JP4578089B2 - Liquid pesticide formulation - Google Patents

Description

  The present invention relates to a liquid agrochemical formulation with improved storage stability.

  As an agrochemical formulation, because of the need to ensure safety to the environment and users, instead of organic solvents that affect these, a liquid or flowable agent in which an agrochemical active ingredient is dissolved or dispersed in safer water is used. Development is underway.

  In the case of such a liquid or flowable agent, crystals may precipitate depending on the type of the pesticidal active ingredient. For the purpose of preventing such crystal precipitation, it is known that an agrochemical active ingredient is dissolved in an organic solvent when a liquid or flowable agent is produced.

  On the other hand, propylene carbonate has little odor, low flammability and harmfulness, and sufficiently dissolves agricultural chemical active ingredients. When propylene carbonate is used as a solvent, It is known to exert an excellent control effect of active ingredients.

（但し、式中Ｘは水素原子またはハロゲン原子を示し、Ｙは低級アルキル基を示す。）
で示されるイソチアゾロン化合物を、炭酸プロピレンまたはこれを主体とする溶剤にて溶解調製してなる非医療用イソチアゾロン液状殺菌製剤（特許文献３参照）。

特開２００１−２５１１号公報 特表２００２−５０３６８２号公報 特開平１−１９７４１３号公報 Examples of such are the following 1) to 3).
1) (a) 1-methyl-2-nitro-3-[(3-tetrahydrofuryl) methyl] guanidine, (b) one polar solvent selected from the group consisting of benzyl alcohol and propylene carbonate, (c) water And (d) a propellant containing 50% by weight or more of dimethyl ether with respect to the total weight of the propellant, and a total amount spray type composition for insecticidal aqueous aerosol (see Patent Document 1).
2) The following composition: a-an agonist or antagonist of an insect nicotinic acetylcholine receptor at a concentration of 0.0001-7.5% by weight, based on the total weight of the formulation;
b-water at a concentration of 20-50% by weight, based on the total weight of the formulation;
c-acyclic alcohols at a concentration of 20-50% by weight, based on the total weight of the formulation;
d-cyclic carbonates at a concentration of 2.5 to 20.0% by weight, based on the total weight of the formulation;
e—In some cases, from thickeners, spreaders, colorants, antioxidants, propellants, preservatives, tackifiers, emulsifiers in concentrations from 0 to 30% by weight, based on the total weight of the formulation. A water-containing preparation applied to the skin for controlling parasitic insects and mites on humans with agonists or antagonists of the nicotinic acetylcholine receptor, comprising further auxiliaries from the group (see patent document 2).
3) General formula (I)

(In the formula, X represents a hydrogen atom or a halogen atom, and Y represents a lower alkyl group.)
A non-medical isothiazolone liquid bactericidal preparation prepared by dissolving and dissolving the isothiazolone compound represented by the formula in propylene carbonate or a solvent mainly composed thereof (see Patent Document 3).

JP 2001-2511 A JP-T-2002-503682 Japanese Patent Laid-Open No. 1-197413

  In liquid agrochemical formulations such as liquids or flowables containing water, when propylene carbonate is used as the organic solvent, the propylene carbonate may generate gas in the presence of water.

  If this gas is generated in the storage container, the pressure in the container is increased, and there is a risk that the chemical solution is scattered when opened and the worker is exposed. Further, due to the internal pressure, the storage container may be deformed and become unsightly, and the commercial value may be lowered. Further, the container may rupture and the chemical solution may leak out, which causes a problem in the distribution and storage of the product.

  Therefore, in liquid agrochemical formulations, it is desired to suppress the generation of gas when using propylene carbonate in the presence of water.

  Accordingly, an object of the present invention is to provide a liquid agricultural chemical formulation containing propylene carbonate, which can suppress gas generation even in the presence of water and has improved storage stability.

  The inventors of the present invention diligently studied a liquid pesticide preparation that does not generate gas and has excellent storage stability even when it contains propylene carbonate and water. As a result, the present invention was completed.

  That is, it was found that a liquid agrochemical formulation characterized by containing an agrochemical active ingredient, propylene carbonate, water and glycols and / or glycol ethers met the above purpose.

