JP6726447B2 - Aqueous pesticide composition - Google Patents

Description

The present invention relates to an aqueous pesticide composition.

Known pesticide compositions include solid preparations such as powders, granules and granules, and liquid preparations such as emulsions, solutions, flowables and oils. Among these, from the viewpoints of environmental protection and improvement of the safety of pesticide sprayers, it is required to use an organic solvent having low toxicity and low risk and to reduce the amount of the organic solvent used.

For example, Patent Document 1 discloses a method in which an N-alkylpyrrolidone solution of an agricultural chemical active ingredient is diluted with water and polyoxyethylene polyoxyalkylene glycol is used as an emulsifier.

JP, 2010-1268, A

However, the agrochemical composition of Patent Document 1 uses N-alkylpyrrolidone, which is an organic solvent, and is not sufficient from the viewpoint of environmental protection and improvement of the safety of agricultural chemical sprayers. It was also found that the use of water in place of the N-alkylpyrrolidone significantly reduces the stability of the pesticide composition and makes it impossible to store it for a long time. Therefore, an object of the present invention is to provide an aqueous pesticide composition having excellent stability even when stored for a long period of time.

In order to solve the above-mentioned subject, the aqueous pesticidal composition according to the present invention contains an agrochemical active ingredient (A), an alkylene oxide adduct of sugars (B) and water (C).

In the aqueous pesticide composition according to the present invention, it is preferable that the alkylene oxide adduct (B) of the saccharide contains 30 to 100 parts by mass of an oxyethylene group with respect to 100 parts by mass of an oxyalkylene group.

In the aqueous pesticide composition according to the present invention, the alkylene oxide adduct (B) of the saccharide preferably has a number average molecular weight of 5,000 to 30,000.

In the aqueous pesticide composition according to the present invention, the saccharide in the alkylene oxide adduct (B) of the saccharide is preferably at least one selected from disaccharides and sugar alcohols.

According to the present invention, an aqueous pesticide composition having excellent stability can be obtained even when stored for a long period of time.

Hereinafter, preferred embodiments of the present invention will be described.

The aqueous pesticide composition of the present embodiment contains the pesticide active ingredient (A), a saccharide alkylene oxide adduct (B) and water (C).

Examples of the agricultural chemical active ingredient (A) used in the present invention include organic phosphorus insecticides, carbamate insecticides, pyrethroid insecticides, nereistoxin insecticides, neonicotinoid insecticides, insect growth regulators, Other synthetic insecticides, natural insecticides, acaricides, nematicides, fumigants, biological insecticides, copper germicides, inorganic germicides, organic sulfur germicides, organophosphorus germicides, melanin biosynthesis Inhibitors, benzimidazole fungicides, dicarboximide fungicides, acid amide fungicides, sterol biosynthesis inhibitors, methoxyacrylate fungicides, synthetic antibacterial agents, soil fungicides, other synthetic fungicides, antibiotics Substance fungicides, natural product fungicides, biological fungicides, phenoxy acid herbicides, carbamate herbicides, acid amide herbicides, urea herbicides, sulfonylurea herbicides, pyrimidyloxybenzoic acid herbicides, Triazine herbicides, diazine herbicides, diazole herbicides, bipyridylium herbicides, dinitriloaniline herbicides, aromatic carboxylic acid herbicides, fatty acid herbicides, organophosphorus herbicides, amino acid herbicides , Other organic herbicides, inorganic herbicides, biological herbicides, plant growth regulators, attractants, repellents, rodenticides, spreading agents and the like. Furthermore, the agrochemical active ingredient etc. which are described in the Agricultural Chemicals Manual (2008 edition) published by the Japan Plant Protection Association are mentioned. These may be used in combination of two or more.

The content of the agricultural chemical active ingredient (A) is preferably 50% by mass or less. Within the above range, the stability becomes more excellent.

Examples of the sugar in the alkylene oxide adduct (B) of the sugar used in the present invention include sugar and sugar alcohol. Examples of sugars include monosaccharides such as glucose, fructose, galactose and mannose, disaccharides such as sucrose, lactose, maltose and trehalose, polysaccharides such as cellulose, amylose and chitin. Examples of sugar alcohols include sorbitol, mannitol, maltitol and erythritol. Of these, disaccharides and sugar alcohols are preferable, and sucrose is more preferable, because they have a relatively low viscosity and are easy to handle, and because they are more stable.

Examples of the alkylene oxide added to the saccharide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol, tetrahydrofuran and the like. Of these, propylene oxide alone or a combination of ethylene oxide and propylene oxide is preferable, and a combination of ethylene oxide and propylene oxide is more preferable, because they are more stable.

