JPH10310501A - Package of aqueous suspension formulation and its dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject package without causing deformation and deterioration of a vessel during preservation, excellent in delivery properties of a formulation from the package, and capable of allowing the used empty vessel to be readily disposed by packing a specific aqueous suspension formulation in the water-impermeable paper vessel. SOLUTION: This package of aqueous suspension formulation is obtained by packing (A) an aqueous suspension formulation comprising (i) 0.1-60 wt.% agrochemical active ingredient such as a herbicidal component, a microbicidal component and an insecticidal component, (ii) 0.1-20 wt.% protective colloidal agent such as a polyvinyl alcohol and methylcellulose, (iii) 0.1-10.0 wt.% thickener such as a heteropolysaccharide and a starch derivative, (iv) 30-95 wt.% water, (v) optionally 1-60 wt.% high boiling point solvent, an antifoamer, an antifreezing agent, an antiseptic and fungicidal agent, a stabilizer of the agrochemical active ingredient, etc., and having 200-1000 mPa.s viscosity (at 20 deg.C) and 2-10 SVI value, in (B) a water impermeable paper vessel preferably having 5-10 cm maximum diameter, and 1-10 fine holes having 1-10 mm inner diameters and covered with a peelable sealing material when preserving.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous suspension preparation package for direct application in a flooded sewage paddy field, which can be directly applied and the used medicine container can be easily disposed of, and a method of application using the same. .

[0002]

2. Description of the Related Art As a method for controlling weeds in a flooded sewage paddy field, an aqueous suspension formulation for direct application in which an active ingredient of pesticide is suspended and dispersed in water is placed in a synthetic resin container and shaken by hand. There is a method of spraying in Tanaka.

[0003] As such an aqueous suspension formulation for direct application, for example, an aqueous suspension formulation in which a herbicide base material having a water solubility of 100 ppm (25 ° C) or less is suspended and dispersed in water using a surfactant. Japanese Patent Publication No. 7-47521), 10 μm
The following finely water-insoluble herbicidal active ingredient is suspended in water, has a viscosity of 180 to 500 centipoise (20 ° C.), an initial water surface spreading speed of 4.0 cm / sec (20 ° C.) or more, and a surface tension of 25. Water-suspended paddy field herbicide having physical properties of 0 to 31.0 dyne / cm (25 ° C.) (JP-A-62-8762)
No. 501), a herbicidally active compound having an average particle size of 0.5 to 5.0 μm and a water solubility of 100 ppm (25 ° C.) or less is suspended in water using a surfactant, and the surface tension is 36 to 50 μm.
Herbicidal aqueous suspension preparations having physical properties of 65 dyne / cm (25 ° C.) (JP-B-7-47522).

[0004] However, all the containers for direct application filled with these aqueous suspension preparations are made of synthetic resin. Deformation, the formulation does not discharge even if the container is shaken during use due to the viscosity of the formulation increasing over time,
There has been a problem that the discharge amount is non-uniform and uneven distribution occurs. Deformation of the container can be avoided to some extent by increasing the amount of synthetic resin to increase the deformation resistance, but when the amount of synthetic resin is increased, the container is likely to deteriorate. Further, containers made of synthetic resin are not easily decomposed by microorganisms or the like, and when incinerated in an incinerator, the amount of heat of the resin is large.

On the other hand, JP-A-8-140552 discloses a labor-saving spraying method in which an agricultural chemical formulation such as an aqueous suspension formulation is placed in a paper container and directly dropped from a fine hole provided in the container into a flooded sewage paddy field. Have been described. However, the ejection property of the preparation from the pores of the paper container is not always satisfactory. Also, a paper container having a plurality of small holes through which a liquid can be poured out in a shower shape is known (Japanese Patent Application Laid-Open No. 5-162747).

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a container which is free from deformation and deterioration during storage, has a good discharge property even when dropped directly from a container filled with an aqueous suspension preparation, and has been used. It is an object of the present invention to provide an aqueous suspension preparation package suitable for labor-saving spraying in a flooded sewage field where empty containers can be easily disposed of.