  The glycols used are preferably monoalkylene glycol or polyalkylene glycol.

  The monoalkylene glycol is particularly preferably ethylene glycol or propylene glycol.

  The polyalkylene glycol is particularly preferably diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol or dimethylethylene glycol.

  The glycol ethers used are preferably monoalkylene glycol ethers or polyalkylene glycol ethers.

  The monoalkylene glycol ether is particularly preferably ethylene glycol monomethyl ether or propylene glycol monomethyl ether.

  The polyalkylene glycol ether is particularly preferably diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether or tripropylene glycol monomethyl ether.

  Furthermore, it is preferable to contain a surfactant. In particular, it has been found that the surfactant is preferably an anionic surfactant and / or a nonionic surfactant for achieving the above object.

When the liquid agrochemical formulation of the present invention is carried out, the following effects are brought about. That is,
(1) Gas generation due to the presence of propylene carbonate in water can be suppressed.
(2) For this reason, an increase in the internal pressure of the storage container can be suppressed, and the chemical liquid is scattered at the time of opening, so that the operator is not exposed to exposure.
(3) Further, since the storage container does not expand and deform or rupture due to an increase in internal pressure, there is no fear of a decrease in commercial value, and there is no fear of leakage of chemicals during storage and distribution.
(4) Since it is a preparation containing water, there are few dangers such as ignitability and flammability, and there are no problems in environmental health due to irritation to human body and odor.

  Next, a method for carrying out the present invention will be specifically described.

  The following are mentioned as an agrochemical active ingredient used for the liquid agrochemical formulation of this invention.

  Insecticidal active ingredients include organophosphorus, carbamate, pyrethroid, nereistoxin, neonicotinoid, and furanicotyl.

  In addition, as bactericidal active ingredients, copper compounds, organic sulfur, organic phosphorus, melanin biosynthesis inhibitors, benzimidazoles, dicarboximides, acid amides, sterol biosynthesis inhibitors, methoxyacrylates, anilinopyrimidines Examples thereof include antibiotics and antibiotics, but are not limited thereto.

  Moreover, even if it uses only 1 type of said thing, or it uses 2 or more types together, there is no problem.

  As herbicidal active ingredients, phenoxy acid, carbamate, acid amide, urea, sulfonylurea, pyrimidyloxybenzoic acid, triazine, diazine, diazole, bipyridium, dinitroaniline, aromatic carboxylic acid, Examples are aliphatic, organophosphorus, amino acid and the like. And even if these herbicidal active ingredients use together 1 type, or 2 or more types, there is no problem.

  These pesticidal active ingredients may be dissolved in propylene carbonate to form a single liquid phase, or may not be dissolved in propylene carbonate and have no problem as a suspension.

  The agrochemical active ingredients are described in “Agricultural Chemicals Handbook 2001” (issued by the Japan Plant Protection Association) or “Kumiai Agricultural Chemicals Summary 2003” (issued by JA Zen-noh).

  The content of these pesticidal active ingredients can be arbitrarily changed depending on the type of active ingredient, but may be added in the range of 0.1 to 60% by weight in the preparation.

  Examples of glycols and glycol ethers used in the present invention include monoalkylene glycols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene having an average molecular weight of 200 to 600. Polyalkylene glycols such as glycol, dipropylene glycol, low molecular weight polypropylene glycol, dimethylethylene glycol; monoalkylenes such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Glycol ethers; Diethylene glycol monomer Examples include, but are not limited to, polyalkylene glycol ethers such as ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. Absent.

  Among the above, monoalkylene glycols are preferable, and ethylene glycol and propylene glycol are more preferable.

  The addition amount of glycols and glycol ethers may be an amount capable of suppressing the gas generation of propylene carbonate, and is 1 to 60% by weight, preferably 3 to 40% by weight in the preparation.

  The amount of propylene carbonate used in the present invention is 1 to 60% by weight, preferably 5 to 40% by weight.

