MXPA06000676A - Aqueous suspension preparation of bactericide for folieage application - Google Patents

Abstract

It is intended to provide an aqueous suspension preparation of (RS)-N-[2-(1, 3-dimethylbutyl) thiophen-3-yl]-1 -methyl-3- trifluoromethyl-1H -pyrazole-4- carboxamide showing stable residual effectiveness while little affected by rainfall. An aqueous suspension preparation for foliage application, which is characterized by containing a bactericidal component (RS)-N-[2-(1, 3-dimethylbutyl) thiophen-3-yl]-1- methyl-3 -trifluoromethyl- 1H-pyrazole-4 -carboxamide together with a polyoxyalkyelne rosin acid ester or liquid paraffin, shows an improved rain resistance on foliage and excellent residual effectiveness.

Description

PREPARATION OF AQUEOUS FUNGICIDE SUSPENSION FOR APPLICATION TO FOLIAGE Field of the Invention The present invention relates to an aqueous suspension formulation for foliar application which is fungicidal and which contains an active fungicidal ingredient, (RS) -N- [2- (1,3-dimethylbutyl) thiophene-3 -yl] -1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, and an ester of polyoxyalkylene resin or liquid paraffin, and having improved rain resistance. Background of the Invention In recent years, the aqueous suspension formulations referred to as "flowable" formulations have become a mainstream of agrochemical formulations for foliar application. A major reason for this is that the aqueous suspension formulations do not cause the generation of dust and therefore, cause a small exposure of the worker to the powder, while the formulations such as wettable powders and powder formulations, they easily cause worker exposure to dust. On the other hand, the persistence of the effect of an active fungicidal ingredient often decreases during the foliar application period. Possible causes for this include the dilution of the active ingredient in the phylloplane, with the growth of the plants, the photodecomposition in the phylloplane and the washout of the active fungicidal ingredient of the phylloplane, due to rain. A fungicide that is not systemic easily suffers a decrease in residual effectiveness due to rain, because the applied active compound remains in the phylloplane without penetrating and transferring into the plant. Therefore, in order to maintain a previously determined fungicidal effect, an excess of agrochemical is applied to impose more labor and economic burden on a worker, thus causing environmental contamination. It is known that an active fungicidal ingredient, (RS) -N- [2-1,3-di methyl butyl) thiof in o-3-yl] -1 methyl-3-trif luoro metí 1-1 H-pirazol- 4-carboxamide used in the present invention exhibits an excellent effect in a wide variety of diseases (European Patent Application Publication No. 0737682). This active compound is insoluble in water and has a high melting point and an aqueous suspension formulation has been studied to use the compound for foliar application. However, only an aqueous suspension formulation produced by wet milling the compound in water is known simply by using a surfactant according to a general formula. In the application of a liquid medicine containing the compound comprised in the present invention to the plants, due to the rain the persistence of the effect subsequently decreased in an important way. In recent years, several means have been studied to avoid a decrease in the agrochemical effect due to rain. For example, Japanese Unexamined Patent Application Publication No. S54-80423 discloses agrochemical coating agents containing α-starch and therefore, have a high resistance to rain. Japanese Unexamined Patent Application Publication No. S59-172401 discloses moistening powders containing an added powdered resin to improve rain resistance. Japanese Unexamined Patent Application Publication No. H02-40301 discloses granules that can be dispersed in water containing polyvinyl alcohol or carboxymethyl cellulose aggregates to improve rain resistance by increasing the tendency to stick. Patent Application WO97 / 46092 discloses emulsions, aqueous suspension emulsions, wettable powders, suspensions and granules that can be dispersed in water, each containing sorbitan trioleate added to improve rain resistance.