[0007]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems. As a result, it is composed of pesticidal active ingredient, protective colloid, thickener and water.
An aqueous suspension formulation having a viscosity at 0 ° C. of 200 to 1000 mPa · s and an SVI value of 2 to 10 or an aqueous suspension formulation obtained by adding a high boiling point solvent to the formulation is placed in a non-water-permeable paper forming container. By filling, the package was not deformed, and it was found that the preparation had excellent dischargeability from the package, thus completing the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Containers formed of impermeable paper which can be used in the present invention are as follows. First, the material of the water-impermeable paper is not particularly limited as long as the aqueous suspension preparation or water does not leak to the outer surface of the container during transportation, storage or spraying. Examples include paper-based polyethylene, polypropylene,
There is no problem with laminating a resin such as polyester or eval or a film such as aluminum, or using a paper base on which a resin or aluminum such as polyethylene, polypropylene, polyester or eval is deposited, or a paraffin or wax coating. There is no. Further, the shape of the molded container is not particularly limited, for example, milk, soft drinks, cubes in the form of paper packs widely used as containers for sake, etc. And various other types can be used. A shape that is easy to hold with one hand and easy to shake and spread over rice fields is desirable. For this purpose, the cube, cylinder, triangular prism, etc. should be provided with some irregularities on the part to be gripped by hand so that they do not slip (for example, glue a few mm thick paper to the outside of the container in a belt shape). It is also preferable to do so. In addition, in order to make it easy to spray, it is good that the container can be easily gripped with one hand, and the maximum diameter is 5 to 10 cm.
Something is good.

[0009] Further, in order to spray the aqueous suspension formulation, it is necessary to provide pores at the upper portion of the container as discharge holes for these drugs, and the number of pores is 1 to 10, preferably 3 to 10.
About six are good. The inner diameter is 1 to 10 mm, preferably 1.5 to 5 mm. Further, it is desirable to cover the pores with a peelable sealing material in order to prevent liquid leakage during storage. Instead of directly drilling into the paper container, it is also possible to join a resin plug having a discharge plug.

The amount of the agricultural chemical formulation of the present invention to be applied to the paddy field depends on the kind and content of the active agricultural chemical.
It may be sprayed in the range of 00 g or 100 to 1000 ml, preferably in the range of 200 to 500 ml.

The pesticidal active ingredient that can be used in the present invention is not particularly limited, but includes those conventionally used as pesticides for paddy fields.

For example, as the herbicidal active ingredient, 2,4-
D, MCP, MCPB, phenothiol, clomeprop, naproanilide, CNP, clomethoxynil, bifenox, MCC, benthiocarb, esprocarb, molinate, dimipeperate, DCPA, butachlor, pretilachlor, bromobutide, mefenacet, dimelone, simethrin, dimethazone, dimethazone, dimethazone, dimethazone , Pyrazolate,
Pyrazoxifene, benzofenap, trifluralin, piperophos, butamiphos, DCBN, ACN, methyl = α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -o-toluate (bensulfuronmethyl), ethyl = 5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)
-1-methylpyrazole-4-carboxylate (pyrazosulfuronethyl), 1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3-
(4,6-dimethoxypyrimidin-2-yl) urea
(Imazosulfuron), 1H-pyrazol-5-sulfonamide, N-(((4,6-dimethoxypyrimidin-2-yl) aminocarbonyl))-1-methyl-4
-(2-methyl-2H-tetrazol-5-yl) (azimsulfuron), 1-{[0- (cyclopropylcarbonyl) phenyl] sulfamoyl} -3- (4,6
-Dimethoxy-2-pyrimidinyl) urea (AC-14
0), N- (2-chloroimidazole [1,2-a] pyridin-3-yl-sulfonyl) -N '-(4,6-
Dimethoxy-2-pyrimidyl) urea (TH-91
3), 3- (4,6-dimethoxy-1,3,5 triazin-2-yl) -1- [2- (2-methoxyethoxy)
Phenylsulfonyl] -urea (cinosulfuron), 3
-(4,6-dimethoxypyrimidin-2-yl) -1-
(2-Ethoxyphenoxysulfonyl) urea (ethoxysulfuron), tenylchlor, dithiopyr, piperophos, symmethylin, pyributicarb, 3- [4-chloro-5- (cyclobentyloxy) -2-fluorophenyl] -5-isopropylidene -Oxazolidine-
2,4-dione (KPP-314), [R-(+)-n
-Butyl-2- (4- (2-fluoro-4-cyanophenoxy) phenoxy) propionate (cyhalofop-butyl), N, N-diethyl-3-mesitylsulfonyl-1H-1,2,4- Triazole-1-carboxamide (CH-900), S (N (4-chlorophenyl)
-N-isopropylcarbamoylmethyl) -O, O-dimethyldithiophosphate (anilophos), methyl = 2-[(4,6-dimethoxypyrimidin-2-yl)
Oxy] -6- [1- (methoxyimino) ethyl] benzoate (KUH-920), 2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethylindane-1,3 -Zeon (MK-243), 4-
(2-chlorophenyl) -N-cyclohexyl-4,5
-Dihydro-N-ethyl-5-oxo-1H-tetrazol-1-carboxamide (NBA-061), 3
-[1- (3,5-Dichlorophenyl) -1-methylethyl] -2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (MY-10
0), 3- [2,4-dichloro-5- (2-propynyloxy) phenyl] -5- (1,1-dimethylethyl)
-1,3,4-oxadiazol-2 (3H) -one (oxadialgyl).

