JPS58124702A - Aqueous suspension of agricultural chemical composition - Google Patents

Abstract

PURPOSE:To obtain the titled agricultural composition having excellent handleability, stability and applicability, by compounding an agricultural chemical which is solid at normal temperature and is hardly water-soluble, with specific amounts of a condensate of aromatic sulfonic acid and formaldehyde, an emulsifier, and a heteropolysaccharide gum as a thickener. CONSTITUTION:The objective composition contains (A) <=50wt% agricultural chemical which is solid at normal temperature and is hardly soluble in water, e.g. a fungicide such as 5-methyl-[1,2,4]triazolo[3,4,b-]benzothiazole. an insecticide such as tricyclohexyltin hydroxide, a herbicide such as 2-chloro-4,6- bis(ethylamino)-1,3,5-triazine, etc., (B) 0.1-3wt% aromatic sulfonic acid-formaldehyde condensate salt which is an anionic surface active agent (C) 3- 12wt% other emulsifier such as dialkyl succinate compound, polyoxyethylene allyl ether, etc., and (D) 0.05-0.5wt% heteropolysaccharide gum as a thickener.

Description

[Detailed Description of the Invention] This invention relates to a water-suspended agricultural chemical formulation in which a pesticide active ingredient that is solid at room temperature and poorly water-soluble is formulated into a dosage form suitable for a spraying agent. There are preparations in the form of rice grains, such as tablets, irrigation tablets, and emulsions. Among these, powder agents have disadvantages such as a large amount of scattering to the surroundings when being sprayed. In addition, hydrating powders have the disadvantage of poor stability, as they tend to settle between the time they are prepared and the time they are applied. Furthermore, emulsions require the active ingredients to be easily dissolved in solvents, so the types of active ingredients that can be emulsified are narrowly limited, and because they use organic solvents, they are flammable, and some crops may suffer from chemical damage. 〇Recently, aerial spraying using liquid agents is often performed from the perspective of labor saving in spraying work, but the conventional formulations mentioned above are not necessarily suitable for this purpose, and new formulations are being developed. A formulation is desired. Suitable preparations for this purpose include a spraying agent (Japanese Patent Publication No. 46-20519) prepared by suspending agricultural chemical ingredients that are poorly soluble in solvents and cannot be emulsified in water or a hydrophilic medium;
In addition, an oil-in-water mayonnaise-like formulation containing a high concentration of an organophosphorus insecticide, which is a liquid organophosphorus insecticide mixed with a hydrophobic organic solvent, a surfactant, a thickener, etc.
8514), etc. However, in order to make the agricultural chemical active ingredient into ultrafine particles, these conventional formulations require wet grinding while suspended in a solvent, and addition of emulsifiers, dispersants, etc. However, it is not always possible to obtain stable properties, such as when the crushed particles are uniformly dispersed or suspended stably in a solvent. This invention was made in order to eliminate the above-mentioned drawbacks of conventional products, and it requires the addition of special emulsifiers and thickeners. This enables uniform and stable suspension of pesticide ingredients, which are solid at room temperature and poorly water-soluble, and is easy to handle, has excellent storage stability, and has excellent dispersibility and suspension during spraying, making it suitable for use as a spraying agent. It is an object of the present invention to provide a water-suspended agricultural chemical formulation suitable for use in water-based agricultural chemicals. 0.1 to 5% by weight, and 5 to 5% of other emulsifiers.
12% by weight and heteropolysaccharide rubber 005
It is a water-suspended agricultural chemical formulation containing ~0.5% by weight.