When the above ethylene oxide and propylene oxide are used in combination, a mixture thereof may be added, or they may be added separately. Of these, those obtained by block-adding propylene oxide and ethylene oxide in this order are preferable because they are more stable at low concentrations.

The method of adding the alkylene oxide is not particularly limited, and for example, a method of introducing the alkylene oxide into a reaction vessel at 70 to 120° C. and 0 to 0.3 MPa in the presence of a saccharide and a catalyst to react with the saccharide. Are listed.

Although the saccharide used in the alkylene oxide addition reaction may be a saccharide alone, it is preferable to use a saccharide dissolved in a compound capable of dissolving the saccharide, from the viewpoint of reducing the viscosity of the reaction solution. Examples of the compound capable of dissolving such saccharides include hydroxyl group-containing compounds other than saccharides such as water, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, and trimethylolpropane. Of these, water is preferred because it has high solubility of saccharides and can be easily distilled off after the addition reaction. In addition, the amount of the compound capable of dissolving the saccharide is preferably 20 parts by mass or less with respect to 100 parts by mass of the saccharide, from the viewpoint of increasing the ratio of alkylene oxide added to the saccharide.

The catalyst used for the alkylene oxide addition reaction is not particularly limited, but examples thereof include alkali metals such as potassium hydroxide and sodium hydroxide, alkaline earth metals such as calcium hydroxide and magnesium hydroxide, diethanolamine and triethylamine. Examples of amines, cationic polymerization catalysts, double metal cyanide complex catalysts, and the like. The amount of the catalyst used is, for example, 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the saccharide.

The alkylene oxide addition reaction product may be further purified. By performing the purification treatment, it becomes possible to maintain the hydrophilicity for a longer period. Examples of such purification treatment include adsorbent treatment and distillation treatment. Of these, the adsorbent treatment is preferable because the manufacturing process is easy.

The method of the adsorbent treatment is not particularly limited, for example, a method of mixing the alkylene oxide addition reaction product and an adsorbent using a stirrer, a method of passing the alkylene oxide addition reaction product through an adsorbent packed column, etc. Are listed. Among these, the method of mixing the alkylene oxide addition reaction product and activated carbon is preferable because the operation is simple. When a solvent such as water or an organic solvent is used, the adsorbent may be added after being mixed with the alkylene oxide addition reaction product in advance, or the adsorbent may be dispersed in the solvent and then mixed with the alkylene oxide addition reaction product. You may.

The adsorbent is for adsorbing and removing impurities contained in the alkylene oxide addition reaction product. The adsorbent may be in the form of powder, granules or pellets, preferably powder. Examples of such an adsorbent include activated carbon and zeolite, and in particular, activated carbon is preferable, and activated carbon having a pH of 4 to 11 in a 1% by mass aqueous suspension is more preferable, because it has more excellent stability. The activated carbon having a pH of 4.5 to 7.5 is more preferable.

The amount of the adsorbent used is not particularly limited, but is preferably 0.1 to 20.0 parts by mass, and 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the alkylene oxide addition reaction product. More preferably. When the amount of the adsorbent used is within the above range, the manufacturing process becomes simpler.

A solvent is preferably used in the adsorbent treatment. By using the solvent, the viscosity of the alkylene oxide addition reaction product is lowered, and the purification treatment can be easily performed.

Further, in the adsorbent treatment, various additives such as an antioxidant and an ultraviolet absorber may be used in addition to the solvent.

The alkylene oxide adduct (B) of the saccharide preferably has an alkylene oxide addition amount of 100 to 600 mol per mol of the saccharide. Within the above range, the stability becomes more excellent. The addition amount of the alkylene oxide is more preferably 120 to 500 mol, further preferably 150 to 450 mol.

The alkylene oxide adduct (B) of the saccharide preferably contains 30 to 100 parts by mass of an oxyethylene group with respect to 100 parts by mass of an oxyalkylene group. Within the above range, the stability becomes more excellent. The content of the oxyethylene group is more preferably 40 to 90 parts by mass, further preferably 50 to 70 parts by mass.

The alkylene oxide adduct (B) of the saccharide preferably has a number average molecular weight of 5,000 to 30,000. Within the above range, the stability becomes more excellent. The number average molecular weight is more preferably 8,000 to 25,000, further preferably 10,000 to 20,000.

The alkylene oxide adduct (B) of the saccharide preferably has an average hydroxyl value of 10 to 100 mgKOH/g. Within the above range, the stability becomes more excellent. The average hydroxyl value is more preferably 20 to 70 mgKOH/g, further preferably 25 to 50 mgKOH/g. The average hydroxyl value can be measured according to JIS K0070.

