JP5232025B2 - Stabilized aqueous suspension formulation - Google Patents

Description

  The present invention contains an agrochemical active ingredient, guanidine or a water-soluble salt of guanidine (hereinafter referred to as “water-soluble guanidines”) as an essential component, so that it has excellent suspension properties even after long-term storage and particle aggregation is suppressed. It is related with the stabilized aqueous suspension pesticide formulation characterized by the above-mentioned.

  Aqueous suspension formulations do not generate dust during use, and are less flammable and less odorous. Therefore, they are superior in terms of safety and environmental hygiene, and are widely used. is there. However, there is a problem of sedimentation separation of dispersoids composed of agrochemical active ingredients and auxiliary ingredients dispersed in water during storage for a long period after production.

  Research on components such as dispersants and thickeners for the purpose of improving suspension and particle aggregation of such aqueous suspensions, and numerous studies on formulation physical properties such as particle size and formulation viscosity of dispersed particles As examples of research for improving suspension and particle aggregation in long-term storage of aqueous suspension preparations, the following studies have been conducted.

  In Japanese Patent Application Laid-Open No. 6-316502 (Patent Document 1), in the presence of a nonionic surfactant having an HLB of 1 to 9 and a nonionic surfactant having an HLB of 10 to 20, a poorly water-soluble solid physiology. A suspension composition having excellent suspension stability and self-dispersibility has been proposed by dispersing an active ingredient in a liquid medium.

In Japanese Patent Application Laid-Open No. 9-175904 (Patent Document 2), a natural or synthetic resin having a softening point of 60 ° C. or more and 100 ° C. or less is coated on a pesticide active ingredient that is solid at room temperature and hardly soluble in water or water insoluble. An agrochemical aqueous suspension composition with suppressed particle growth has been proposed.
In Japanese Patent Application Laid-Open No. 2007-77044 (Patent Document 3), by including a liquid agrochemical component, a solid agrochemical component, an oil and fat, and a nonionic surfactant, decomposition, precipitation, and aggregation of the components are suppressed, which is favorable. Proposals have been made of water-suspendable agricultural chemical formulations that ensure suspension and dispersion.

  In the above-mentioned patent document, Patent Document 1 is an example in which the suspension property of the aqueous suspension preparation is improved, but the inhibitory effect on particle aggregation is insufficient. Moreover, although patent document 2 is an example which improved the particle aggregation of the aqueous suspension formulation, the maintenance effect of suspension property is inadequate. Thus, in order to improve both the physical properties of suspension and particle aggregation, the material for improving suspension and the material for improving particle aggregation are added. There was a problem that both effects of coagulation improvement were canceled. Further, Patent Document 3 is an example in which the suspension property and particle aggregation are improved, but there is still room for improvement with respect to the effect of maintaining the suspension property and the effect of suppressing particle aggregation.

For this reason, an aqueous suspension preparation is expected in which both the physical properties of maintaining the suspension and suppressing the particle aggregation are maintained at a high level even after long-term storage.
On the other hand, there has been no research on aqueous suspension preparations containing water-soluble guanidines, and the knowledge that these components continue to maintain the suspension and dispersibility of aqueous suspension preparations at a very high level for long-term storage Was not found at all. In addition, the following studies have been conducted as examples of the use of water-soluble guanidines in agricultural chemical formulations other than aqueous suspension formulations.

  In JP-A-1-238506 (Patent Document 4), a urea aldehyde condensate having anti-soil plant virality, 2-oxo-6-ureido-hexahydropyrimidine, 2-oxo-4-methyl-6-hydroxy -Powdery anti-soil plant having both fertilizer effect and viral disease prevention effect, comprising as an active ingredient one or more compounds selected from hexahydropyrimidine, 4-methyl-hydrouracil, β-uracil butyric acid, guanyl urea and guanidine Viral fertilizer compositions have been proposed.

  In JP-A-11-92310 (Patent Document 5), 2-methoxycarbonyl-4-chlorotrifluoromethanesulfoanilide and N- (2-ethylhexyl) bicyclo [2.2.1] hept-5-ene-2,3 -Insecticides, which are extremely effective for controlling various pests, especially mites inhabiting indoors, using dicarboximide as an active ingredient, and used in the form of smoke, heat transpiration mat preparation, sheet preparation, An acaricidal composition has been proposed.

  In the above-mentioned patent document, in Patent Document 4, guanidine is used as an additive for improving the anti-soil plant virus property of urea aldehyde condensate, and in Patent Document 5, an insecticidal and acaricidal composition in the document is burned. When used as a smoking agent, guanidine sulfamate and guanidine nitrate are used as the exothermic regulator. However, in any patent document, they are not applied to liquid preparations, and long-term storage of aqueous suspension preparations of the components There is no description about the contribution effect to the suspension property and dispersibility in.

JP-A-6-316502 JP-A-9-175904 JP 2007-77044 A JP-A-1-238506 JP-A-11-92310

  An object of the present invention is to provide an aqueous suspension preparation which is excellent in suspension property after long-term storage and in which particle aggregation is suppressed.

The present inventors diligently studied to solve the above problems. As a result, aqueous suspension preparations containing agrochemical active ingredients and water-soluble guanidines as essential ingredients have excellent long-term storage stability, that is, suspension properties are maintained even after long-term storage, and particle aggregation is suppressed. I found it.
Further examination revealed that in the above aqueous suspension preparation, the amount of water-soluble guanidine added to the pesticidal active ingredient is 0.1 to 2.5 times by weight%, and the water-soluble guanidine is guanidine hydrochloride, The inventors have found that the case of guanidine sulfamate is more preferable, and have completed the invention.

〔式（Ｉ）中、 ｎは１〜３の整数を示し、ｎ＝１のとき、ＸはＨＣｌあるいは、ＨＮＯ_３、ＮＨ_３ＳＯ₃のいずれかを示し、ｎ＝２のとき、ＸはＨ_２ＣＯ_３を示し、ｎ＝３のとき、ＸはＨ_３ＰＯ_４を示す。〕で表されることを特徴とする〔１〕に記載の水性懸濁製剤。
〔３〕前記のグアニジンの水溶性塩が塩酸グアニジンもしくはスルファミン酸グアニジンであることを特徴とする〔１〕に記載の水性懸濁製剤。
〔４〕前記のグアニジンまたはグアニジンの水溶性塩の農薬活性成分に対する添加量が重量％比で０．１倍〜２．５倍であることを特徴とする〔１〕〜〔３〕のいずれかに記載の水性懸濁製剤。 Therefore, the gist of the present invention is summarized as follows.
[1] An aqueous suspension preparation comprising a) an agrochemical active ingredient and b) guanidine or a water-soluble salt of guanidine.
[2] The water-soluble salt of guanidine is represented by the formula (I)

[In the formula (I), n represents an integer of 1 to 3, and when n = 1, X represents either HCl or HNO ₃ , NH ₃ SO ₃ , and when n = 2, X represents H _{2 represents} CO _3, and when n = 3, X represents H ₃ PO ₄ . ] The aqueous suspension formulation of [1] characterized by the above-mentioned.
[3] The aqueous suspension preparation according to [1], wherein the water-soluble salt of guanidine is guanidine hydrochloride or guanidine sulfamate.
[4] Any one of [1] to [3], wherein the guanidine or the water-soluble salt of guanidine is added in an amount of 0.1 to 2.5 times by weight ratio. An aqueous suspension formulation as described in 1. above.