However, when any of the materials described in the aforementioned documents or a commercially available general dispersing agent which function as an adjuvant for the active fungicidal ingredient of the present invention were used, no material was found to avoid ( improve the resistance to rain) a decrease in the persistence of the effect of the compound due to rain. [Patent Document 1] Japanese Unexamined Patent Application Publication No. S54-80423 [Patent Document 2] Unexamined Japanese Patent Application Publication No. S59-172401 [Patent Document 3] Japanese Patent Application Publication without Examination No. H02-40301 [Patent Document 4] Patent Application WO97 / 46092 [Patent Document 5] Publication of European Patent Application No. 0737682 Summary of the Invention An object of the present invention is to provide an aqueous suspension formulation containing an active fungicidal ingredient, (RS) -N- [2-1, 3-dimethylbutyl) thiophene-3-yl] -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide having an improved adhesion of the active ingredient in the phylloplane in the foliar application, and therefore, has an improved persistence of the effect of the active ingredient. As a result of the study to solve the problem described above, the inventors surprisingly discovered that among the known conventional dispersing agents, only a polyoxyalkylene resin ester or liquid paraffin can improve the rain resistance of the active agrochemical ingredient comprised in the present invention, leading to the achievement of the present invention. That is, an aqueous suspension formulation for application of a fungicide to the foliage of the present invention comprises an active fungicidal ingredient (RS) -N- [2- (1,3-dimethylbutyl) thiophene-3-yl] -1-methyl -3-trifluoromethyl-1 H -pyrazol-4-carboxamide and polyoxyalkylene resin acid ester or liquid paraffin. The present invention can provide an aqueous suspension formulation having improved rain resistance of the active ingredient (RS) -N- [2- (1,3-dimethylbutyl) thiophene-3-yl] -1-methyl-3 -tri fluoromet il-1 H-pyrazole-4-carboxamide in the phylloplane of the foliar application, and therefore, has an excellent residual effectiveness. Detailed Description of the Invention The present invention relates to an aqueous suspension formulation for the foliar application of a fungicide comprising an active fungicidal ingredient and a polyoxyalkylene resin acid ester or liquid paraffin added to improve the rain resistance. The active fungicidal ingredient (RS) -N- [2- (1,3-dimethylbutyl) thiophene-3-yl] -1-met l-3-tr-fluoro methyl-1 H -pyrazole-4-carboxamide, used in the present invention it is an effective compound for a variety of diseases, such as the powdery blight of the grape (Uncinula necator), the powdery blight of the apple (Podosphaera leucotricha), scab of the apple (Venturia inaequalis), alternating blotches of the apple (Alternaria mali), apple rust (Gymnosporangium yamadae), withered apple bud (Aclerotinia mali), black spot of the pear (Alternaria kikuchiana), pear rust (Venturia nashicola), rust pear ( Gymnosporangium haraeanum), brown peach rot (Sclerotinia cinerea), peach rust (Cladosporium carpophilum), powdery mildew of cucurbit (Sphaerotheca fuliginea), mold of tomato leaf (Cladosporium fulvam), powdery mildew of eggplant plant ( Erysiphe cichoracoarum), gray mold (Botrytis cinerea) and putrefac of sclerotinia or trunk rot (Sclerotinia sclerotiorum) in vegetables, such as cucumbers, tomatoes, strawberries and grapes. In the present invention, an auxiliary agent for imparting rain resistance to the fungicidal ingredient is the polyoxyalkylene resin or liquid paraffin acid ester. The polyoxyalkylene resin acid ester is produced by adding an alkylene oxide to a resin acid. Specific examples of the polyoxyalkylene resin acid ester include acid esters of polyoxyethylene resin obtained by the addition of ethylene oxide to the resin acids, esters of polyoxypropylene resin acid obtained by the addition of propylene oxide to the resin acids and acid esters of polyoxyethylene-polyoxypropylene resin obtained by adding ethylene oxides and propylene oxides to the resin acids. The polyoxyalkylene rosin acid esters are produced by adding alkylene oxides to the rosin acid in the resin acids. Examples of the polyoxyalkylene rosin acid esters include polyoxyethylene rosin acid ester obtained by the addition of ethylene oxide to the resin acids, polyoxypropylene rosin acid ester obtained by the addition of propylene oxide to the resin acids, and polyoxyethylene-polyoxypropylene rosin acid ester obtained by the addition of ethylene oxide and propylene oxide to the resin acids. Rosin acid is a diterpene