The agricultural chemical active ingredient as an active ingredient applicable to this invention is not particularly limited as long as it is solid at room temperature and poorly soluble (including insoluble) in water; for example, 5-methyl-[1,
2,4] triazolo[5゜4-b]pe/dithiazole (
tridiclazole), 2-methyl-5'-isobroboxybenzanilide (mepronil L 4?5-6
- Fungicides such as 7-titrachlorophthalide, 0,0'
Insecticides such as dimethyl 2-chloro-1-(2,4-dichlorophenyl) vinyl phosphate, tolyl N-methyl carbamate, tricyclohexyltin hydroxide, 2-chloro-4,6-bis( Ruamino)
-1,3,5-) riazine, 2-chloro4-4-ethylamino-6-ipropylamino-1.5-5-triazine, and other herbicides.

Depending on the purpose, these drug substances may be used alone, as a mixture of two or more, or as a mixture with other agricultural chemical substances, such as liquid or water-soluble ones. Sometimes used. The blending ratio of the above pesticide ingredients is 50
weight - less than or equal to 10 to 50% by weight 0 Aromatic sulfonic acid formalin condensate salts are anionic surfactants, such as sodium salts, calcium salts, ammonium salts of β-naphthalene sulfonic acid formalin condensates This includes salts, or sodium salts, calcium salts, ammonium salts, etc. of alkylnaphthalene sulfonic acid formalin condensates. The blending ratio of the aromatic sulfonic acid formalin condensate salt is 0.01 to 61 to 6% by weight or 0.01 to 61 to 6% by weight.
It is 1 to 1% by weight.

There are no particular restrictions on other emulsifiers, and those conventionally used for formulations can be used. In particular, as anionic surfactants, dialkylcophosphates (e.g., sodium salt of dibutylsulfosuccinate, calcium salts, sodium salts of dioctyl sulfosuccinate, calcium salts, etc.), alkyl sulfonic acid series (e.g. nonylphenyl sulfonic acid, sodium alkylbenzenesulfonate, etc.), and ligno/sulfo/acid series, and non-ionic As a surfactant, polyoxyethylene allyl ether type (e.g. polyoxyethylene styrylphenyl ether, polyoxyethylene nonylphenyl ether), polyoxyethylene alkyl ether type (e.g. polyoxyethylene nonyl ether, polyoxyethylene dodecyl ether, etc.) ,
and polyoxyethylene alkyl allyl ether sulfate (e.g., polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene dodecyl phenyl ether sulfate, etc.) It is preferable to include one or more selected emulsifiers. Only one type of these emulsifiers is used. You can also combine it alone! , or more may be mixed, and the mixing ratio in the case of mixing may be arbitrarily selected. The blending ratio of the emulsifier is 3 to 12% by weight.

Heteropolysaccharide rubber is compounded as a thickener, and is generally called xanthan gum. It is a high molecular weight linear extracellular substance produced by the action of bacteria of the genus Xanthomonas, and has a molecular weight of 20,000 to 1,000,000.
Water is the main solvent used in the water-suspended agricultural chemical formulation of the present invention, and water alone may be used;
When it is necessary to consider physicochemical properties such as viscosity and specific gravity, use hydrophilic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, chrycerin, polyethylene glycol, ethylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. , or optionally a hydrophobic solvent selected from xylene, toluene, orthochlorotoluene, kerosene, mineral oil, vegetable oil, liquid paraffin, etc.
More than one type of organic solvent may be blended. When blending a solvent, the blending ratio is 1 to 60% by weight, preferably 10 to 20% by weight.
The water-suspended agricultural chemical formulation of the present invention contains 5% by weight in addition to the above components.
An antifoaming agent having a weight φ or less, for example, a silicone antifoaming agent mainly composed of dimethylpolysiloxane, may be entirely blended, and other components may also be entirely blended as necessary.Next, the formulation of the present invention An example of the manufacturing process is shown below.

First, a predetermined amount of heteropolysaccharide rubber as a thickener is dissolved and mixed in water using a stirrer so that the concentration is 90.1 to 0.6% by weight. Next, predetermined amounts of the agricultural chemical raw material, surfactant, antifoaming agent, organic solvent, and forceful water are weighed in this order and placed in a mixing tank, and the mixture is crushed and mixed using a high-speed stirrer for 50 to 90 minutes. Next, these mixtures are processed using a wet grinder.
The agricultural chemical raw material is pulverized to a particle size of 4 μm or less, preferably 0.5 to 5 μm to obtain a product.