The bactericidal active ingredients include, for example, inorganic copper, organic nickel, thiuram, fusalide, IBP, EDD
P, thiophanate methyl, benomyl, iprodione,
Mepronil, Flutolanil, Teclophthalium, Pencyclon, Metalaxyl, Triflumizole, Prochloraz, Pefurazoate, Blasticidin S, Kasugamycin, Polyoxin, Validamycin, Hydroxyisoxazole, Metasulfocarb, Organic arsenical, Benthiazole, Diclomedine, Ferimzone, Probenazole , Isoprothiolane, tricyclazole, oxolinic acid, and the like.

As the insecticidally active ingredient, for example, MP
P, MEP, diazinon, isoxathion, pyridafenthion, chlorpyrifosmethyl, bamidion, marathon, PAP, dimethoate, ethyl thiomethone, P
MP, monocrotophos, BRP, CVMP, dimethylvinphos, propaphos, acephate, DEP, EPN,
NAC, MTMC, MIPC, BPMC, PHC, MP
MC, XMC, carbosulfan, benfracarb, mesomil, thiodicarb, cycloprotoline, etofenprox, cartap, thiocyclam, bensultap, buprofezin, pyrethrin and the like.

The names of these compounds are common names described in "Agrochemical Handbook 1994 Edition" (published by the Japan Plant Protection Association). These herbicidal active ingredients, fungicidal active ingredients, and insecticidal active ingredients can be used alone or in combination of two or more, and can be used in combination with the fungicidal and / or insecticidal active composition part and the herbicidal active ingredients. The content of the pesticidal active ingredient in the preparation can be arbitrarily changed depending on the kind of the pesticidal active ingredient, but is in the range of 0.1 to 60% by weight in the preparation.

The protective colloid agent usable in the present invention includes:
For example, in addition to polyvinyl alcohol, gum arabic, gelatin, albumin, water-soluble cellulose ethers such as hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, water-soluble soybean polysaccharides (trade name: Soyafive), sodium alginate, etc. But polyvinyl alcohol, hydroxypropylcellulose, methylcellulose and hydroxypropylmethylcellulose are preferred.

The above-mentioned polyvinyl alcohol may have an average degree of polymerization of 2,000 or less and a degree of saponification of 69 to 90 mol%, for example, Kuraray Povar PVA-405.
(Kuraray Co., Ltd., average polymerization degree 500, saponification degree 80-83 mol%), Kuraray Povar PVA-210
(Kuraray Co., Ltd., average polymerization degree 1000, saponification degree 87-89 mol%), Kuraray Povar PVA-42
0 (trade name of Kuraray Co., Ltd., average degree of polymerization 2000, saponification degree 78-81 mol%), Kuraray Povar L-8 (trade name of Kuraray Co., Ltd., average degree of polymerization 1000 or less, saponification degree 69.5-6.5) 72.5 mol%).

The above-mentioned methylcellulose and hydroxypropylmethylcellulose are those in which two of three OH groups in one glucose residue contained in cellulose are substituted with a methoxy group, and a methoxy group is contained in the molecule. 2
It refers to methylcellulose containing 7 to 32% by weight, or hydroxypropylcellulose in which a part of the methoxy group of methylcellulose is further substituted with a hydroxypropoxy group. For example, as methylcellulose, a trade name “MARPOLOWS M” of Matsumoto Yushi Seiyaku Co., Ltd. (methoxy group substitution rate 27.5 to 31.5%, thermal gelation temperature 50 to 5)
5 ° C), Shin-Etsu Chemical Co., Ltd.
M "(methoxy group substitution rate: 27.5-31.5%, thermal gelation temperature: about 52 ° C.) and the like. ~ 30
%, Hydroxypropoxy group substitution rate 7 to 12%, thermal gelation temperature 58 to 64 ° C), "MARPOROS 65MP" (methoxy group substitution rate 27 to 30%, hydroxypropoxy group substitution rate 4 to 7.5%, hot gel Formation temperature 62-68 ° C),
"MARPOROS 90MP" (Methoxy group substitution rate 19-2
5%, hydroxypropoxy group substitution rate 4-12%, thermal gelation temperature 70-90 ° C.), “MARPOROS MP” (methoxy group substitution rate 16.5-20%, hydroxypropoxy group substitution rate 60-70%, heat Gelation temperature of 60 to 70 ° C.).