monocarboxylic acid type acid, distributed in pine plants and containing abietic acid and pimaric acid as the main ingredients. Polyoxyalkylene rosin acid esters are commercially available, and for example, the DRA (produced by TOHO Chemical Industry Co., Ltd.) is a series that is available. In order to improve the rain resistance of the fungicidal ingredient according to the present invention, the polyoxyethylene resin acid esters and polyoxyethylene-polyoxypropylene resin acid esters between the polyoxyalkylene resin acid esters are preferred. , and the polyoxyethylene rosin acid ester and the polyoxyethylene-polyoxypropylene rosin acid ester are more preferred. In the present invention, among the polyoxyethylene resin acid esters, a polyoxy resin acid ester produced by the addition of 1 to 12 moles of ethylene acid per mole of resin acid is preferred to improve the resistance to rain of the fungicidal ingredient, and the most preferred is a polyoxyethylene rosin acid ester produced by the addition of 1 to 12 moles of ethylene oxide per mole of rosin acid. Among the polyoxyethylene-polyoxypropylene resin acid esters and the polyoxyethylene-polyoxypropylene rosin acid ester, the polyoxyethylene-polyoxypropylene resin acid ester and the polyoxyethylene-polyoxypropylene rosin acid esters each having a HLB (Hydrophilic-Lipophilic Balance), from 2 to 13 are preferred to improve the rain resistance of the fungicidal ingredient of the present invention, and the polyoxyethylene-polyoxypropylene rosin acid ester having an HLB of from 5 to 11 is the particularly preferred. In the present invention, HLB is generally used as a numerical value which indicates the hydrophilicity-hydrophobicity balance of a surfactant. The surfactant becomes insoluble to water being lipophilic when a HLB value is low, whereas a surfactant becomes water soluble in being hydrophilic when the HLB value is high. The HLB value used in the present invention is calculated by the following equation (1): (Equation 1) HLB = (molecular weight of the hydrophilic group / total molecular weight part) x (100/5) In this equation, the The molecular weight of the hydrophilic group part corresponds to the added molecular weight of the ethylene oxide. In order to achieve the effect of improving the rain resistance of the fungicidal ingredient of the present invention, the mixing amount of the polyoxyalkylene resin acid ester is generally in a range of 1 to 70 parts by weight regardless of the type of the alkylene group. In particular, during the use of the polyoxyethylene rosin acid ester or the polyoxyethylene-polyoxypropylene rosin acid ester, a suitable mixing amount is in the range of 10 to 50 parts by weight. With a minor mix amount of this range, the effect is unstable, while with a quantity of mixture higher than this range, the viscosity of the suspension increases and as a consequence, the physical properties of the suspension tend to degrade. Liquid paraffin exhibiting the same effect of polyoxyalkylene resin acid esters contains alkylnaphthenic hydrocarbons, as the main component, belongs to lubricants in view of their boiling point, and comprises a mixture of saturated liquid hydrocarbons with very high purity . Liquid paraffin is different from the materials we usually refer to as "normal paraffin" and "isoparaffin". In order to achieve the effect of improving the rain resistance of the fungicidal ingredient of the present invention, the mixing amount of the liquid paraffin in the formulation is generally in a range of 1 to 80 parts by weight, and preferably in the range of 20 to 60 parts by weight. Examples that can be used as liquid paraffin include CRYSTOL N52, CRYSTOL N72, CRYSTOL N82, CRYSTOL N122, CRYSTOL N172, CRYSTOL N262, CRYSTOL N352, and CRYSTOL 542 (produced by Exxon Mobile Co., Ltd.); COSMO WHITE P60, COSMO WHITE P70, COSMO WHITE P120, COSMO WHITE P200, COSMO WHITE P260, and COSMO WHITE 350, (produced by Cosmo Oil Lubricants Co., Ltd); Dufny Oil KP8, Dufny Oil KP15, Dufny Oil KP32, Dufny Oil KP68, Dufny Oil KP100, Dufny Oil CP12N, Dufny Oil CP15N, and Dufny Oil CP32N (produced by Idemitsu Kosan Co., Ltd); and MORESCO WHITE P60, MORESCO WHITE P100, MORESCO WHITE P120, MORESCO WHITE P230, and MORESCO WHITE P350P (produced by Matsumura Oil Research Corp.). However, liquid paraffin is not limited to these examples. The aqueous suspension formulation of the present invention can be produced by the following two methods: A first production method comprises: the mixture of the fungicidal ingredient of the present invention, the polyoxyalkylene resin ester or liquid paraffin, a surfactant, a water with exchanged ions, and if required, a foam removal agent and an antifreeze