocarb, molinate,
DCPA, butachlor, asylum, DCMU,
Linuron, Simazine, Ametrine, Promethrin, Renacil, Oxadiazone, Pyrazolate,
Dazomet, triflurane, DBN, picloram,
Alloxydim, sodium chlorate, glyphosate, etc. Examples of plant growth regulators 4-chlorophenoxyacetic acid, maleic hydrazide, 2-chloroethylphosphonic acid, 2,3,5
-triiodobenzoic acid, 5-chloro-1H-3-
Indazolylacetic acid, gibberellin, 6-(N-benzylamino)purine, etc. Also, mixtures of each pesticide active ingredient can be used. Furthermore, spreading agents, repellents, attractants, and rodenticides can also be used. In the present invention, sodium alginate, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, polyvinylpyrrolidone, sodium polyacrylate, etc. can also be used in combination with the pullulan resin. A surfactant can also be added to improve the solubility of the molded product of the present invention in water. As a surfactant, for example, dodecyl sulfate, dodecylbenzene sulfonate, lignin sulfonate, butylnaphthalene sulfonate, naphthalene sulfonic acid formalin condensate salt, alkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene Nonyl phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene alkyl ether sulfate, polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene styrenated phenyl sulfate, alkyl betaine, alkyl amine salt, quaternary ammonium salt, polyoxyethylene alkylamine,
Examples include polyoxyethylene soybean oil amine and polyoxyethylene oleylamine, and mixtures thereof can also be used. The alkyl group herein refers to saturated and unsaturated or higher fatty acid residues having 8 to 20 carbon atoms. Preferred salts include sodium, calcium, ammonium, and diethanolamine. A plasticizer can also be added if necessary. Examples of the plasticizer include glycerin, diethylene glycol, triethylene glycol, polyethylene glycol, and the like. Furthermore, emetics, corrosion inhibitors, odorants, decomposition inhibitors, pigments, and the like can be added to the molded product of the present invention. For example, emetics include sodium tripolyphosphate and sodium pyrophosphate, corrosion inhibitors include sodium metaborate, sodium nitrite, and sodium benzoate, and odorants include alkylpyridine and n-benzoate. Examples include grass acid and tetrahydrothiophene. In the present invention, the pullulan resin is blended in an amount of 0.1 to 20 parts by weight per 1 part by weight of the agrochemical active ingredient. Further, the content of the active ingredient is preferably 5% or more in consideration of the pesticidal effect or drug administration. The molded product of the present invention can be obtained by simply dissolving (1) the agricultural chemical active ingredient in the solution by preparing an aqueous solution of the pullulan resin, and (2) simply dissolving the agricultural chemical active ingredient in the solution. In the case of hydrophobic solids, a small amount of a finely divided carrier such as white carbon, calcium carbonate, diatomaceous earth, or clay and a surfactant such as sodium dodecylbenzenesulfonate or sodium ligninsulfonate may be used. In addition, impact crushers, jet-o-mizers, etc.
A finely ground highly concentrated wettable powder is prepared and dispersed. (3) If the active ingredient of the pesticide is liquid at room temperature, the active ingredient is attached to white carbon, talc, clay, diatomaceous earth, calcium carbonate, etc.
Prepare and disperse a high concentration wettable powder as in case (2), or add a small amount of solvent and emulsifier to the active ingredient, dissolve and mix to prepare a high concentration emulsion, emulsify and disperse, and then cast the mixture into a solution. It can be manufactured by placing it on a smooth casting surface. A doctor blade or other means may be used to obtain the desired film thickness. Examples are given below to specifically explain the present invention, but the present invention is not limited to these examples. In addition, all parts in the examples mean parts by weight. Example 1 A casting solution prepared by dissolving 1 part of acephate in 3 parts of a 10% by weight aqueous solution of pullulan (molecular weight 100,000) was poured onto a glass plate and dried to obtain acephate 75 of the present invention.
%-containing film-like molded product is obtained. Example 2 80 parts MEP, 5 parts xylene, Solpol 3005X
Add 15 parts (trade name of emulsifier manufactured by Toho Chemical Industry Co., Ltd.), dissolve and mix to prepare a high concentration emulsion. A casting solution in which a part of this is emulsified and dispersed in 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 100,000) is poured onto a glass plate and dried to obtain a film-like molded product containing 40% MEP of the present invention. Example 3 Add 80 parts of NAC, 5 parts of clay, and 15 parts of sodium lignin sulfonate, and grind and mix with an impact grinder.