The content of the alkylene oxide adduct (B) of the saccharide is preferably 0.1 to 30% by mass in the aqueous pesticide composition. Within the above range, the stability becomes more excellent. More preferably, the content is 0.5 to 10% by mass.

The content of the alkylene oxide adduct (B) of the saccharide is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the agricultural chemical active ingredient (A). Within the above range, the stability becomes more excellent. The content is more preferably 5 to 50 parts by mass.

The method for producing the aqueous pesticidal composition of the present invention is not particularly limited, and examples thereof include a method of simultaneously mixing the pesticide active ingredient (A), the saccharide alkylene oxide adduct (B) and water (C), and the saccharide alkylene oxide addition. Examples include a method of mixing a mixture of the substance (B) and water (C) and the agrochemical active ingredient (A).

Any component may be added to the aqueous pesticide composition of the present invention within a range that does not impair the effect. Optional ingredients include clay minerals/fillers, colorants, surfactants, solvents/oils, glycols/sugars, water-soluble polymers, preservatives, antifreezing agents, inorganic salts, UV shielding agents. , Latexes, emulsions, defoamers, pH adjusters, fragrances/deodorants, fertilizers and the like.

Examples of the clay minerals/fillers include alumina, zirconia, frog clay, kaolinite, kaolin, calcium bentonite, chromite sand, silica sand, silica silica, zirconium silicate, silica powder, diatomaceous earth, aluminum nitride, barium carbonate. , Saponite, colemanite, calcined diatomaceous earth, shirasu, shirasu balloon, silicon carbide, zircon sand, zircon, zircon flower, aluminum hydroxide, zeolite, quartz glass powder, sodium bentonite, sodium montmorillonite, feldspar powder, porcelain stone, Halosite, borax, magnesia, kibushi clay, rouxite, perlite, cement, calcium carbonate, mica, kaolin clay, talc, stone stone, soap stone, glass beads, alumina, calcium phosphate, wollastonite, wollastonite, light Calcium carbonate, synthetic hydrotalcite, synthetic mica, ground calcium carbonate, calcined clay, silk powder, slaked lime, serinite, calcium carbonate, ultrafine zinc oxide, precipitated barium sulfate, dolomite powder, nylon powder, barium sulfate, fine particles Examples thereof include aluminum hydroxide, polyethylene wax, white carbon, organic bentonite, fused silica, and wax stone.

Examples of the colorant include zinc white, cuprous oxide, lead monoxide, watching red, chlorine titanium oxide pigment, oil furnace black, yellow lead, yellow iron oxide, oxysulfide phosphor, cadmium yellow, cadmium red, ultramarine blue. , Fluorescent pigment, graphite, black iron oxide, ultrafine calcium carbonate, cobalt blue, cobalt green, cobalt purple, white powder, dark blue, thermal black, chromium oxide, titanium oxide (Atanace), titanium oxide (rutile), terbium oxide, oxidation Copper, disazo yellow, red iron oxide, granulated carbon black, brown iron oxide, channel black, ultrafine particulate titanium oxide, iron black, natural graphite powder, natural earth graphite, copper phthalocyanine blue, copper phthalocyanine green, permanent red, Examples thereof include vanadate phosphor, fine particle titanium oxide, fast yellow 10G, red iron oxide, molybdenum red and the like.

Examples of the surfactant include an anionic surfactant, a nonionic surfactant other than the alkylene oxide adduct (B) of the saccharide, a cationic surfactant, an amphoteric surfactant, and the like.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, fatty acid salt, alkane sulfonate, olefin sulfonate, naphthalene sulfonate condensate, lignin sulfone. Examples thereof include acid salts, alkyl sulfosuccinic acid ester salts, polyoxyalkylene alkyl ether sulfosuccinic acid salts, alkyl phosphoric acid ester salts, polyoxyalkylene alkyl ether phosphoric acid ester salts, and polyoxyalkylene alkyl ether acetate salts. Examples of the above salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, and amine salts such as ammonia and alkanolamine.

Examples of the nonionic surfactant other than the alkylene oxide adduct of sugar (B) include polyoxyalkylene alkyl ether, polyoxyalkylene acyl ester, alkyldiethanolamide, polyoxyalkylene triglyceride ether, sorbitan fatty acid ester, sucrose fatty acid. Examples thereof include esters, polyoxyalkylene sorbitan fatty acid esters, alkyl polyglycosides, polyoxyethylene polyoxypropylene block polymers and the like.