The water-suspended agricultural chemical formulation of the present invention is formulated with a combination of special emulsifiers and thickeners, so that it can uniformly and stably suspend agricultural chemical ingredients that are solid at room temperature and are poorly water-soluble, and has good dispersibility. As a result, it is easy to handle throughout the period of manufacture and use, has very little sedimentation even during long-term storage, has excellent storage stability, and has good dispersibility and suspension when sprayed. In each example, parts indicate weight.

Example 1 0.2 parts of heteropolysaccharide rubber was added to 62.2 parts of water, and the mixture was dissolved and mixed for 20 minutes using a regular stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.: Homomixer HV-M type).
Methyl-[1,2,4))riazolo(3,,!1-h)
20 parts of benzothiazole, 0.5 part of sodium β-naphthalene sulfonate formalin condensation, polyoxyethylene styrylphenyl ether/polyoxyethylene nonylphenyl ether sulfate/sodium diptylsulfosuccinate mixture (mixed weight ratio 44/47/6)
7 parts of ethylene glycol and 10 parts of ethylene glycol were weighed and placed in a mixing tank, pulverized and mixed for 4 minutes using a high-speed stirrer (SRB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.), and 0.1 part of an antifoaming agent ( A wet grinder with a capacity of 81 cells (manufactured by Igarashi Kikai Seizo Co., Ltd.: 2G) was added with silicone AP-128 (manufactured by Asahi Chemical Industry Co., Ltd.) and filled with 4/1 hard glass beads of 1.0 to 1.5 mm after stirring. The mixture was pulverized using a sand grinder (Model SL) at a liquid feeding rate of 201/hour to obtain 100 parts of a homogeneous water-suspended agricultural chemical formulation.

Example 2 0.1 part of heteropolysaccharide rubber to 42°8 parts of water,
40 parts of 2-methyl-3-ingloboxyhenzanilide as agricultural chemical ingredients, i and o parts of calcium formalin condensate β-naphthalene sulfonate, polio and diethylene nonylphenyl ether/polyoxyethylene nonyl ether mixture as other emulsifiers. 7 parts and 9 parts of ethylene glycol monoethyl ether as a solvent were weighed into a mixing tank and pulverized and mixed for 90 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). Antifoaming agent (manufactured by Asahi Chemical Industry Co., Ltd.: silicone, AF-128) f: In addition, liquid feeding speed of wet crusher '5
The formulation io was prepared in the same manner as in Example 1, except that 01/hour was used.
Obtained part o.

Example 3 57.5 parts of water, 0.1 part of heteropolysaccharide rubber,
Usually stirred for 50 minutes, 5-methyl-[1,
2,4) Triazolo[5,4-A)benzothiazole 1
0 parts and 20 parts of S-penzyldiisoprobyl phosphorothiolate, 0.5 parts of sodium diptylnaphthalene sulfonate formalin condensate, and other emulsifiers such as sodium lignin sulfonate/phorioxyethylene styryl phenyl ether/nonylphenyl sulfone. 5 parts of the sodium acid mixture and 7 parts of liquid paraffin as a solvent were weighed and placed in a mixing tank, and pulverized and mixed for 90 minutes using a high-speed stirrer (manufactured by Shimazaki Seisakusho Co., Ltd. = RB type stirrer).
Add 0.1 part of an antifoaming agent (Silicone AP-128 manufactured by Asahi Chemical Industry Co., Ltd.) to this, and
Formulation 10 was prepared in the same manner as in Example 1 except that the time was 0.017 hours.
I got 0 copies.