  The aqueous suspension preparation of the present invention is excellent in suspension property even after long-term storage, and particle aggregation is suppressed, so that problems such as loss of product value due to sedimentation separation do not occur. Furthermore, since the configuration is simple, the cost is also excellent.

Hereinafter, the aqueous suspension preparation of the present invention will be specifically described.
<Constituents>
(A) Agrochemical active ingredient In the present invention, the agrochemical active ingredient (a) used in the preparation of the aqueous suspension preparation is generally an agrochemical activity such as an insecticide, fungicide, herbicide, plant growth regulator and the like. If it is used as a component, it will not specifically limit, The following are mention | raise | lifted as such a pesticidal active ingredient (a).

  For example, organophosphorus [MEP (O, O-dimethyl-O-4-nitro-m-tolyl-6-methylpyrimidin-4-ylthiophosphate)] and carbamate [BPMC (2-secondary butyl) as insecticides Phenyl-N-methylcarbamate)], pyrethroids [permethrin ((R, S) -α-cyano-3-phenoxybenzyl- (1RS, 3RS)-(1RS, 3SR) -3- (2,2-dichloro) Vinyl) -2,2-dimethylcyclopropanecarboxylate)), benzoylhydrazide, neonicotinoid, triazine, thiourea, oxadiazine, phenylpyrazole, nereistoxin and benzoylphenylurea Insecticides, insect growth regulators [tebufenozide (2′-tert-butyl- '-(4-ethylbenzoyl) -3,5-dimethylbenzohydrazide), buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one), etc.], natural Insecticides, biopesticides, acaricides, nematicides and the like.

  Examples of the disinfectant include inorganic coppers, organic coppers, inorganic sulfur agents, organic sulfur agents, organic phosphorus-based, benzimidazole-based, dicarboximide-based, acid amide-based [flutoranyl (α, α, α-tri Fluoro-3′-isopropoxy-o-toluanilide)], triazole-based [tetraconazole ((±) -2- (2,4-dichlorophenyl) -3- (1H-1,2,4-triazole-1) -Yl) propyl = 1,1,2,2-tetrafluoroethyl = ether), imibenconazole (4-chlorobenzyl = N- (2,4-dichlorophenyl) -2- (1H-1,2,4- Triazol-1-yl) thioacetimidate)], imidazole, piperazine, methoxyacrylate, oxazolidinedione, strobilurin, anilinopi Bactericides such as midine, dithiolane, quinoxaline, aminopyrimidine, phenylpyrrole, triazine, cyanoacetamide, guanidine, phthalide [fusalide (4,5,6,7-tetrachlorophthalide), etc.] An antibiotic fungicide [Kasugamycin ([5-amino-2-methyl-6- (2,3,4,5,6-pentahydroxy-cyclohexyloxy) tetrahydropyran-3-yl] amino-α-imino Acetic acid)), natural product disinfectants and biological pesticides.

  Examples of the herbicide include phenoxy acid [MCPA thioethyl (S-ethyl = 2- (4-chloro-2-methylphenoxy) thioacetate)], carbamate, acid amide [tenyl chlor (2-chloro-N- (3-methoxy-2-enyl) -2 ′, 6′-dimethylacetanilide), butachlor (2-chloro-2 ′, 6′-diethyl-N- (butoxymethyl) acetanilide), etc.], acetanilide, urea , Sulfonylurea, pyrimidyloxybenzoic acid, triazine [cimetrine (2-methylthio-4,6-bis (ethylamino) -S-triazine) etc.], diazine, diazole [pyrazolate (4- (2,4 -Dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl-toluene-4-sulfone Etc.), bipyridylium, dinitroaniline, aromatic carboxylic acid, imidazolinone, fatty acid, organic phosphorus, amino acid, diphenyl ether [biphenox (5- (2,4-dichlorophenoxy) -2- Nitrile, cyclohexanedione, phenylphthalimide, cineole, indandione, benzofuran, triazolopyrimidine, oxazinone, allyltriazolinone, isourazole, pyrimidinylthiophthalide Type, triazolinone type, inorganic herbicide, biological pesticide and the like.

Examples of plant growth regulators include ethylene, auxin, cytokinin, and gibberellin.
The agrochemical active ingredient (a) may be used alone or in combination of two or more.

  In addition, specific agricultural chemical active ingredients contained in these include, for example, “Agricultural Chemicals Handbook 2005 Edition” (Japan Plant Protection Association, issued on October 11, 2005), “SHIBUYA INDEX 12th Edition” (SHIBUYA INDEX) Research Group, published on June 25, 2007), “The Pesticide Manual Fourteenth Edition” (published by British Crop Protection Council).

In addition, as the pesticidal active ingredient (a) used in the present invention, conventionally known pesticidal active ingredients other than those described above may be used as long as they serve the same purpose as the present invention and are applied as an aqueous suspension preparation. Can be applied.
The amount of the agrochemical active ingredient added is usually 0.01 to 60% by weight, preferably 0.1 to 50% by weight, based on the total amount of the aqueous suspension preparation.

(B) Water-soluble guanidines In the aqueous suspension preparation of the present invention, it is essential that water-soluble guanidines are contained.
About the contribution effect to the dispersion stability of the aqueous suspension formulation of water-soluble guanidines is inferred as follows.

  When water-soluble guanidines are used in an aqueous suspension preparation, guanidine molecules are oriented around the dispersoid particles, and the guanidine molecules form hydrogen bonds with water as a dispersion medium. Such hydrogen bonds interact multiple times to form a hydrogen bond network between the dispersoid particles via water, improving the suspension stability without increasing the viscosity. Furthermore, particle aggregation is suppressed by improving the dispersion stability by preventing coalescence and aggregation of the dispersoid particles by the steric effect and electron repulsion effect of the guanidine molecule.

  The effect of improving the suspension property and particle aggregation by the water-soluble guanidines is exhibited regardless of whether the dispersoid is solid or liquid. Conventionally, in order to improve both physical properties of suspension and particle aggregation, materials for improving suspension and particles aggregation must be added. In some cases, both effects of particle aggregation improvement are canceled out. Since water-soluble guanidines have both effects of maintaining suspension and suppressing particle aggregation, it is not necessary to consider this disadvantage.

The water-soluble guanidines used in the present invention are generally industrially used in the following applications, but there are no examples of use in agrochemical aqueous suspension preparations, and the present invention does not contain these components. We discovered for the first time the findings that contribute to the dispersion stability and suspension stability of aqueous suspension formulations.
(1) Protein denaturant, solubilizer (guanidine hydrochloride)
(2) Organic synthetic raw materials such as pharmaceuticals and agricultural chemicals (guanidine, guanidine hydrochloride, guanidine sulfamate, guanidine nitrate, guanidine carbonate)
(3) Antistatic agent for fibers (guanidine hydrochloride)
(4) Flame retardant, fire extinguishing agent (guanidine sulfamate, guanidine phosphate)
(5) Rocket propellant (guanidine nitrate)
(6) Antioxidant (guanidine carbonate)
(7) pH adjuster (guanidine carbonate)

  Examples of water-soluble guanidines that can be used in the present invention include the following, but the water-soluble guanidines are not limited to these as long as they are water-soluble compounds that can exist as guanidine molecules when dissolved in water. Two or more types may be used in combination. For example, guanidine, guanidine hydrochloride, guanidine nitrate, guanidine sulfamate, guanidine carbonate, guanidine phosphate and the like can be mentioned, and guanidine hydrochloride and guanidine sulfamate are particularly preferable.