Examples of the cationic surfactant include monoalkylamine salt, dialkylamine salt, trialkylamine salt, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkyldimethylaminopropylamide and the like. Examples of the above salt include halogen such as chlorine and bromine.

Examples of the amphoteric surfactant include alkyl betaine, fatty acid amidopropyl betaine, 2-alkyl-N-carboxylmethyl-N-hydroxyethyl-imidazolinium betaine, alkyldiethylenetriaminoacetic acid, dialkyldiethylenetriaminoacetic acid and alkylamine oxide. Are listed.

Examples of the solvents and oils include ethanol, isopropanol, 1-butanol, propylene glycol, polyethylene glycol, polypropylene glycol, acetic acid, acetic anhydride, acetopheno, methyl oleate, coconut oil, rapeseed oil, soybean oil, castor oil, linseed oil. Oil, paraffin oil, kerosene, higher alcohols, cyclohexanol, benzyl alcohol, ethylene glycol, hexylene glycol, propylene glycol monopropyl ether, propyl cellosolve, γ-butyrolactone, fatty acid methyl ester, methylpyrrolidone, dimethyl sulfoxide, chlorobenzene, chlorotoluene , Dichloroaniline, toluene, xylene, alkylbenzene, normal paraffin, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monobutyl ether, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, cyclohexanone, acetonitrile, kerosene, Machine oils, aromatic solvents, etc. may be mentioned. Two or more of these may be mixed.

Examples of glycols/sugars include diol compounds, glycerin and its derivatives, pentaerythritol, sorbitol, xylitol, sucrose, glucose and fructose.

As the water-soluble polymer, for example, xanthan gum, carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, lignin sulfonate, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, starch, dextrin, bentonite, polyvinyl. Examples include pyrrolidone.

Examples of the preservatives include benzoate, sorbate, parabens, 1,2-benzthiazolin-3-one and the like.

Examples of the antifreezing agent include ethylene glycol, diethylene glycol, propylene glycol and the like.

Examples of the ultraviolet shielding agent include salicylic acid-based agents and benzophenone-based agents.

Examples of fertilizers include nitrogenous fertilizers, phosphate fertilizers, potash fertilizers, calcareous fertilizers, magnesia fertilizers, siliceous fertilizers, trace element fertilizers, animal material fertilizers, and plant fertilizers.

The method of using the aqueous pesticide composition of the present invention is not particularly limited, and for example, it can be used by a method such as spraying or coating. When used, the aqueous pesticide composition may be used as it is, or may be diluted with water.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In this example, as the alkylene oxide adduct (B) of the saccharide, the alkylene oxide adducts (b-1) to (b-6) of the saccharide obtained in Production Examples 1 to 6 below were used.

(Production Example 1)
A stainless steel autoclave was charged with 34.2 g (0.1 mol) of sucrose, 7 g of water and 0.3 g of potassium hydroxide, and the inside of the reactor was replaced with nitrogen. The temperature was raised to 80° C. to dissolve sucrose, then the temperature was raised to 100° C., and 464 g (8 mol) of propylene oxide was introduced while keeping the internal pressure at 0.3 MPa or less. After the introduction of propylene oxide was completed, the reaction was carried out at 100° C. for 2 hours. Subsequently, 661 g (15 mol) of ethylene oxide was introduced while keeping the internal pressure at 100° C. and 0.3 MPa or less. After completion of the introduction, the reaction was further continued at 100° C. for 2 hours to obtain an alkylene oxide adduct.
100 g of the obtained alkylene oxide adduct and 30 g of water were mixed and adjusted to 50° C., and acetic acid was further added to adjust the pH to 6. Subsequently, 10 g of powdered activated carbon (trade name: Strong Shirasagi A (manufactured by Nippon EnviroChemicals, pH of a 1% aqueous solution: 4.9) was added and stirred at 50° C. for 2 hours. Thereafter, the activated carbon was removed by filtration. By removing water at 90° C. under reduced pressure, a sucrose-propylene oxide (80 mol)-ethylene oxide (150 mol) block adduct (b-1) was obtained (oxy with respect to 100 parts by mass of oxyalkylene group). Ethylene group content: 59% by mass, number average molecular weight: 11600, average hydroxyl value: 39 mgKOH/g)

(Production Example 2)
The same operation as in Production Example 1 was repeated except that the amount of propylene oxide used was 523 g (9 mol) and the amount of ethylene oxide used was 969 g (22 mol), and sucrose-propylene oxide (90 mol)-ethylene oxide (220 mol). ) Adduct (b-2) was obtained. (Content of oxyethylene group based on 100 parts by mass of oxyalkylene group: 65% by mass, number average molecular weight: 15300, average hydroxyl value: 29 mgKOH/g)