agent, wet the resulting mixture to a desired particle diameter, and then mixing the prepared mixture with an aqueous thickener solution containing an agent antiseptic to blast proof. A second production method comprises: the mixture of the fungicidal ingredient, a surfactant, and water with exchanged ions, and if required, a foam removal agent and an antifreeze agent, the wet milling of the resulting mixture to a particle diameter desired, and then further mixing the prepared mixture with an emulsion prepared separately from the polyoxyalkylene resin or liquid paraffin acid ester, a surfactant, and a water with exchanged ions, and an aqueous solution of thickener containing an antiseptic agent. blast test. In this method, the emulsion of the polyoxyalkylene resin acid ester or liquid paraffin may be prepared by a known method, such as a phase inversion emulsification method, or a mechanical emulsification method. Examples that can be used as the surfactant for the aqueous suspension formulation of the present invention include nonionic surfactants, such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, esters of polyoxyethylene fatty acid, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, polyoxyethylene castor oil, polyoxyethylene alkyl ethers, alkyl phenyl polyoxyethylene esters, dialkyl phenol polyoxyethylene esters, formalin condensates of alkyl phenyl ethers polyoxyethylene, polyoxyethylene-polyoxypropylene block polymers, alkyl polyoxyethylene-polyoxypropylene block polymer ethers, alkyl phenyl polyoxyethylene-polyoxypropylene block polymer esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, bisphenyl polyoxyethylene esters, benzyl phenyl polyoxyalkylene esters no, polyoxyalkylene styryl phenyl esters, and polyoxyalkylene adducts of higher alcohol, or polyoxyethylene ether, or ester type silicone, or fluorine surfactants composed of; anionic surfactants, such as alkyl sulphates, alkyl polyoxyethylene ether sulfates, alkyl phenyl polyoxyethylene ether sulfates, benzyl phenyl polyoxyethylene ether sulfates, styryl phenyl polyoxyethylene ether sulfates, polyoxyethylene-polyoxypropylene block polymer sulfates, paraffin sulfonates, sulfonates alkane, AOS, dialkyl sulfosuccinates, alkylbenzene sulfonates, naphthalene sulfonates, dialkyl naphthalene sulfonates, formalin condensates of naphthalene sulfonates, alkyl diphenyl ether disulfonates, lignin sulfonates, alkyl phenyl polyoxyethylene ether sulfonates, acidic esters polyoxyethylene alkyl ether sulphosuccinic, fatty acid salts, N-methyl fatty acid sarcosinates, resin acid salts, alkyl polyoxyethylene ether phosphate, phenyl polyoxyethylene ether phosphates, dialkyl phenyl polyoxyethylene ether phosphates, ether benzyl phosphates polyoxyethylene phenyl, ether phosphates polyphenylene phenyl polyoxyethylene, styryl phenyl polyoxyethylene ether phosphates, styryl phenyl phenyl polyoxyethylene ether phosphates, polyoxyethylene-polyoxypropylene block polymer phosphates, phosphatidylcholine, phosphatidyl ethanol imine and alkyl phosphates; polyanionic polymer surfactants derived from acrylic acid, acrylonitrile and acrylamidomethyl propanesulfonic acid; cationic surfactants such as alkyltrimethylammonium chloride, methyl chloride polyoxyethylene alkylammonium, N-methylpyridinium bromide alkyl, monomethylammonium chloride, dialquilmetilamonio chloride dichloride alquilpentametilpropilenoamina of alquildimetilbenzalconio benzatonio chloride and chloride; and ampholytic surfactants, such as dialkyldiaminoethyl betaine and alkyldimethylbenzyl betaine. However, the surfactant is not limited to these examples. Also, the antiseptic to test mildew agent such as 1, 2-benzisothiazolin-3-one, the agent defoaming as a silicone compound, the thickener such as xanthan gum and antifreeze agent such as propyleneglycol can be added, as occasion demands. Although the present invention will be described in more detail below with reference to the examples, the present invention is not limited to these examples. [Comparative Example 1] Five parts by weight of (RS) -N- [2- (1, 3-dimethylbutyl) thiophen-3-yl] -1-methyl-3-trifluoromethyl-1H-pyrazole-4 -carboxamide (which we refer to hereinafter as an "agent fungicidal active"), 5 parts by weight of sodium salt of a formaldehyde condensate of naphthalenesulfonic acid, 1 part by weight of aryl phenyl ether, polyoxyethylene 5 parts weight of propylene glycol, 0.1 parts by weight of a silicone-based foam remover, 0.2 parts by weight of xanthan gum and 83.7 parts by weight of water with exchanged ions were mixed to form a paste. Then, the resulting paste was milled in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous fungicidal suspension formulation.