The content of the water-soluble guanidine in the aqueous suspension preparation is 0.1 to 50% by weight, preferably 1 to 25% by weight.
Moreover, it is preferable that the addition amount with respect to an agrochemical active ingredient of water-soluble guanidine is the range of 0.1 times-10 times by weight% ratio. When the added amount is less than 0.1 times, the dispersion stabilizing effect of the agrochemical active ingredient particles as a dispersoid tends to be weakened, and when it exceeds 2.5 times, the dispersion stabilizing effect tends to reach a peak.

(C) Other adjuvants The aqueous suspension preparation of the present invention may contain the following components as supplements in addition to the above-described essential components as long as the effects of the present invention are not lost.
For example, examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkylate, polyoxyethylene phenyl ether polymer, polyoxyethylene alkyl ether Examples thereof include oxyethylene alkylene allyl phenyl ether, polyoxyethylene alkylene glycol, and polyoxyethylene-polyoxypropylene block polymer.

  Examples of the anionic surfactant include alkyl allyl sulfonate, lignin sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl aryl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene styryl phenyl ether sulfate, and lauryl. Examples include sulfates.

Examples of the cationic surfactant include alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, and alkylpyridinium salts.
Examples of amphoteric surfactants include dialkylaminoethyl betaine and alkyldimethylbenzyl betaine.

  The surfactant that can be used in the present invention is not limited to these examples, and one or more kinds may be used in combination. The content of the surfactant in the aqueous suspension preparation is preferably 0.1 to 20% by weight.

  Examples of the thickener include heteropolysaccharides such as xanthan gum, welan gum, and rhamzan gum, dextrin, starch derivatives such as starch phosphate, tragacanth gum, casein, colloidal hydrous aluminum silicate, colloidal hydrous magnesium silicate, colloidal hydrous silica. Examples thereof include, but are not limited to, aluminum oxide / magnesium and silicon dioxide, and there is no problem even if one or more of these are used in combination. The content of the thickener in the aqueous suspension preparation is preferably 0.1 to 10% by weight.

  Examples of antifoaming agents include silicone-based and fatty acid-based materials, anti-freezing agents such as ethylene glycol, propylene glycol, and glycerin. Antiseptic anti-biotic agents include potassium sorbate, p-chloro-m-xylenol, and p-oxy. As pH adjusters such as butyl benzoate, citric acid, phosphoric acid, magnesium carbonate, etc. As stabilizers for agricultural chemical active ingredients, antioxidants, ultraviolet inhibitors, crystal precipitation inhibitors, etc. may be added. However, it is not limited to the adjuvant illustrated here.

<Method for preparing aqueous suspension formulation>
Although the preparation method of the aqueous suspension formulation of this invention is not specifically limited, For example, it can prepare by the following method.
(1) When using a solid agricultural chemical active ingredient After adding water-soluble guanidines (b) to water, the agricultural chemical active ingredient (a) finely pulverized in advance with a Jet mill or the like and other auxiliary agents as necessary ( c) a method of preparing by dissolving or dispersing, or after adding water-soluble guanidines (b), agrochemical active ingredients (a) and other auxiliary agents (c) as necessary to water, glass beads, etc. Method of preparing aqueous suspension preparation by wet pulverization using, or wet pulverization using glass beads etc. after adding agrochemical active ingredient (a) and other auxiliary agent (c) as necessary to water Any of the methods for preparing an aqueous suspension preparation by adding the water-soluble guanidines (b) to the obtained dispersion liquid may be employed.

(2) When using liquid pesticidal active ingredients Water-soluble guanidines (b), pesticidal active ingredients (a) and other auxiliary agents (c) as necessary are added to water and then emulsified to form an aqueous suspension. A method for preparing a preparation, an agrochemical active ingredient and, if necessary, other auxiliary agent (c) are added to water, and then an aqueous suspension preparation is prepared by adding and mixing water-soluble guanidines (b) to the emulsified liquid. It is good also as the method of preparing.

(3) When using a solid and a liquid agrochemical active ingredient together A liquid agrochemical active ingredient (a) and another adjuvant (c) as needed are added to water, and it is set as an emulsion liquid (i).
Further, the water-soluble guanidines (b) may be preliminarily dissolved in water, and the liquid pesticidal active ingredient (a) and other auxiliary agent (c) as necessary may be added and emulsified for use ( Emulsion (ii)).

  When preparing using this emulsified liquid (i), the solid agrochemical active ingredient (a), water-soluble guanidines (b), and other auxiliary substances that have been finely pulverized in advance with a Jet mill or the like are added to the emulsified liquid (i). A method of preparing an aqueous suspension preparation by dissolving or dispersing the agent (c), and the solid agrochemical active ingredient (a), water-soluble guanidines (b) and other supplements as necessary in the emulsion (i) A method of preparing an aqueous suspension preparation by adding the agent (c) to water and then wet-grinding with glass beads or the like, or a solid agrochemical active ingredient (a), a water-soluble guanidine (b) and as required Accordingly, after adding the other auxiliary agent (c) to water, the aqueous suspension is prepared by mixing the dispersion liquid wet-ground using glass beads and the emulsion (i) or (ii) prepared in advance. Preparing a suspension Method, solid agrochemical active ingredient (a) and other auxiliary agent (c) as necessary, after adding water and then using a glass bead, etc., a wet dispersion and an emulsion (i ) And water-soluble guanidines (b) may be used, and any method for preparing an aqueous suspension preparation may be employed.

  Moreover, when preparing using an emulsion (ii), melt | dissolve or disperse | distribute solid agrochemical active ingredient (a) and other adjuvant (c) which were previously pulverized with a Jet grinder etc. to an emulsion (ii). A method for preparing an aqueous suspension preparation, and after adding a solid agrochemical active ingredient (a) and other auxiliary agent (c) as necessary to water in an emulsion (ii), using glass beads or the like Wet pulverization to prepare an aqueous suspension formulation, or wet pulverization using glass beads etc. after adding the solid agrochemical active ingredient (a) and other auxiliary agent (c) as necessary to water Any of the methods for preparing an aqueous suspension preparation by mixing the prepared dispersion and the previously prepared emulsion (ii) may be employed.

<Usage form of aqueous suspension preparation>
The aqueous suspension preparation prepared by the above method is, for example, a method of diluting about 1.5 to 5 times with a stock solution or water and directly spraying it on a paddy field, or a solution diluted about 50 to 5000 times with a stock solution or water. Can be applied by spraying stalks and leaves on crops and weeds using a sprayer, etc., or by using a helicopter or the like from the air and spraying the raw solution as it is or diluting it 2 to 100 times with water. However, it is not limited to these.

〔Example〕
Hereinafter, although the method to obtain the aqueous suspension formulation with improved long-term storage stability of this invention based on an Example is demonstrated concretely, this invention is not limited to these Examples.
In the examples, “parts” are all parts by weight.

  After dissolving 8 parts of guanidine hydrochloride (water-soluble guanidines) in 67.7 parts of water, 1 part of polyoxyethylene alkyl ether (surfactant) and 5 parts of propylene glycol (freezing agent) are added. -Add 10 parts of fusaride (phthalide fungicide) finely pulverized to an average particle size of 2.5 μm using O-mizer (manufactured by Seishin Enterprise Co., Ltd.) and 0.3 part of colloidal hydrous aluminum silicate (thickener) Then, the mixture is stirred and mixed at 5000 rpm for 10 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 8 parts of a 2% xanthan gum aqueous solution (thickening agent) is added to this mixed liquid, and mixed uniformly with a three-one motor (manufactured by HEIDON), whereby an aqueous solution having a dispersed particle size of 2.5 μm and a viscosity of 520 mPa · s (20 ° C.). A suspension formulation was obtained.