Prepare highly concentrated hydrating powders. A casting solution in which a part of this is dispersed in 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 200,000) is poured onto a glass plate and dried to obtain a film-like molded product containing 40% NAC of the present invention. Example 4 To 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 100,000), 0.5 part of methomyl and 0.05 part of diethylene glycol
A casting solution containing 32% methomil is poured onto a glass plate and dried to obtain a film-like molded product containing 32% methomil of the present invention. Example 5 10% by weight of acetylated pullulan (molecular weight 100,000)
A casting solution prepared by dissolving 1 part of acephate in 10 parts of an aqueous solution is poured onto a glass plate and dried to obtain a film-like molded product containing 50% acephate of the present invention. Example 6 A casting solution in which 0.1 part of kasugamycin was dissolved in 15 parts of a 10% aqueous solution of pullulan (molecular weight 200,000) was poured onto a glass plate and dried to form a film-like molded product containing 6% kasugamycin of the present invention. obtain. Example 7 80 parts of Daifortan, 8 parts of clay, and 12 parts of sodium dodecylbenzenesulfonate were added and mixed by pulverization using an impact pulverizer to prepare a highly concentrated wettable powder. Add part of this to a 10% aqueous solution of pullulan (molecular weight 100,000).
A casting solution dispersed in 12 parts is poured onto a glass plate and dried to obtain a film-like molded product containing 40% difluortan of the present invention. Example 8 80 parts of benomyl, 5 parts of clay, 5 parts of sodium laurate, and 10 parts of sodium naphthalene sulfonic acid formalin condensate were added and pulverized and mixed using an impact pulverizer to prepare a highly concentrated wettable powder. A part of this is poured onto a glass plate with a casting solution containing 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 200,000) and dried to obtain a film-like molded product containing 40% benomyl of the present invention. Example 9 A casting solution prepared by dissolving 1 part of 2,4-PA amine salt in 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 300,000) was poured onto a glass plate, dried, and the 2.
A film-like molded product containing 50% of 4-PA amine salt is obtained. Example 10 80 parts of DCMU, 5 parts of clay, and 15 parts of sodium alkylnaphthalene sulfonate were added and mixed by pulverization using an impact pulverizer to prepare a highly concentrated wettable powder. One part of this was added to 10% of pullulan (molecular weight 100,000) containing 1% by weight of polyoxyethylene nonyl phenyl ether.
A casting solution dispersed in 10 parts by weight of an aqueous solution is poured onto a glass plate and dried to obtain a film-like molded product containing 40% DCMU of the present invention. Example 11 Maleic acid hydrazide diethanolamine salt added to 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 100,000)
Pour the casting solution in which 1.4 parts of
By drying, a film-like molded product containing 58% maleic acid hydrazide diethanolamine salt of the present invention is obtained. Example 12 A casting solution prepared by dissolving 0.7 parts of 2-chloroethylphosphonic acid in 10 parts of a 10% by weight aqueous solution of pullulan (molecular weight 200,000) was poured onto a glass plate and dried to produce the 2-chloroethylphosphonic acid of the present invention. A film-like molded product containing 41% acid is obtained. Example 13 10% by weight of etherified pullulan (molecular weight 100,000)
A casting solution in which 3 parts of basic copper chloride are dispersed in 10 parts of an aqueous solution is poured onto a glass plate and dried to obtain a sheet-like molded product containing basic copper chloride (containing 44% copper) of the present invention. Next, the usefulness of the present invention will be illustrated by test examples. Test example 1 Drift test A fan is installed at a height of 0.8 m, and a point where the wind speed from there is 2 m/s is determined.
A single head nozzle was installed at a height of 1.5 m, and a butt (32 cm x 25 cm) was installed to collect the sprayed liquid from that point.
cm x 2 cm) was installed at a distance of 2.5 m. 0.05% of a blue dye was added to a spray solution prepared by diluting the molded product of the present invention prepared in the example with water to a predetermined concentration. The amount of spraying is 600ml at a time, and the spray pressure is 4.
Kg/ ^cm2 . This test was repeated twice, and the average value was used. The results are shown in Table 1.