(Production Example 3)
Sucrose-propylene oxide (20 mol)-ethylene oxide (150 mol) adduct (b-3) was obtained by performing the same operation as in Production Example 1 except that the amount of propylene oxide used was 116 g (2 mol). .. (Content of oxyethylene group based on 100 parts by mass of oxyalkylene group: 85% by mass, number average molecular weight: 8100, average hydroxyl value: 55 mgKOH/g)

(Production Example 4)
The same operation as in Production Example 1 was conducted except that the amount of propylene oxide used was 1162 g (20 mol) and the amount of ethylene oxide used was 1013 g (23 mol), and sucrose-propylene oxide (200 mol)-ethylene oxide (230 Mol) adduct (b-4) was obtained. (Content of oxyethylene group based on 100 parts by mass of oxyalkylene group: 47% by mass, number average molecular weight: 22000, average hydroxyl value: 20 mgKOH/g)

(Production Example 5)
The same operation as in Production Example 1 was carried out except that 34.4 g (0.1 mol) of maltitol was used instead of sucrose, and a maltitol-propylene oxide (80 mol)-ethylene oxide (150 mol) block adduct ( b-5) was obtained. (Content of oxyethylene group based on 100 parts by mass of oxyalkylene group: 59% by mass, number average molecular weight: 11600, average hydroxyl value: 39 mgKOH/g)

(Production Example 6)
The same operation as in Production Example 1 was conducted except that 68.8 g (0.2 mol) of trehalose was used in place of sucrose, and a trehalose-propylene oxide (80 mol)-ethylene oxide (150 mol) block adduct (b- 6) was obtained. (Content of oxyethylene group based on 100 parts by mass of oxyalkylene group: 59% by mass, number average molecular weight: 11600, average hydroxyl value: 39 mgKOH/g)

The following materials were used as raw materials other than the alkylene oxide adduct of sugars.
・Agrochemical active ingredient (A)
(A-1) Machine oil/other components (b'-1) Polyoxyethylene polyoxyalkylene glycol (trade name: Epan U-108, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
(B'-2) Polyoxyethylene polyoxyalkylene glycol (trade name: Epan 450, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
(B'-3) Polyethylene glycol (number average molecular weight: 10,000)
(B'-4) Polyoxypropylene glycol (number average molecular weight: 3000)
(Anti-freezing agent) Propylene glycol (preservative) 1,2-Benzthiazolin-3-one

(Examples 1 to 6, Comparative Examples 1 to 4)
The components were mixed in the proportions shown in Table 1. This was stirred for 10 minutes at 8000 rpm using a high speed stirrer (trade name: TK Homomixer HV-M, manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an aqueous pesticide composition. The stability was evaluated by the following method using the obtained aqueous pesticide composition. The results are shown in Table 1.

(Stability)
The aqueous pesticide composition adjusted to 40° C. was put into a 100 mL graduated cylinder so that the height was 100 mm. After allowing this to stand at 40° C. for 5 minutes and for 1 month, the presence or absence of separation was evaluated according to the following criteria.
A: No separation is seen B: Separation of more than 0 mm and less than 2 mm is seen C: Separation of 2 mm or more and less than 5 mm is seen D: Separation of 5 mm or more and less than 10 mm is seen E: Separation of 10 mm or more is seen To be

(Dilution stability)
Using an aqueous pesticide composition diluted 10-fold with water, the stability was evaluated in the same manner as the above.

As is clear from Table 1, the aqueous pesticide composition of the present invention has excellent stability over a long period of time. Further, it is excellent in stability over a long period of time even at a low concentration such as when diluted. On the other hand, when the alkylene oxide adduct (B) of saccharide is not used as in Comparative Examples 1 to 4, the stability is poor.

The aqueous pesticide composition of the present invention can be used as an insecticide, a fungicide, a herbicide, and the like.

Claims (2)

An aqueous pesticide composition comprising an agrochemical active ingredient (A), a sugar alkylene oxide adduct (B) and water (C) ,
The alkylene oxide adduct (B) of the saccharide has a number average molecular weight of 5,000 to 30,000,
The aqueous pesticide composition, wherein the saccharide in the alkylene oxide adduct (B) of the saccharide is at least one selected from disaccharides and sugar alcohols. The aqueous pesticide composition according to claim 1, wherein the alkylene oxide adduct (B) of the saccharide contains 30 to 100 parts by mass of an oxyethylene group with respect to 100 parts by mass of an oxyalkylene group.