  Formulation composition: 10 parts of fusaride (phthalide fungicide), 26 parts of guanidine hydrochloride (water-soluble guanidines), 1 part of polyoxyethylene arylphenyl ether (surfactant), 5 parts of propylene glycol (antifreeze), colloidal Prepared in the same manner as in Example 1 except that 0.3 part of hydrous aluminum silicate (thickener), 9 parts of 2% xanthan gum aqueous solution (thickener), and 48.7 parts of water were used, and the dispersed particle size was 2.5 μm. An aqueous suspension preparation having a viscosity of 540 mPa · s (20 ° C.) was obtained.

  Formulation composition: 10 parts of fusaride (phthalide fungicide), 0.5 parts of guanidine sulfamate (water-soluble guanidines), 1 part of polyoxyethylene-polyoxypropylene block polymer (surfactant), propylene glycol (freezing agent) ) Prepared in the same manner as in Example 1 except that 5 parts, colloidal hydrous aluminum silicate (thickener) 0.3 parts, 2% xanthan gum aqueous solution (thickener) 8 parts, water 75.2 parts, An aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 510 mPa · s (20 ° C.) was obtained.

  Formulation composition: 10 parts of fusaride (phthalide fungicide), 18 parts of guanidine phosphate (water-soluble guanidines), 1 part of polyoxyethylene alkyl ether phosphate (surfactant), 5 parts of propylene glycol (freezing agent), colloid The same procedure as in Example 1 was conducted except that 0.3 part of aqueous hydrated aluminum silicate (thickener), 9 parts of 2% xanthan gum aqueous solution (thickener), and 56.7 parts of water were used. An aqueous suspension preparation having a viscosity of 5 μm and a viscosity of 520 mPa · s (20 ° C.) was obtained.

After dissolving 10 parts of guanidine hydrochloride (water-soluble guanidine), 5 parts of propylene glycol (freezing agent) and 2 parts of polyoxyethylene arylphenyl ether (surfactant) in 56.6 parts of water, buprofezin (insect growth regulator) ) 20 parts colloidal hydrous magnesium silicate (thickening agent) 0.4 part, so that the average particle size of the pulverized liquid is 2.5 μm in Dynomill KDL type (Willy A. Bachofen AG) Finely pulverized. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C.
As the grinding media, hard glass beads having a diameter of 0.7 to 1.2 mm were used. 6 parts of a 2% xanthan gum aqueous solution is added to this pulverized liquid and mixed uniformly with Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 540 mPa · s (20 ° C.). It was.

  Formulation composition is 20 parts of buprofezin (insect growth control agent), 1.6 parts of guanidine sulfamate (water-soluble guanidines), 3 parts of polyoxyethylene-polyoxypropylene block polymer (surfactant), propylene glycol (freezing agent) ) Prepared in the same manner as Example 5 except that 5 parts, colloidal hydrous magnesium silicate (thickener) 0.4 part, 2% xanthan gum aqueous solution (thickener) 7 parts, water 63 parts, dispersed particles An aqueous suspension preparation having a diameter of 2.5 μm and a viscosity of 560 mPa · s (20 ° C.) was obtained.

  The formulation is 20 parts buprofezin (insect growth regulator), 18 parts guanidine carbonate (water-soluble guanidines), 3 parts sodium polyacrylate (surfactant), 5 parts propylene glycol (antifreeze), colloidal hydrous silica Prepared in the same manner as in Example 5 except that 0.4 parts of magnesium acid (thickener), 6 parts of 2% xanthan gum aqueous solution (thickener), and 47.6 parts of water were used. An aqueous suspension preparation of 530 mPa · s (20 ° C.) was obtained.

  Formulation composition is 20 parts buprofezin (insect growth regulator), 0.6 parts guanidine (water-soluble guanidines), 5 parts polyoxyethylene styryl phenyl ether (surfactant), 5 parts propylene glycol (freezing agent), colloid Prepared in the same manner as in Example 5 except that 0.4 part of aqueous hydrated magnesium silicate (thickening agent), 6 parts of 2% xanthan gum aqueous solution (thickening agent), and 63 parts of water were used. An aqueous suspension preparation having a viscosity of 550 mPa · s (20 ° C.) was obtained.

  After dissolving 2 parts of guanidine sulfamate (water-soluble guanidines), 5 parts of propylene glycol (freezing agent) and 5 parts of polyoxyethylene styrylphenyl ether (surfactant) in 63.6 parts of water, MEP ( 10 parts of organophosphorus insecticide) and 0.4 parts of colloidal hydrous aluminum silicate (thickener) are added, and the average particle size of the emulsion is 2 with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Emulsified to 5 μm. 14 parts of a 2% xanthan gum aqueous solution was added to this emulsion and mixed uniformly with a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 520 mPa · s (20 ° C.). It was.

  Formulation composition is 10 parts of MEP (organophosphorus insecticide), 0.6 parts of guanidine hydrochloride (water-soluble guanidines), 8 parts of polyoxyethylene arylphenyl ether sulfate (surfactant), propylene glycol (freezing agent) 5 Partly, colloidal hydrous aluminum silicate (thickener) 0.4 parts, 2% xanthan gum aqueous solution (thickener) 14 parts, water 62 parts, An aqueous suspension preparation having a viscosity of 0.5 μm and a viscosity of 540 mPa · s (20 ° C.) was obtained.

  Formulation composition: MEP (organophosphorus insecticide) 10 parts, guanidine nitrate (water-soluble guanidines) 5 parts, polyoxyethylene arylphenyl ether (surfactant) 6 parts, propylene glycol (freezing agent) 5 parts, colloid The same as in Example 9 except that 0.4 parts of aqueous hydrated aluminum silicate (thickener), 13 parts of 2% xanthan gum aqueous solution (thickener), and 60.6 parts of water were used. An aqueous suspension preparation having a viscosity of 5 μm and a viscosity of 540 mPa · s (20 ° C.) was obtained.

  Formulation composition: 10 parts of MEP (organophosphorus insecticide), 0.5 part of guanidine phosphate (water-soluble guanidines), 6 parts of polyoxyethylene arylphenyl ether phosphate (surfactant), propylene glycol (freezing agent) Prepared and dispersed in the same manner as in Example 9 except that 5 parts, colloidal hydrous aluminum silicate (thickener) 0.4 parts, 2% xanthan gum aqueous solution (thickener) 13 parts, and water 65.1 parts were used. An aqueous suspension preparation having a particle size of 2.5 μm and a viscosity of 530 mPa · s (20 ° C.) was obtained.

After dissolving 20 parts of guanidine hydrochloride (water-soluble guanidine), 5 parts of propylene glycol (freezing agent) and 2 parts of polyoxyethylene styrylphenyl ether sulfate (surfactant) in 53.6 parts of water, imibenconazole (triazole) 10 parts of colloidal hydrous magnesium silicate (thickener) is added, and the average particle size of the pulverized liquid is 2.5 μm with Dynomill KDL type (made by Willy A. Bachofen AG). Finely pulverized so that At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C.
As the grinding media, hard glass beads having a diameter of 0.7 to 1.2 mm were used. 9 parts of a 2% xanthan gum aqueous solution was added to this pulverized liquid and mixed uniformly with a three-one motor (HEIDON) to obtain an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 540 mPa · s (20 ° C.). It was.