[Comparative Example 2] Five parts by weight of the active fungicidal ingredient, 40 parts by weight of a polyoxyethylene rosin acid ester (number of moles of ethylene oxide added, 15), 5 parts by weight of sodium salt of the condensate of formaldehyde of naphthalenesulfonic acid, 1 part by weight of aryl phenyl polyoxyethylene ether, 5 parts by weight of propylene glycol, 0.1 part by weight of silicone-based foam removing agent, 0.2 parts by weight of xanthan gum and 43.7 parts by weight of Water with exchanged ions was mixed to form a paste. Then, the resulting paste was milled in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous fungicidal suspension formulation. [Comparative Example 3] Five parts by weight of the active fungicidal ingredient, 1 part by weight of aryl phenyl polyoxyethylene ether, 0.1 part by weight of silicone-based foam removing agent, and 13.7 parts by weight of water with exchanged ions were mixed to form a paste. Then, the resulting paste was milled wet in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous suspension. The resulting aqueous suspension was mixed with an emulsion to prepare an aqueous fungicidal suspension formulation. The emulsion was prepared by mechanical emulsification of 40 parts by weight of normal paraffin, 2 parts by weight of a polyanionic polymer surfactant (produced by Kao Corporation) and 38.2 parts by weight of water with ions exchanged with a Mark-Mixer. II (produced by Tokushu Kogyo Co., Ltd.). [Comparative Example 4] Five parts by weight of the active fungicidal ingredient, 1 part by weight of aryl phenyl polyoxyethylene ether, 0.1 part by weight of silicone-based foam removing agent, and 13.7 parts by weight of water with exchanged ions were mixed for form a paste. Then, the resulting paste was milled wet in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous suspension. The resulting aqueous suspension was mixed with an emulsion to prepare an aqueous fungicidal suspension formulation. The emulsion was prepared by mechanical emulsification of 40 parts by weight of soparaffin, 2 parts by weight of a polyanionic polymer surfactant (produced by Kao Corporation), and 38.2 parts by weight of water with ions exchanged with a Mark homo-mixer. -II (produced by Tokushu Kika Kogyo Co., Ltd.).

[Example 1] Five parts by weight of the active fungicidal ingredient, 40 parts by weight of polyoxyethylene rosin acid ester (number of moles of ethylene oxide added, 12), 5 parts by weight of sodium salt of formaldehyde condensate of naphthalenesulfonic acid, 1 part by weight of aryl phenyl polyoxyethylene ether, 5 parts by weight of propylene glycol, 0.1 part by weight of a silicone-based foam remover, 0.2 parts by weight of xanthan gum and 43.7 parts by weight of water with exchanged ones they were mixed to form a paste. Then, the resulting paste was milled in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous fungicidal suspension formulation. [Example 2] The same operation as in Example 1 was carried out to prepare an aqueous fungicidal suspension except that 40 parts by weight of a polyoxyethylene rosin acid ester (number of moles of ethylene oxide added: 6) were used. [Example 3] Five parts by weight of the active fungicidal ingredient, 1 part by weight of aryl phenyl polyoxyethylene ether, 0.2 part by weight of xanthan gum, 0.1 part by weight of a silicone-based foam remover and 33.7 parts by weight of water with exchanged ones were mixed to form a paste. Then, the resulting paste was milled wet in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.,) using 0.75 mm diameter glass beads to prepare an aqueous suspension. The resulting aqueous suspension was mixed with an emulsion to prepare an aqueous fungicidal suspension formulation. The emulsion was prepared by phase inversion emulsification of 40 parts by weight of polyoxyethylene rosin acid ester (number of moles of added ethylene oxide: 3), 2 parts by weight of aryl phenyl polyoxyethylene ether sulfate, parts by weight of polyoxyallyl ether polymer and 16 parts by weight of water with exchanged ions. [Example 4] The same operation as in Example 3 was performed to prepare the aqueous fungicidal suspension formulation except that 15 parts by weight of polyoxyethylene rosin acid ester (number of moles of ethylene oxide