Example 4 449 parts of water, 05 parts of heteropolysaccharide rubber, stirring usually for 50 minutes, dimethyl 2-chloro-1 as agricultural chemical raw material
-(2,4-dichlorophenyl)vinyl phosphate 2
0 parts and m-) 20 parts of lyl methyl carpamate, 7 parts of dibutylnaphthalene sulfonate calcium formalin condensate, etc. Polyoxyethylene styrylphenyl ether/sodium dioctyl sulfosuccinate/polyoxyethylene nonylphenyl ether as an emulsifier Weigh out 8 parts of the sulfate mixture, 3 parts of kerosene as a solvent, and 6 parts of orthochlorotoluene in that order, put them into a mixing tank, and pulverize and mix for 60 minutes with a high-speed stirrer (manufactured by Shimazaki Manufacturing Co., Ltd. = RB type stirrer/machine). Add 0.1 part of antifoaming agent (Silicone AF-12 manufactured by Asahi Chemical Industry Co., Ltd.) to this.
8) was added, and 100 parts of a preparation was obtained in the same manner as in Example 1, except that the liquid feed rate of the wet grinder was set to 301/hour.

Example 5 44 parts water, 4 parts heteropolysaccharide rubber 0.5 part,
40 parts of 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine as a pesticide raw material, stirring usually for 60 minutes, 0.2 part of sodium formalin condensate dioctylnaphthalene sulfonate, and other emulsifiers. 6 parts of polyoxyethylene styrylphenyl ether/polyoxyethylene nonyl ether/polyoxyethylene dodecyl phenyl ether sulfate mixture, 40 parts of isopropyl alcohol as a solvent, and s parts of polyethylene glycol (average molecular weight 2OO) were weighed and placed in a mixing tank. , pulverized and mixed for 0 minutes with a high-speed stirrer (manufactured by Shimazaki Manufacturing Co., Ltd.: RB type stirrer), and 0.1 part of an antifoaming agent (manufactured by Asahi Chemical Industry Co., Ltd.: Silicone Ar-128) k
In addition, 100 parts of a preparation was obtained in the same manner as in Example 1, except that the liquid feed rate of the wet grinder was changed to 2017 hours.

Example 6 56.1 parts of water, 03 parts of heteropolysaccharide rubber, 25 parts of tricyclohexyltine hydroxyoxide as the agricultural chemical raw material, 0.5 parts of formalin condensate of sodium β-naphthalene sulfonate, polyoxyethylene styrylphenyl as other emulsifiers 8 parts of the ether/diptylsulfokonosodium phosphate mixture and 10 parts of ethylene glycol as a solvent were weighed in this order, placed in a mixing tank, and ground for 0 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). Example 1 except that 0.1 part of an antifoaming agent (Silicone AP-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added to the pulverizer, and the liquid feed rate of the wet pulverizer was set to 501/hour.
100 parts of the preparation was obtained in the same manner as in Example 7. 0.05 parts of heteropolysaccharide rubber was added to 52.95 parts of water.
of 5-methyl-[1,2,4) triazolo Ij, 4- h
] 20 parts of benzothiazole and 7 parts of polyoxyethylene styrylphenyl ether/polyoxyethylene alkyl allyl ether sulfate/sodium dibutyl sulfosuccinate mixture were weighed in this order and placed in a mixing tank, using a high-speed stirrer (manufactured by Shimazaki Manufacturing Co., Ltd.: Model RB). stirrer)
Grind and mix for 60 minutes with 41 hard glass beads with a 1.0 to 1.5 r surface! Fine grinding was carried out using a wet grinder (manufactured by Igarashi Kikai Seizo Co., Ltd. = 2G Sand Grinder SL type) with a capacity of 81 cells filled in a tank at a liquid feed rate of 201/hour, and further 25 parts of liquid paraffin, 5 parts of kerosene,
Add 10 parts of ethylene glycol and use a Satake portable stirrer (
(manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.) for 50 minutes to obtain 100 parts of a homogeneous preparation. Reference Example 1 44.7 parts of water, heteropolysaccharite comb D, 2
part, usually stirred for 20 minutes, as a pesticide active ingredient 4.5°6.7
15 parts of 1-tet-2-chlorophthalide and 20 parts of S-penzyl diimpropyl phosphorothiolate, 10 parts of ethylene glycol, and polyoxyethylene nonylphenyl ether/alkylbenzene as an emulsifier without adding any aromatic sulfonic acid formalin condensate salt. Weigh out 10 parts of the sodium sulfonate mixture in order and place them in a mixing tank, pulverize and mix for 40 minutes using a high-speed stirrer (2RB type stirrer manufactured by Shimazaki Seisakusho Co., Ltd.).
Reference Example 2 5-methyl- [1,2,m]) Riazoro [6°4-b]
20 parts of benzothiazole, 1 part of polyvinyl alcohol,
10 parts of polyoxyethylene nonyl phenyl ether and 44 parts of water were pulverized for 5 hours using a wet pulverizer (Niatriter manufactured by Mitsui Miike Manufacturing Co., Ltd.), and then 2 parts of water was added.
5 parts were added to obtain 100 parts of the formulation.