  Formulation composition 10 parts imibenconazole (triazole fungicide), 0.4 parts guanidine sulfamate (water-soluble guanidines), 2 parts polyoxyethylene arylphenyl ether (surfactant), propylene glycol (freezing agent) Prepared and dispersed in the same manner as in Example 13 except that 5 parts, colloidal hydrous magnesium silicate (thickener) 0.4 parts, 2% xanthan gum aqueous solution (thickener) 9 parts, and water 73.2 parts were used. An aqueous suspension preparation having a particle size of 2.5 μm and a viscosity of 530 mPa · s (20 ° C.) was obtained.

  Formulation composition 10 parts imibenconazole (triazole fungicide), 27 parts guanidine carbonate (water-soluble guanidine), 3 parts polyoxyethylene-polyoxypropylene block polymer (surfactant), propylene glycol (freezing agent) Prepared and dispersed in the same manner as in Example 13 except that 5 parts, colloidal hydrous magnesium silicate (thickener) 0.4 part, 2% xanthan gum aqueous solution (thickener) 9 part, and water 45.6 parts were used. An aqueous suspension preparation having a particle diameter of 2.5 μm and a viscosity of 520 mPa · s (20 ° C.) was obtained.

66.7 parts of water, 5 parts of propylene glycol (antifreeze), 1 part of sodium dodecylbenzenesulfonate (surfactant), 5 parts of tenyl chlor (acid amide herbicide), colloidal hydrous aluminum silicate (thickener) ) 0.3 part was added and finely pulverized with a Dynomill KDL type (manufactured by Willy A. Bachofen AG) so that the average particle size of the pulverized liquid was 2.5 μm. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C.
As the grinding media, hard glass beads having a diameter of 0.7 to 1.2 mm were used. After adding 12 parts of guanidine sulfamate (water-soluble guanidines) to this pulverized liquid, 10 parts of 2% xanthan gum aqueous solution was added and mixed uniformly with a three-one motor (manufactured by HEIDON) to obtain a dispersed particle size of 2.5 μm, An aqueous suspension preparation having a viscosity of 520 mPa · s (20 ° C.) was obtained.

  Formulation composition: 5 parts tenyl chlor (acid amide herbicide), 15 parts guanidine hydrochloride (water-soluble guanidine), 1 part polyoxyethylene alkyl ether phosphate (surfactant), 5 parts propylene glycol (freezing agent), colloid Prepared in the same manner as in Example 16 except that 0.3 part of aqueous hydrated aluminum silicate (thickener), 10 parts of 2% xanthan gum aqueous solution (thickener) and 63.7 parts of water were used. An aqueous suspension preparation having a viscosity of 5 μm and a viscosity of 550 mPa · s (20 ° C.) was obtained.

  The formulation composition is 5 parts tenyl chlor (acid amide herbicide), 20 parts guanidine carbonate (water-soluble guanidine), 0.5 part polyoxyethylene alkyl ether (surfactant), 5 parts propylene glycol (freezing agent), Prepared in the same manner as in Example 16 except that the colloidal hydrous aluminum silicate (thickener) was 0.3 part, the 2% xanthan gum aqueous solution (thickener) was 10 parts, and the water was 59.2 parts. An aqueous suspension preparation having a viscosity of 0.5 μm and a viscosity of 560 mPa · s (20 ° C.) was obtained.

  Formulation composition: 5 parts of cimetrin (triazine herbicide), 0.45 parts of guanidine (water-soluble guanidines), 1 part of sodium polycarboxylate (surfactant), 5 parts of propylene glycol (freezing agent), colloidal water content Prepared in the same manner as in Example 1 except that 0.3 part of aluminum silicate (thickener), 9 parts of 2% xanthan gum aqueous solution (thickener) and 79.25 parts of water were used, and the dispersed particle size was 2.5 μm. An aqueous suspension preparation having a viscosity of 540 mPa · s (20 ° C.) was obtained.

  Formulation composition: 5 parts of cimetrin (triazine herbicide), 0.45 parts of guanidine hydrochloride (water-soluble guanidines), 0.5 part of polyoxyethylene styrylphenyl ether sulfate (surfactant), propylene glycol (freezing agent) Prepared and dispersed in the same manner as in Example 1 except that 5 parts, colloidal hydrous aluminum silicate (thickener) 0.3 parts, 2% xanthan gum aqueous solution (thickener) 9 parts, and water 79.75 parts were used. An aqueous suspension preparation having a particle size of 2.5 μm and a viscosity of 510 mPa · s (20 ° C.) was obtained.

  To 48.7 parts of water, 5 parts of propylene glycol (freezing agent) and 4 parts of polyoxyethylene styryl phenyl ether (surfactant) are added, and 12 parts of butachlor (acid amide herbicide) is added to the mixture, containing colloidal water. 0.3 parts of aluminum silicate (thickener) was added, and emulsified with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) so that the average particle size of the emulsion was 2.5 μm. After adding 18 parts of guanidine hydrochloride (water-soluble guanidine) to this emulsion, 12 parts of a 2% xanthan gum aqueous solution is added and mixed uniformly with a three-one motor (manufactured by HEIDON). An aqueous suspension formulation of 550 mPa · s (20 ° C.) was obtained.

  Formulation composition is 12 parts butachlor (acid amide herbicide), 0.6 part guanidine sulfamate (water-soluble guanidine), 3 parts polyoxyethylene arylphenyl ether (surfactant), propylene glycol (freezing agent) 5 Parts, colloidal hydrous aluminum silicate (thickener) 0.3 parts, 2% xanthan gum aqueous solution (thickener) 12 parts, water 67.1 parts, prepared in the same manner as in Example 21 and dispersed particles An aqueous suspension preparation having a diameter of 2.5 μm and a viscosity of 560 mPa · s (20 ° C.) was obtained.

  Formulation composition is 12 parts butachlor (acid amide herbicide), 33.6 parts guanidine nitrate (water-soluble guanidines), 4 parts polyoxyethylene arylphenyl ether sulfate (surfactant), propylene glycol (freezing agent) 5 Parts, colloidal hydrous aluminum silicate (thickener) 0.3 parts, 2% xanthan gum aqueous solution (thickener) 12 parts, and water 33.1 parts. An aqueous suspension preparation having a diameter of 2.5 μm and a viscosity of 570 mPa · s (20 ° C.) was obtained.

    55.7 parts of water and 0.8 part of colloidal hydrous aluminum silicate (thickening agent) were mixed and stirred and mixed at 6000 rpm for 20 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and then guanidine hydrochloride (Water-soluble guanidines) 16.8 parts, kasugamycin (antibiotic fungicide) 1.2 parts, imibenconazole (triazole fungicide) 10 parts, polyoxyethylene arylphenyl ether (surfactant) 1 part, Add 5 parts of propylene glycol (antifreeze) and mix. Next, these mixtures were finely pulverized using a Dinomill KDL type (manufactured by Willy A. Bachofen AG) so that the average particle diameter of the pulverized liquid became 2.5 μm. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C. Next, 9.5 parts of a 2% xanthan gum aqueous solution (thickening agent) was uniformly mixed with these dispersions with a three-one motor (manufactured by HEIDON), so that the dispersed particle diameter was 2.5 μm and the viscosity was 590 mPa · s (20 ° C.). An aqueous suspension formulation was obtained.