  The surfactant that can be used in the present invention is not limited to a specific surfactant. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, Polyoxyethylene sorbitan alkylate, polyoxyethylene phenyl ether polymer, polyoxyethylene alkylene aryl phenyl ether, polyoxyalkylene aryl phenyl ether, polyoxyethylene alkylene glycol, polyoxyethylene polyoxypropylene block polymer, fluorosurfactant ( Perfluoroalkylcarboxylic acid), silicone surfactant (polyoxyalkylene dimethyl polysiloxane copoly) Chromatography, etc.), an acetylene glycol-based surfactant (2, 4, 7, 9, - tetramethyl - such decyne-4,7-diol) it is like, but is not limited only to these examples.

  Examples of anionic surfactants include polycarboxylic acid type surfactants, lignin sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether sulfates, alkyl naphthalene sulfonates, polyoxy Examples include ethylene styryl phenyl ether sulfate, alkylbenzene sulfonate, and alkyl sulfate, but are not limited to these examples.

  Moreover, you may add a thickener, an antifoamer, antiseptic | preservative antibacterial agent, a stabilizer, etc. as an auxiliary | assistant as needed.

  In this case, the thickener may be any commonly used one. For example, as the water-soluble thickener, xanthan gum, lambzan gum, pullulan, tragacanth gum, gum arabic, locust bean gum, sodium alginate, water-soluble soybean Polysaccharides (soya five), casein, dextrin, polyvinyl alcohol, and water-soluble cellulose ethers such as methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc., and inorganic substances include colloidal hydrous aluminum silicate, colloid Hydrated magnesium silicate, colloidal hydrated aluminum magnesium silicate, and the like, but are not limited to these, and one or more of these may be used in combination. No no problem.

  Examples of antifoaming agents include silicon-based and fatty acid-based materials, antiseptic and anti-biotic agents include potassium sorbate, p-chloro-metaxylenol, and butyl p-oxybenzoate. Stabilizers include antioxidants, Although an ultraviolet-ray inhibitor etc. may be added, it is not limited to the adjuvant illustrated here.

  The liquid pesticide preparation of the present invention can be applied by a usual method.

  For example, in an agricultural scene, a liquid pesticide preparation may be diluted with an undiluted solution or with water to an appropriate concentration (usually about 8 to 3000 times) and sprayed onto a target crop using a sprayer. At this time, not only on the ground but also using a manned aircraft, helicopter or unmanned RC helicopter, it is possible to spray from the air. In the paddy field, it can be sprayed and applied in a labor-saving manner by directly dropping or spraying the original solution or a solution diluted with water at a high concentration about 2 to 5 times from the shore to the paddy field.

  Although the preparation method of the liquid agrochemical formulation of this invention is not specifically limited, For example, it can prepare by the following method.

Preparation method 1 (when pesticide active ingredient is dissolved in propylene carbonate)
Agrochemical active ingredients are dissolved in propylene carbonate, glycols and / or glycol ethers. Water, if necessary, a surfactant and an auxiliary agent are added to the dissolved liquid to make 100 parts, and mixed using a three-one motor to obtain a liquid pesticide preparation.

Preparation method 2 (when the agrochemical active ingredient is not dissolved in propylene carbonate)
A surfactant is dissolved or dispersed in water, and an agrochemical active ingredient that does not dissolve in propylene carbonate is added thereto. The obtained mixed solution is wet pulverized with a 4-cylinder sand grinder (trade name, manufactured by Imex Co., Ltd.) using glass beads having a diameter of 0.7 to 1.2 mm as a pulverizing medium.

  Add this wet pulverized liquid to a mixed liquid of propylene carbonate and glycols and / or glycol ethers, add an auxiliary if necessary, add water to make 100 parts, and evenly using a three-one motor. Mix to obtain a liquid pesticide formulation.

Preparation method 3 (when the pesticidal active ingredient is dissolved in propylene carbonate and further contains the pesticidal active ingredient not dissolved in propylene carbonate)
A surfactant is dissolved or dispersed in water, and an agrochemical active ingredient that does not dissolve in propylene carbonate is added thereto. The obtained mixed solution is wet pulverized with a 4-cylinder sand grinder (trade name, manufactured by Imex Co., Ltd.) using glass beads having a diameter of 0.7 to 1.2 mm as a pulverizing medium.

  This wet pulverized liquid is added to a solution obtained by dissolving an agrochemical active ingredient in propylene carbonate and glycols and / or glycol ethers. If necessary, an auxiliary agent is added, and water is added to make 100 parts. To obtain a liquid pesticide formulation.