added: 3) was used. . [Example 5] Five parts by weight of the active fungicidal ingredient, 40 parts by weight of polyoxyethylene-polyoxypropylene rosin acid ester (number of moles of ethylene oxide added, 12; number of moles of propylene oxide added, 6) (HLB 9.1) 5 parts by weight of sodium salt of condensate of formaldehyde of naphthalenesulfonic acid, 1 part by weight of aryl phenyl polyoxyethylene ether, 5 parts by weight of propylene glycol, 0.1 part by weight of silicone-based foam removing agent, 0.2 parts by weight of xanthan gum and 43.7 parts by weight of water with exchanged ions were mixed to form a paste. Then, the resulting paste was milled in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous fungicidal suspension formulation. [Example 6] Five parts by weight of the active fungicidal ingredient, 1 part by weight of polyoxyethylene aryl phenyl ether, 0.2 parts by weight of xanthan gum, 0.1 parts by weight of silicone-based foam removing agent and 33.7 parts by weight of water with exchanged ions were mixed to form a paste. Then, the resulting paste was milled wet in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous suspension. The resulting aqueous suspension was mixed with an emulsion to prepare an aqueous fungicidal suspension formulation. The emulsion was prepared by phase inversion emulsification of 40 parts by weight of polyoxyethylene-polyoxypropylene rosin acid ester (number of moles of ethylene oxide added, 12, number of moles of propylene oxide added, 12) (HLB 7.0), 2 parts by weight of aryl phenyl polyoxyethylene ether sulfate, 2 parts by weight of polyoxyallyl ether polymer, and 16 parts by weight of water with exchanged ions. [Example 7] The same operation as in Example 6 was performed to prepare the aqueous fungicide suspension formulation, except that 40 parts by weight of polyoxyethylene-polyoxypropylene rosin acid ester (number of moles of ethylene oxide added) were used. , 3, number of moles of propylene oxide added, 3) (HLB 4.5). [Example 8] Five parts by weight of the active fungicidal ingredient, 1 part by weight of an aryl phenyl polyoxyethylene ether, 0.1 parts by weight of silicone-based foam removing agent, and 13.7 parts by weight of water with exchanged ions were mixed for form a paste. Then, the resulting paste was milled wet in a Dyno Mili KDL mill (produced by Shinmaru Enterprise Co.) using 0.75 mm diameter glass beads to prepare an aqueous suspension. The resulting aqueous suspension was mixed with an emulsion to prepare an aqueous fungicidal suspension formulation. The emulsion was prepared by mechanical emulsification of 40 parts by weight of liquid paraffin (trade name COSMO WHITE P70 (produced by Cosmo Oil Lubricants Co., Ltd.)), 2 parts by weight of polyanionic polymer surfactant (produced by Kao Corporation) , and 38.2 parts by weight of water exchanged with a Mark-II homo-mixer (produced by Tokushu Kika Kogyo Co., Ltd.). [Example 9] The same operation as in Example 1 was performed to prepare the aqueous fungicide suspension, except that 20 parts by weight of liquid paraffin was used (trade name COSMO WHITE P70 (produced by Cosmo Oil Lubricants Co., Ltd.) ). [Example 10] The same operation as in Example 1 was performed to prepare the aqueous fungicide suspension, except that 40 parts by weight of liquid paraffin was used (trade name MORESCO WHITE OIL P230 (produced by Matsumura Oil Research Corp.)). [Test Example 1] Evaluation of rain resistance The aqueous fungicide suspension formulation prepared in each of Comparative Examples 1 to 4 and examples 1 to 10 was diluted with tap water, so that the concentration of the active fungicidal ingredient was 100 ppm. Then, the application to the foliage was carried out in such a way that 40 ml of the diluted solution per pot of two bean plants (cotyledon stage) in each of the two pots, then the cotyledon leaves of the bean plants were sprinkled. One day later, 20 ml of rain was applied during 20 minutes of an artificial rain forming device. After drying in the air, six leaves of the cotyledon were cut, and the surface area of each leaf was measured by an AREA METER mk2 meter (produced by DELTA-T DEVICES LTD). Then, the leaves were immersed in 75% methanol for 1 minute to extract the chemical, and the extract was filtered with gauze