  35 parts of water and 0.5 part of colloidal hydrous aluminum silicate (thickener) were mixed and stirred and mixed for 20 minutes at 6000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), followed by guanidine sulfamate ( 17.5 parts of water-soluble guanidines), 15 parts of fusaride (phthalide fungicide), 20 parts of buprofezin (insect growth control agent), 1 part of polyoxyethylene alkyl ether (surfactant), sodium dodecylbenzenesulfonate (interface) 2 parts of activator) and 5 parts of propylene glycol (freezing agent) are added and mixed. Next, these mixtures were finely pulverized using a Dinomill KDL type (manufactured by Willy A. Bachofen AG) so that the average particle diameter of the pulverized liquid became 2.5 μm. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C. Next, 4 parts of a 2% xanthan gum aqueous solution (thickening agent) is uniformly mixed with these dispersions with a three-one motor (manufactured by HEIDON), whereby an aqueous solution having a dispersed particle size of 2.5 μm and a viscosity of 600 mPa · s (20 ° C.). A suspension formulation was obtained.

  41.5 parts of water, 4 parts of guanidine sulfamate (water-soluble guanidines), 4 parts of polyoxyethylene allyl phenyl ether (surfactant), 0.5 parts of polyoxyethylene alkyl ether (surfactant), kasugamycin (antibiotics) 0.6 parts of a substance-based disinfectant and 5 parts of propylene glycol (an antifreezing agent) were dissolved. In this solution, 25 parts of MEP active substance (organophosphorus insecticide), 0.4 part of colloidal hydrous aluminum silicate (thickener), and Jet-O-mizer (manufactured by Seishin Enterprise Co., Ltd.) Add 10 parts finely pulverized fusalide (phthalide fungicide) to 2.5 μm in diameter and stir so that the average particle diameter becomes 2.5 μm with TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Mixed. Subsequently, 9 parts of a 2% xanthan gum aqueous solution is added to these mixed solutions, and the mixture is uniformly mixed with a three-one motor (manufactured by HEIDON), whereby an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 590 mPa · s (20 ° C.). Got.

  34 parts of water, 8 parts of guanidine hydrochloride (water-soluble guanidines), 8 parts of polyoxyethylene styryl phenyl ether (surfactant), 0.6 parts of kasugamycin (antibiotic antibiotic), propylene glycol (freezing agent) 5 Part was dissolved. A premix in which 25 parts of MEP active ingredient (organophosphorus insecticide) and 1 part of calcium dodecylbenzenesulfonate (surfactant) were mixed in this solution, colloidal hydrous aluminum silicate (thickener) 0.4 10 parts of a fuslide base (phthalide fungicide) finely pulverized to an average particle size of 2.5 μm using Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.), and TK homomixer (Special Machine Industries) The product was stirred and mixed so that the average particle size was 2.5 μm. Next, 8 parts of a 2% xanthan gum aqueous solution is added to these mixed solutions, and mixed uniformly with a three-one motor (manufactured by HEIDON), whereby an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 610 mPa · s (20 ° C.). Got.

[Comparative Example 1]
The formulation was prepared in the same manner as in Example 1 except that 8 parts of guanidine hydrochloride (water-soluble guanidines) were subtracted from Example 1 to obtain 11 parts of a 2% xanthan gum aqueous solution and 72.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 670 mPa · s (20 ° C.).

[Comparative Example 2]
The formulation was prepared in the same manner as in Example 1 except that 26 parts of guanidine hydrochloride (water-soluble guanidines) were subtracted from Example 2 to obtain 16 parts of a 2% xanthan gum aqueous solution and 67.7 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 690 mPa · s (20 ° C.).

[Comparative Example 3]
The formulation was prepared in the same manner as in Example 3 except that 0.5 part of guanidine sulfamate (water-soluble guanidine) was subtracted from Example 3 to obtain 2 parts of a 2% xanthan gum aqueous solution and 75.7 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 660 mPa · s (20 ° C.).

[Comparative Example 4]
The formulation was prepared in the same manner as in Example 4 except that 18 parts of guanidine phosphate (water-soluble guanidines) were subtracted from Example 4 to obtain 14 parts of a 2% xanthan gum aqueous solution and 69.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 700 mPa · s (20 ° C.).

[Comparative Example 5]
The formulation was prepared in the same manner as in Example 5 except that 10 parts of guanidine hydrochloride (water-soluble guanidines) were subtracted from Example 5 to obtain 10 parts of a 2% xanthan gum aqueous solution and 62.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 640 mPa · s (20 ° C.).

[Comparative Example 6]
The formulation was prepared in the same manner as in Example 6 except that 1.6 parts of guanidine sulfamate (water-soluble guanidines) was subtracted from Example 6 to obtain 7.6 parts of a 2% xanthan gum aqueous solution and 64 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 660 mPa · s (20 ° C.).

[Comparative Example 7]
The formulation was prepared in the same manner as in Example 7, except that 18 parts of guanidine carbonate (water-soluble guanidines) were subtracted from Example 7 to obtain 13 parts of a 2% xanthan gum aqueous solution and 58.6 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 690 mPa · s (20 ° C.).

[Comparative Example 8]
The formulation was prepared in the same manner as in Example 8, except that 0.6 part of guanidine (water-soluble guanidine) was subtracted from Example 8 to obtain 6.6 parts of 2% xanthan gum aqueous solution and 63 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 630 mPa · s (20 ° C.).

[Comparative Example 9]
The formulation was prepared in the same manner as in Example 9 except that 2 parts of guanidine sulfamate (water-soluble guanidines) were subtracted from Example 9 to obtain 15 parts of a 2% xanthan gum aqueous solution and 64.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 670 mPa · s (20 ° C.).

[Comparative Example 10]
The formulation was prepared in the same manner as in Example 10 except that 0.6 part of guanidine hydrochloride (water-soluble guanidine) was subtracted from Example 10 to obtain 15 parts of a 2% xanthan gum aqueous solution and 61.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 650 mPa · s (20 ° C.).

[Comparative Example 11]
The formulation was prepared in the same manner as in Example 11 except that 5 parts of guanidine nitrate (water-soluble guanidine) was subtracted from Example 11 to obtain 15 parts of a 2% xanthan gum aqueous solution and 63.6 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 690 mPa · s (20 ° C.).

[Comparative Example 12]
The formulation was prepared in the same manner as in Example 12 except that 0.5 part of guanidine phosphate (water-soluble guanidine) was subtracted from Example 12 to obtain 14 parts of a 2% xanthan gum aqueous solution and 64.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 700 mPa · s (20 ° C.).

[Comparative Example 13]
The formulation was prepared in the same manner as in Example 13 except that 20 parts of guanidine hydrochloride (water-soluble guanidines) was subtracted from Example 13 to obtain 12 parts of a 2% xanthan gum aqueous solution and 70.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 670 mPa · s (20 ° C.).

[Comparative Example 14]
The formulation was prepared in the same manner as in Example 14 except that 0.4 part of guanidine sulfamate (water-soluble guanidine) was subtracted from Example 14 to obtain 9 parts of a 2% xanthan gum aqueous solution and 73.6 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 630 mPa · s (20 ° C.).

[Comparative Example 15]
The formulation was prepared in the same manner as in Example 15 except that 27 parts of guanidine carbonate (water-soluble guanidines) were subtracted from Example 15 to obtain 12 parts of a 2% xanthan gum aqueous solution and 69.6 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 660 mPa · s (20 ° C.).

[Comparative Example 16]
The formulation was prepared in the same manner as in Example 16 except that 12 parts of guanidine sulfamate (water-soluble guanidines) was subtracted from Example 16 to obtain 14 parts of a 2% xanthan gum aqueous solution and 74.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 630 mPa · s (20 ° C.).