Reference example 5 2-chloro-4,6-bis(ethylamino)-1,3,
5-) Add 40 parts of riazine, 1 part of polyvinyl algol, 10 parts of polyoxyethylene nonylphenyl ether, and 30 parts of water, and grind the powder using the wet grinder of Reference Example 2 for 5 hours, and then add 19 parts of water to prepare a formulation. 0 Reference Example 4 10 parts of ethylene glycol and 3 parts of high-purity montmorillonite were obtained.
594 parts of water, 594 parts of water, 5-methyl-(1,2°4) triazolo(:!1.4
-h) Weigh out 20 parts of benzothiazole, 0.5 parts of sodium β-naphthalene sulfonate formalin condensate, and 7 parts of polyoxyethylene styrylphenyl ether/phorioxyethylene alkyl allyl ether sulfate/sodium diptylsulfosuccinate mixture, respectively. and put it in a mixing tank using a high-speed stirrer (manufactured by Shimazaki Seisakusho Co., Ltd.).
Grind and mix for 50 minutes using an RB type stirrer, and add 0.
1 part antifoaming agent (manufactured by Asahi Chemical Industry Co., Ltd.: Sili: 1-yA
F-128) vi- Added and stirred, 8I was filled into 1.0-1.5 mm hard glass beads 4J'! The mixture was finely pulverized by a wet pulverizer (Igarashi Kikai Seizo Co., Ltd., Model 2G Sand Grinder SL) with a capacity of Bethel at a liquid feed rate of 201/hour to obtain 100 parts of a uniform preparation.

Reference Example 5 1 part of Aerosil 200 (silicon dioxide manufactured by Nippon Aerosil) was added to 42.9 parts of water, and dissolved and mixed for 20 minutes using a regular stirrer (Homomixer HV-M type manufactured by Tokushu Kika Kogyo Co., Ltd.). 40 parts of 2-methyl-3-improboxypenzanilide, 7 parts of polyoxyethylene nonylphenyl ether/polyoxyethylene styrylphenyl ether mixture, 9 parts of ethylene glycol monoethyl ether, antifoaming agent (Asahi Chemical Industry Co., Ltd.) Manufactured by: Silicone AF-1
28) Weigh 1 part of each in order, put them in a mixing tank, and grind and mix for 90 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). 8I filled with! The mixture was finely pulverized using a wet pulverizer (manufactured by Igarashi Kikai Seizo Co., Ltd., Model 2G Sand Grinder SL) with a Betucel capacity at a liquid feeding rate of 'rO1/hour to obtain 100 parts of a uniform preparation.