  Next, examples of the liquid agricultural chemical formulation of the present invention will be given, but the present invention is not limited to these examples.

  In the following examples, “parts” means “parts by weight”.

(1) Composition Kasugamycin drug substance 5 parts Propylene carbonate 10 parts Ethylene glycol 20 parts Water 65 parts Total 100 parts (2) Preparation
10 parts of propylene carbonate and 20 parts of ethylene glycol were added to 5 parts of kasugamycin base and dissolved. 65 parts of water was added to the obtained uniform solution and mixed using a three-one motor to obtain a liquid agrochemical formulation.

  A liquid agrochemical formulation was obtained in the same manner as in Example 1, except that 20 parts of ethylene glycol was changed to 20 parts of ethylene glycol monomethyl ether.

  A liquid agrochemical formulation was obtained in the same manner as in Example 1 except that 20 parts of ethylene glycol was changed to 20 parts of diethylene glycol.

  A liquid agrochemical formulation was obtained in the same manner as in Example 1 except that 20 parts of ethylene glycol was changed to 20 parts of diethylene glycol monomethyl ether.

(1) Composition Kasugamycin base 5 parts Propylene carbonate 10 parts Ethylene glycol 30 parts Polyoxyethylene alkyl ether 2 parts Water 53 parts Total 100 parts (2) Preparation
10 parts of propylene carbonate and 30 parts of ethylene glycol were added to 5 parts of the kasugamycin base and dissolved. To the obtained uniform solution, 2 parts of polyoxyethylene alkyl ether and 53 parts of water were added and mixed using a three-one motor to obtain a liquid agrochemical formulation.

  Of the formulation composition of Example 5, prepared according to Example 5 except that 10 parts of propylene carbonate was 5 parts of propylene carbonate, 30 parts of ethylene glycol was 40 parts of ethylene glycol, and 53 parts of water was 48 parts of water. As a result, a liquid pesticide preparation was obtained.

  Of the formulation composition of Example 5, prepared according to Example 5 except that 10 parts of propylene carbonate was 50 parts of propylene carbonate, 30 parts of ethylene glycol was 20 parts of ethylene glycol, and 53 parts of water was 23 parts of water. As a result, a liquid pesticide preparation was obtained.

  Of the formulation composition of Example 5, 30 parts of ethylene glycol is 10 parts of ethylene glycol, 2 parts of polyoxyethylene alkyl ether is 2 parts of polyoxyethylene alkyl ether and 1 part of alkylbenzene sulfonate, and 53 parts of water is 72 parts of water. A liquid pesticide preparation was obtained in the same manner as in Example 5 except that the amount was part.

(1) Composition Kasugamycin base 5 parts Propylene carbonate 20 parts Ethylene glycol 20 parts Fusaride base 10 parts Polyoxyethylene alkyl ether 2 parts Xanthan gum 1 part Water 42 parts Total 100 parts (2) Preparation
A homogeneous solution was obtained by adding 20 parts of propylene carbonate and 20 parts of ethylene glycol to 5 parts of the kasugamycin base. Separately, 2 parts of polyoxyethylene alkyl ether is added to 42 parts of water and dissolved, 10 parts of a fusalide base and 1 part of xanthan gum are added thereto, and glass beads having a diameter of 0.7 to 1.2 mm as a grinding medium. Was wet pulverized with a 4-cylinder sand grinder (trade name, manufactured by Imex Co., Ltd.). The obtained wet pulverized liquid was added to a liquid prepared by dissolving the kasugamycin base prepared in advance as described above, and mixed until uniform using a three-one motor to obtain a liquid pesticide preparation.

  Of the formulation composition of Example 9, except that 20 parts of propylene carbonate was 5 parts of propylene carbonate, 1 part of xanthan gum was 0.5 part of colloidal hydrous aluminum silicate, and 42 parts of water was 57.5 parts of water. A liquid agrochemical formulation was obtained according to Example 9.

  Of the formulation composition of Example 1, except 5 parts of kasugamycin was 2 parts of phenocarb, 10 parts of propylene carbonate was 20 parts of propylene carbonate, 20 parts of ethylene glycol was 50 parts of ethylene glycol, and 65 parts of water was 28 parts of water. Was prepared according to Example 1 to obtain a liquid agrochemical formulation.