[Comparative Example 17]
The formulation was prepared in the same manner as in Example 17 except that 15 parts of guanidine hydrochloride (water-soluble guanidines) were subtracted from Example 17 to obtain 15 parts of a 2% xanthan gum aqueous solution and 73.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 650 mPa · s (20 ° C.).

[Comparative Example 18]
The formulation was prepared in the same manner as in Example 18 except that 20 parts of guanidine carbonate (water-soluble guanidines) were subtracted from Example 18 to obtain 16 parts of a 2% xanthan gum aqueous solution and 73.2 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 680 mPa · s (20 ° C.).

[Comparative Example 19]
The formulation was prepared in the same manner as in Example 19 except that 0.45 part of guanidine (water-soluble guanidine) was subtracted from Example 19 to obtain 9 parts of a 2% xanthan gum aqueous solution and 79.7 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 680 mPa · s (20 ° C.).

[Comparative Example 20]
The formulation was prepared in the same manner as in Example 20 except that 0.45 part of guanidine hydrochloride (water-soluble guanidine) was subtracted from Example 20 to obtain 9 parts of a 2% xanthan gum aqueous solution and 80.2 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 690 mPa · s (20 ° C.).

[Comparative Example 21]
The formulation was prepared in the same manner as in Example 21, except that 18 parts of guanidine hydrochloride (water-soluble guanidines) were subtracted from Example 21 to obtain 14 parts of a 2% xanthan gum aqueous solution and 64.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 650 mPa · s (20 ° C.).

[Comparative Example 22]
The formulation was prepared in the same manner as in Example 22 except that 0.6 part of guanidine sulfamate (water-soluble guanidine) was subtracted from Example 22 to obtain 12 parts of a 2% xanthan gum aqueous solution and 67.7 parts of water. The dispersed particle size was 2.5 μm and the viscosity was 670 mPa · s (20 ° C.).

[Comparative Example 23]
The formulation was prepared in the same manner as in Example 23 except that 33.6 parts of guanidine nitrate (water-soluble guanidine) was subtracted from Example 23 to obtain 15 parts of a 2% xanthan gum aqueous solution and 63.7 parts of water. The dispersed particle diameter was 2.5 μm, and the viscosity was 680 mPa · s (20 ° C.).

[Comparative Example 24]
81 parts of water and 0.8 part of colloidal hydrous aluminum silicate (thickener) were mixed and stirred and mixed for 20 minutes at 6000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 1.2 parts, imibenconazole (triazole fungicide) 10 parts, polyoxyethylene distyrenated phenyl ether (HLB17) (surfactant) 1 part, polyoxyethylene nonylphenyl ether (HLB5. 7) Add 1 part of (surfactant) and 5 parts of propylene glycol (antifreeze) and mix. Next, these mixtures were finely pulverized using a Dinomill KDL type (manufactured by Willy A. Bachofen AG) so that the average particle diameter of the pulverized liquid became 2.5 μm. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C. The obtained aqueous suspension preparation had physical properties of a dispersed particle size of 2.5 μm and a viscosity of 190 mPa · s (20 ° C.).

[Comparative Example 25]
After mixing 55 parts of water and 1.0 part of colloidal hydrous aluminum silicate (thickener), the mixture was stirred and mixed at 6000 homomixer (made by Tokushu Kika Kogyo Co., Ltd.) at 6000 rpm for 20 minutes. 15 parts sterilizer, 20 parts buprofezin (insect growth control agent), 2 parts polyoxyethylene distyrenated phenyl ether (HLB17) (surfactant), polyoxyethylene nonylphenyl ether (HLB 5.7) (surfactant) 2 parts and 5 parts of propylene glycol (freezing agent) are added and mixed. Next, these mixtures were finely pulverized using a Dinomill KDL type (manufactured by Willy A. Bachofen AG) so that the average particle diameter of the pulverized liquid became 2.5 μm. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C. The obtained aqueous suspension preparation had physical properties of a dispersed particle size of 2.5 μm and a viscosity of 195 mPa · s (20 ° C.).

[Comparative Example 26]
77.6 parts of water, 5 parts of propylene glycol (freezing agent), 1 part of polyoxyethylene arylphenyl ether (surfactant), 5 parts of tenyl chlor (acid amide herbicide), rosin (softening point 80 ° C.) (aggregation) Inhibitor) 0.1 part, colloidal hydrous aluminum silicate (thickener) 0.3 part was added, and the average particle size of the pulverized liquid was 2.5 μm using Dynomill KDL type (Willy A. Bachofen AG). It was pulverized to become. At this time, pulverization was performed while cooling so that the temperature of the pulverized liquid did not exceed 20 ° C.
Note that hard glass beads having a diameter of 0.7 to 1.2 mm were used as the powder adopting media. 11 parts of a 2% xanthan gum aqueous solution was added to this pulverized liquid and mixed uniformly with a three-one motor (HEIDON) to obtain an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 620 mPa · s (20 ° C.). It was.

[Comparative Example 27]
4 parts of polyoxyethylene-polyoxypropylene block polymer (surfactant) was dissolved in 37 parts of water. In this solution, 0.6 parts of kasugamycin (antibiotic antibiotic), 5 parts of propylene glycol (freezing agent), 25 parts of MEP active ingredient (organic phosphorus insecticide) and 10 parts of soybean oil (oil and fat) are mixed. Dissolved premix, 0.4 parts of colloidal hydrous aluminum silicate (thickener), finely pulverized phthalide (phthalide) to an average particle size of 2.5 μm using Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.) 10 parts) was added and stirred and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) so that the average particle size was 2.5 μm. Next, 8 parts of a 2% xanthan gum aqueous solution is added to these mixed solutions, and mixed uniformly with a three-one motor (manufactured by HEIDON), whereby an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 610 mPa · s (20 ° C.). Got.

[Comparative Example 28]
6 parts of polyoxyethylene styryl phenyl ether (surfactant) was dissolved in 38 parts of water. In this solution, 0.6 parts of kasugamycin (antibiotic antibiotic), 5 parts of propylene glycol (freezing agent), 25 parts of MEP active ingredient (organic phosphorus insecticide) and 8 parts of liquid paraffin (oil) Dissolved premix, 0.4 parts of colloidal hydrous aluminum silicate (thickener), finely pulverized phthalide (phthalide) to an average particle size of 2.5 μm using Jet-O-Mizer (manufactured by Seishin Enterprise Co., Ltd.) 10 parts) was added and stirred and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) so that the average particle size was 2.5 μm. Next, 7 parts of a 2% xanthan gum aqueous solution is added to these mixed solutions, and mixed uniformly with a three-one motor (manufactured by HEIDON), whereby an aqueous suspension preparation having a dispersed particle size of 2.5 μm and a viscosity of 620 mPa · s (20 ° C.). Got.

[Comparative Example 29]
It was prepared in the same manner as in Example 27 except that the formulation composition was changed from 8 parts of guanidine hydrochloride (water-soluble guanidines) in Example 27 to 8 parts of urea. The dispersed particle diameter was 2.5 μm, and the viscosity was 590 mPa · s (20 ° C.).

[Test Example 1 (viscosity measurement)]
The viscosity of the aqueous suspension pesticide immediately after preparation was measured using a B-type viscometer [manufactured by Tokimec Co., Ltd.] in rotor No. 2, rotation speed 12r. p. m, measured at a temperature of 20 ° C.
The results are shown in Tables 1 and 2.