【table】

[Table]
Test example 2 Adhesion test Rice (cultivar Asahi 5-6 leaf stage) in a 1 m ² wooden frame
Example 2 of the present invention
A 1000-fold diluted solution of the molded product prepared according to the method was uniformly sprayed using an auto spray (Oki, air pressure 2 kg/cm ² ) at a rate of 100 per 10 ares. After that, cut it from about 8 cm from the base of the plant and put it in a plastic bag.
The MEP on the rice plants was extracted with 200 ml of acetone, and the MEP per fresh weight of the rice plants was quantitatively analyzed using gas chromatography. The results are shown in Table 2. The molded product of the present invention was able to improve adhesion by more than twice that of conventional formulations.

[Table] Test example 3 Cotton aphid control test Eggplant (variety: Senryo 2) in a 6 cm square pot
No.) was planted, and one of the five-leaf eggplants grown was
15 cotton aphids were inoculated per pot. After being left in a greenhouse for a day and night, the number of all parasites was investigated, and 15 ml of a diluted solution of the drug of Example at a predetermined concentration (500 ppm) was sprayed onto each pot using a spray gun. Five days after the spraying treatment, the number of all parasites was investigated, and the control value (%) was calculated using the following formula. Note that this test was conducted in 5-pot repetition. The results are shown in Table 3. Control value (%) = (1-Ta/Tb/Ua/Ub) x 100 Ta: Total number of parasites after treatment in treated area Tb: 〃 〃 Previous 〃 Ua: Total number of parasites after treatment in untreated area Number Ub: 〃 〃 previous 〃

[Table] Compared to the wettable powder used in the comparative example, the molded product of the present invention, which prevented dust from forming during the preparation of the diluted solution, had an improved pest control effect and no chemical damage was observed. In addition, handling was very simple and efficient. Test Example 4 Tomato Phytophthora Control Efficacy Test Tomato (variety: Sekai No. 1) seedlings at the 5-leaf stage grown in pots with a diameter of 9 cm were sprayed with a predetermined concentration solution of the chemical prepared according to Example 7 using a small sprayer. A sufficient amount was sprinkled on the front and back surfaces. One day after spraying, tomato late blight fungus (Phytophthora infestans;
The cells were inoculated by spraying with a zoosporangial suspension of Phytophthora infestance. After inoculation with the pathogen, it was stored in a humid room at 20°C (relative humidity 100%). In the disease onset investigation, the lesion area ratio (%) on the first to fourth leaves was measured 3 days after inoculation with the pathogen, and the control value (%) was calculated using the following formula. This test was conducted using a 3-pot system in 1 section. The results are shown in Table 4. Control value (%) = (1 - average lesion area ratio in treated area / average lesion area ratio in untreated area) x 100

【table】

[Table] In the table, the numbers in brackets for untreated areas indicate the average lesion area ratio (%) for untreated areas.
The molded product of the present invention, which prevented dust from forming during the preparation of the diluted solution, had an improved pest control effect and no chemical damage was observed compared to the wettable powder used in the comparative example. In addition, handling was very simple and efficient. Test Example 5 Herbicidal Effect Test A plastic pot measuring 20cm long, 12cm wide, and 8cm deep was filled with field soil (alluvial loam), and seeds of crabgrass, chickweed, purslane, goldenrod, and knotweed were sown at about 20 seeds per pot. , and was evenly mixed into the soil surface layer of about 1 cm. For the crop, three soybean seeds (variety: Enrei) were sown in rows per pot. After sowing, the seeds were thoroughly irrigated and kept in a glass greenhouse. Three days after sowing, a predetermined amount of the drug prepared according to Example 10 was diluted in 100 m/10 are of water and applied to the entire surface of the soil. After 30 days of chemical treatment, surviving weeds were extracted according to grass type, the weight (g) of the fresh grass was measured, and the weed killing rate (%) was determined using the following formula. This test was conducted using a 3-pot system in 1 area, and the average weed killing rate (%) was calculated. The results are shown in Table 5. Weed killing rate (%) = (1 - weight of fresh weeds in treated area (g) / weight of fresh weeds in non-treated area (g)) x 100

[Table] The molded product of the present invention, in which dust was prevented during the preparation of the diluted solution, had the same herbicidal effect as the wettable powder used as a comparative example, and no chemical damage was observed. Moreover, handling was simple and efficient.

Claims (1)

[Claims] 1. A molded agrochemical product characterized by impregnating a pullulan resin with an agrochemical active ingredient and molding the resultant product.