  Of the formulation composition of Example 1, 5 parts of kasugamycin were 2 parts of phenothiol, 10 parts of propylene carbonate were 20 parts of propylene carbonate, 20 parts of ethylene glycol were 40 parts of ethylene glycol, and 65 parts of water were 38 parts of water. Except for the above, a liquid pesticide preparation was obtained according to Example 1.

Comparative Example 1
A liquid pesticide preparation was obtained in the same manner as in Example 1 except that 20 parts of ethylene glycol of Example 1 was not added with ethylene glycol and 65 parts of water was 85 parts of water.

Comparative Example 2
A liquid pesticide preparation was obtained in the same manner as in Example 1 except that 20 parts of ethylene glycol in Example 1 was changed to 20 parts of ethanol.

Comparative Example 3
A liquid pesticide preparation was prepared according to Example 1 except that 5 parts of kasugamycin of Example 1 was 1 part of kasugamycin, 20 parts of ethylene glycol was 45 parts of isopropylene alcohol, and 65 parts of water was 44 parts of water. Obtained.

Comparative Example 4
A liquid pesticide preparation was obtained in the same manner as in Example 5 except that 30 parts of ethylene glycol in Example 5 was changed to 30 parts of propyl alcohol.

Comparative Example 5
A liquid pesticide preparation was obtained in the same manner as in Example 8 except that 10 parts of ethylene glycol in Example 8 was changed to 10 parts of isopropyl alcohol.

Comparative Example 6
A liquid pesticide preparation was obtained in the same manner as in Example 9 except that 20 parts of ethylene glycol in Example 9 was changed to 20 parts of methyl ethyl ketone.

Comparative Example 7
A liquid pesticide preparation was obtained in the same manner as in Example 11 except that 50 parts of ethylene glycol in Example 11 was changed to 50 parts of isopropyl alcohol.

Comparative Example 8
A liquid pesticide preparation was obtained in the same manner as in Example 12 except that 40 parts of ethylene glycol in Example 12 was changed to 40 parts of glycerin.

  Next, the usefulness of the liquid agrochemical formulation of the present invention is specifically shown by test examples.

Test Example 1 Bag Expansion Test 30 ml of the prepared liquid pesticide preparation is placed in an aluminum bag for 100 g, heat sealed, stored at 40 ° C., after 1 month (corresponding to storage at room temperature for 1 year), and 3 months Later (corresponding to storage at room temperature for 3 years), the bag expansion rate was calculated by the following formula.

  The results are shown in Tables 1 and 2.

Test Example 2 Plastic Bottle Expansion Test 40 ml of the prepared liquid pesticide preparation is placed in a 50 ml plastic bottle, stored at 40 ° C., and the state of the plastic bottle is observed after 1 month and 3 months.
○: Expansion of the plastic bottle is not recognized.
Δ: Slight expansion of the plastic bottle is observed.
X: Expansion of the plastic bottle is clearly observed.

  The results are shown in Tables 1 and 2.

Claims (10)

  A liquid agrochemical formulation comprising an agrochemical active ingredient, propylene carbonate, water and glycols and / or glycol ethers.   2. The liquid agrochemical formulation according to claim 1, wherein the glycol is a monoalkylene glycol.   The liquid pesticide preparation according to claim 2, wherein the monoalkylene glycol is ethylene glycol and / or propylene glycol.   2. The liquid agrochemical formulation according to claim 1, wherein the glycol is a polyalkylene glycol.   The liquid agrochemical formulation according to claim 4, wherein the polyalkylene glycol is selected from diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and dimethylethylene glycol.   The liquid agrochemical formulation according to claim 1, wherein the glycol ether is a monoalkylene glycol ether.   The liquid agrochemical formulation according to claim 1, wherein the glycol ether is a polyalkylene glycol ether.   The liquid agrochemical formulation according to claim 7, wherein the polyalkylene glycol ether is selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.   The liquid agrochemical formulation according to claim 1, comprising a surfactant.   The liquid agrochemical formulation according to claim 9, wherein the surfactant is an anionic surfactant and / or a nonionic surfactant.