[Test Example 2 (suspension test)]
30 mL of the prepared aqueous suspension preparation is placed in a test tube having a capacity of 30 mL (φ17 mm × length 180 mm), sealed, and left standing at 20 ° C. for 90 days and 40 ° C. for 90 days. After the storage test, the preparation in the test tube settled in the lower layer, and the water layer (upper skid layer) formed in the upper layer and the height (cm) of all layers were measured and calculated according to the following formula.

Moreover, the sample after a test was taken out from the test tube, and about the sample, the dispersion | distribution particle diameter (micrometer) was measured with Shimadzu Corporation SALD-2000J (laser diffraction type particle size distribution measuring apparatus), and particle aggregation was evaluated.
The results are shown in Tables 1-3.

(Explanation of the table)
The test results described in Tables 1 to 3 are as follows. Examples 1 to 27 are comparative examples 1 to 29 in terms of long-term storage stability (suspension, presence / absence of particle aggregation) at 20 ° C. for 90 days and 40 ° C. for 90 days. It is clearly superior to
Examples 1-27 showed good results in both the suspension and particle cohesive aspects.

  Examples 1, 5, 9, and 13 containing guanidine hydrochloride or guanidine sulfamate as water-soluble guanidines, and the addition ratio thereof is in the range of 0.1 to 2.5 times by weight% with respect to the agrochemical active ingredient. , 16, 21, and 24-27, not only maintained very high suspension at 20 ° C. and 40 ° C., but also did not aggregate particles. Furthermore, it can be applied to a large number of pesticidal active ingredients, and as shown in Examples 24 to 27, even if two or more kinds are used in combination or a water-soluble pesticidal active ingredient is used, good suspension and particle aggregation suppression effect showed that.

  Examples 2 and 17 which contain guanidine hydrochloride or guanidine sulfamate as water-soluble guanidines and whose addition ratio exceeds 2.5 times by weight with respect to the pesticidal active ingredient are also 20 ° C. and 40 ° C. conditions. In addition to maintaining a very high suspension property, no particle aggregation was observed, but the dispersion stabilizing effect on the amount of water-soluble guanidines reached its peak.

  About Examples 3, 6, 10, 14, 20, and 22 containing guanidine hydrochloride or guanidine sulfamate as water-soluble guanidines, and the addition ratio is less than 0.1 times by weight percent with respect to the pesticidal active ingredient. Under the 20 ° C. condition, very high suspension was maintained, and under the 40 ° C. condition, the suspension was maintained at a high level without any practical problems. Moreover, although some particle agglomeration was observed, it was at a level causing no practical problems.

  Examples 4, 7 and 7 containing water-soluble guanidines other than guanidine hydrochloride or guanidine sulfamate, and the addition ratio thereof is in the range of 0.1 to 10 times by weight percent with respect to the agricultural chemical active ingredient. For No. 11, very high suspension was maintained under the condition of 20 ° C., and high suspension without any practical problem was maintained although it was slightly reduced under the condition of 40 ° C. As for the particle aggregation, no aggregation was observed at 20 ° C., and some aggregation was observed at 40 ° C., but it was at a level causing no practical problem.

  Examples 15, 18, and 23 containing water-soluble guanidines other than guanidine hydrochloride or guanidine sulfamate, and the addition ratio exceeds 10 times by weight ratio with respect to the pesticidal active ingredient, also at 20 ° C. In the case of No. 4, the suspension was maintained at a very high level, and although it dropped slightly at 40 ° C., the suspension was maintained at a high level without any practical problems. As for the particle aggregation, no aggregation was observed at 20 ° C., and some aggregation was observed at 40 ° C., but it was at a level causing no practical problem.

  For Examples 8, 12, and 19 containing water-soluble guanidines other than guanidine hydrochloride or guanidine sulfamate, and the addition ratio is less than 0.1 times by weight with respect to the pesticidal active ingredient, Although it dropped slightly under the conditions of 40 ° C., high suspension without any practical problems was maintained. As for the particle aggregation, no aggregation was observed at 20 ° C., and some aggregation was observed at 40 ° C., but it was at a level causing no practical problem.

  On the other hand, in Comparative Examples 1 to 23, which are preparation compositions in which the water-soluble guanidines in Examples 1 to 23 are replaced with other compositions, the preparation viscosity is about 100 to 180 mPa · s higher than those in Examples 1 to 23. Nevertheless, the pendency was remarkably reduced, and significant particle aggregation was observed.

  In Comparative Examples 1 to 23, a clear upper skid was produced in both the 20 ° C. and 40 ° C. conditions on the suspension surface, and clear particle aggregation was confirmed on both the 20 ° C. and 40 ° C. conditions in the particle aggregation surface. In particular, the particle aggregation is remarkable under the condition of 40 ° C., resulting in practical problems in both the suspension property and the particle aggregation property.

  Comparative Examples 1 to 23 are formulation compositions obtained by removing water-soluble guanidines from Examples 1 to 23, and there is a clear difference in suspension and particle aggregation between the Examples and Comparative Examples. It is clear that it is derived from the class.

  In Comparative Examples 24 and 25 prepared according to Japanese Patent Laid-Open No. 6-316502 (Patent Document 1), the suspension has a slightly good value at 20 ° C., and the sedimentation and the supernatant are largely separated at 40 ° C. As for particle agglomeration, clear agglomeration was observed under both conditions of 20 ° C. and 40 ° C.

  Moreover, about the comparative example 26 prepared according to Unexamined-Japanese-Patent No. 9-175904 (patent document 2), suspension property remarkably falls in 20 degreeC and 40 degreeC both conditions in suspension property, and about 20 degreeC about particle aggregation property, An inhibitory effect was observed under both conditions at 40 ° C.

In Comparative Examples 27 and 28 prepared according to Japanese Patent Application Laid-Open No. 2007-77044 (Patent Document 3), both a suspension effect and a particle aggregation suppression effect were observed.
However, all the preparations of Comparative Examples 24-28 were inferior in both the suspension maintaining effect and the particle aggregation suppressing effect as compared to Examples 24-27 using the same agrochemical active ingredient.

  In addition, although Comparative Example 29 using urea having a chemical structure similar to guanidine as a substitute for water-soluble guanidines showed both a certain degree of suspension maintenance effect and particle aggregation suppression effect, guanidine hydrochloride was used. Compared to Example 27, the results were slightly inferior in any aspect of maintaining suspension and suppressing particle aggregation.

  From the results of Test Examples 1 and 2, it is indispensable to contain water-soluble guanidines to maintain suspension properties that can withstand long-term storage and to suppress particle aggregation. This indicates that the addition ratio is 0.1 to 2.5 times by weight, and that the water-soluble guanidine is guanidine hydrochloride or guanidine sulfamate is an advantageous condition in terms of cost and effect.

Claims (4)

  An aqueous suspension preparation comprising a) an agrochemical active ingredient, and b) guanidine or a water-soluble salt of guanidine. The water-soluble salt of guanidine is represented by the formula (I)

[In the formula (I), n represents an integer of 1 to 3, and when n = 1, X represents either HCl or HNO ₃ , NH ₃ SO ₃ , and when n = 2, X represents H _{2 represents} CO _3, and when n = 3, X represents H ₃ PO ₄ . The aqueous suspension preparation according to claim 1, wherein   2. The aqueous suspension preparation according to claim 1, wherein the water-soluble salt of guanidine is guanidine hydrochloride or guanidine sulfamate.   The aqueous suspension according to any one of claims 1 to 3, wherein the amount of the guanidine or the water-soluble salt of guanidine added to the pesticidal active ingredient is 0.1 to 2.5 times by weight. Suspended preparation.