and a syringe filter of 0.45 μm to prepare a sample. The deposition of the active fungicidal ingredient in the leaves was measured by high performance liquid chromatographic analysis under the following conditions, and the residual proportion was calculated according to the calculation equation (2) below. The results are shown in table 1. (Equation 2) Residual proportion = (deposition of the active fungicidal ingredient after rain / deposition of active fungicidal ingredient before rain) x 100 HPLC conditions Mobile phase; methanol: water = 75:25 (v / v) Wavelength; 250 nm Flow range; 1.0 ml / min. Column; Water Symmetryshild RP 8.5 μ, diameter 4.6 mm, length 250 mm Pump; LC-6A produced by Shimadzu Corporation Detector; SPD-6A produced by Shimadzu Corporation Table 1 [Test Example 2] Effect on the gray mold of the bean Two bean plants were planted in a pot having a diameter of 7.5 cm. Eighty milliliters of the aqueous suspension formulation prepared in each of Examples 1, 3, 5, and 8 were applied by four plastic pots to the leaves of the bean cotyledon (from kidney bean, "green" varieties, leaves). cotyledon separated). One day later, 20 mm rain was applied for 1 hour from an artificial rain apparatus. After drying in the air, the leaves of the cotyledon of the bean plant were cut and placed in a closed container (a 9 cm diameter ice cup) with a moistened filter paper content. On the other hand, a spore suspension with a content of 1x106 / ml spores of gray mold fungi (Botrytis cinerea) was prepared, and an 8 mm diameter filter paper was impregnated with the spore suspension that was placed on the leaves of the bean for inoculation. After the leaves were allowed to remain at a temperature of 20 ° C for 4 days in the dark, the diameter of the spot was measured to determine a preventive value according to the equation (Equation 3). The results are shown in Table 2. (Equation 3) Preventive value = (diameter of the spot in the untreated region - diameter of the spot in the treated region) / diameter of the spot in the untreated region x 100. Table 2 Tables 1 and 2 indicate that the foliar application of the fungicidal suspension of the present invention containing polyoxyethylene rosin acid ester, polyoxyethylene-polyoxypropylene rosin acid ester having a HLB of 2 to 13, or liquid paraffin , the resistance to rain is significantly improved, compared to the application to the foliage of the suspension that does not contain the polyoxyethylene rosin acid ester, polyoxyethylene-polyoxypropylene rosin acid ester having a HLB value of 2. to 13, or liquid paraffin.

Claims (6)

1. CLAIMS 1. An aqueous fungicide suspension formulation for foliar application, comprising an active fungicidal ingredient, (RS) -N- [2- (1,3-dimethylbutyl) thiophene-3-yl] -1-methyl- 3-trifluoromethyl-1 H-pyrazole-4-carboxamide, and an ester of polyoxyalkylene resin or liquid paraffin.
2. 2. The aqueous fungicidal suspension formulation for foliar application as described in claim 1, characterized in that the polyoxyalkylene resin acid ester is a polyoxyethylene resin acid ester or a polyoxyethylene resin acid ester. -polyoxypropylene.
3. 3. The aqueous fungicidal suspension formulation for foliar application as described in claim 2, characterized in that the polyoxyethylene resin acid ester or polyoxyethylene-polyoxypropylene resin acid ester is an acid ester of polyoxyethylene rosin or a polyoxyethylene-polyoxypropylene rosin acid ester.
4. 4. The aqueous fungicidal suspension formulation for foliar application as described in claim 3, characterized in that the average number of moles of ethylene oxide added to the polyoxyethylene rosin acid ester is from 1 to 12 per cent. mole of rosin acid.
5. 5. The aqueous fungicidal suspension formulation for foliar application as described in claim 3, characterized in that the polyoxyethylene-polyoxypropylene rosin acid ester has an HLB value of 2 to 13 calculated according to the following equation: (Equation 1) HLB = (molecular weight of the hydrophilic part / total molecular weight) x (100/5).
6. 6. The aqueous fungicidal suspension formulation for foliar application as described in claim 1, which comprises from 1 to 70 parts by weight of polyoxyalkylene resin acid ester or from 1 to 80 parts by weight of liquid paraffin.