Test Example 1 Physical Property Test Regarding the preparations obtained in the above Examples and Reference Examples,
Specific gravity, viscosity, cold resistance, heat resistance, and degree of separation were measured using the following methods, and the results are shown in Table 1.

Specific gravity: Measured according to JIS K-4101iCj.

Viscosity: Measure using a B-type viscometer while maintaining the product temperature at 20°C.

Tokyo Keiki Co., Ltd. 8M type cold and heat resistant: 4 pieces of each composition in a 50Tnt capacity wax bottle.
0- Seal tightly and store at -5°C and 50°C for 7 days, and check for separation and sedimentation. Those with little separation and sedimentation are considered to be acceptable □ Separation degree: After putting 80% of each composition into a 100 td container equipped with an ultracentrifuge, it is placed in a frame and rotated at 12,000 rpm for 25 minutes to check for sedimentation. investigate.

Table 1 Physical property test example 2 of each composition Rice blast control effect test Four-leaf stage rice grown from rice seeds (variety Tokoku) in clay pots with a diameter of 9 cm were arranged in a 1 g wooden frame. The preparations produced in Example 1 and Reference Example 2 and left at room temperature for one month were diluted with water to a predetermined dilution ratio, and 1 ward Atashi 100- was sprayed with a ladle-type sprayer. . Two days after spraying, a spore suspension of blast fungus was inoculated by spraying in a humid room. After 10 days, the number of lesions per 10 leaves was investigated, and the disease index was determined according to the following criteria. The results are shown in Table 2.

Judgment criteria 5: No disease 4: Slight disease 6: Slight disease 2: Heavy disease 1: Severe disease Table 2 Blast control effect From the above results, the examples of the present invention have excellent cold resistance, heat resistance and dispersibility. It can be seen that the activity as a pesticide is also high.

Claims (1)

[Scope of Claims] (1) As active ingredients, 50% by weight or less of a pesticide active ingredient that is solid at room temperature and poorly water-soluble, and 0.1 to 5% by weight of aromatic sulfonic acid formalin condensate salt. Add other emulsifiers to 6~
12% by weight and 0.0% heteropolysaccharide rubber
Water-suspended pesticide formulation containing 5 to 0.5% by weight (2) The pesticide active ingredient is 5-methyl-(1,2,4))riazolo(3,4-5)benzothiazole, 2-methyl-6 ′
-isoproboxybenzanilide, 4.5. 6.7
-titrachlorophthalide, 0. Ol-Dimethyl 2-chloro-1-(2,4-dichlorophenyl)vinyl phosphate, Tolyl N-methylcarbamate, Tricyclohexyltin hydroxide, 2-chloro-4,6-
Bis(ethylamino)-1,3,5-)riazine and 2-chloro-4-ethylamino-6-itupropylamino1. ! The water-suspended agricultural chemical formulation (5) aromatic sulfonic acid formalin condensate salt according to claim 1, which is one or more selected from β-1, 5-) riazine, The water-suspended agricultural chemical formulation according to claim 1 or 2, which is one or more selected from sodium salt, calcium salt, or ammonium salt of acid formalin condensate or alkylnaphthalene sulfonic acid formalin condensate. (4) Other emulsifiers are selected from dialkyl succinic acid, alkylaryl sulfonic acid, lignin sulfonic acid, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkyl allyl ether sulfate. (5) A patent in which the solvent is mainly water and an organic solvent is blended therein. Aqueous suspension type agricultural chemical formulation according to any one of claims 1 to 4 (6) The organic solvent is methyl alcohol, ethyl alcohol, isopropyl alcohol, glycerin 1 polyethylene glycol, ethylene glycol, ethylene glycol monomethyl. The water-suspended agricultural chemical formulation according to claim 5, which is one or more selected from ether, ethylene glycol monoethyl ether, xylene, toluene, orthochlorotoluene, kerosene, mineral oil, vegetable oil, and liquid paraffin.