There is no problem if one or more of these protective colloids are used in combination. The content of the protective colloid in the preparation is 0.1 to 20% by weight, preferably 0.5 to 20% by weight.
１５15% by weight.

The thickener used in the present invention is not particularly limited, and may be any commonly used one. Examples thereof include heteropolysaccharides such as xanthan gum, welan gum and ramzan gum, dextrin,
Starch derivatives such as starch phosphate, tragacanth gum, casein, colloidal hydrated aluminum silicate, colloidal hydrated magnesium silicate, colloidal hydrated aluminum / magnesium silicate, silicon dioxide and the like, but are not limited thereto. There is no problem even if one or more of these are used in combination. The thickener may be added at 0.1 to 10.0% in the preparation.

SVI (Structural Visc)
Osity Index (structural viscosity index) value is a measure of the non-Newtonian nature of a liquid, and is a value obtained by measuring the viscosity while changing the shear rate and dividing the viscosity at the lower shear rate by the viscosity at the higher shear rate. . A simple measurement method using a B-type viscometer is shown in an SVI value test in a reference test of Japanese Industrial Standard JIS K 7117, and the measurement can also be performed by this method. However, in the method using a B-type viscometer, the shear rate cannot be increased continuously and linearly with respect to time, and two kinds of shear rates must be measured with the same spindle. For this reason, it is desirable to use a measuring instrument such as a stress detection type rheometer that can change the shear rate continuously and linearly with time.

However, the viscosity and the SVI value are not uniquely determined by the type of the thickener, but depend on the type and amount of the pesticidal active ingredient, the protective colloid, and the thickener. The viscosity of the aqueous suspension formulation (25 ° C.) is 200
１０００1000 mPa · s and SVI value is 2２10
, A uniform discharge property can be obtained from the start to the end of spraying.

The water content in the aqueous suspension preparation is from 30 to 95.
%, Preferably 50 to 90% by weight.

If necessary, as an auxiliary agent, for example,
An antifoaming agent, an antifreezing agent, a preservative and antibacterial agent, and a pesticide active ingredient stabilizer can be used.

For example, antifoaming agents include silicon-based and fatty acid-based substances; antifreezing agents such as ethylene glycol, propylene glycol and glycerin; and antiseptic and antibiotic agents such as sorbic acid, potassium sorbate, p
As a stabilizer for the pesticidal active ingredient such as -chloro-metaxylenol and p-butyl benzoate, an antioxidant, an ultraviolet ray inhibitor, a crystal precipitation inhibitor and the like may be added. It is not limited to agents.

The specific gravity of the aqueous suspension preparation of the present invention at 20 ° C. is not particularly limited, but is in the range of 0.9 to 1.10 in consideration of the diffusivity in a paddy field after application, but is outside this range. In this case, the specific gravity can be adjusted to a preferable range by adding a high boiling point solvent. In the case of a pesticidal active ingredient having a low melting point, by dissolving it in a high-boiling solvent, the pesticidal active ingredient does not become liquefied or crystallized, or the suspension stability of the preparation does not deteriorate. In the case of a pesticidal active ingredient which is liquid at ordinary temperature, the liquid pesticidal active ingredient is dissolved in a high-boiling-point solvent and emulsified and dispersed, or separately emulsified and dispersed in water to prevent decomposition of the active ingredient and suspend the formulation. A formulation with good stability can be obtained. Examples of the high boiling point solvent that can be used in the present invention include Solvesso 150
(Trade name of Exxon Chemical Co., Ltd.), Hisol E, Hisol F (trade name of Nippon Petrochemical Co., Ltd.), Cactus Solvent P100, Cactus Solvent P150,
Cactus Solvent P187, Cactus Solvent P2
00 (trade name of Nippon Mining Co., Ltd.), Alken 56N,
Alkylbenzene solvents such as alkene 60NH, alkene L (trade name of Nippon Petrochemical Co., Ltd.), Cactus Solvent 220, Cactus Solvent P240 (trade name of Nippon Mining Co., Ltd.), Solvesso 200 (trade name of Exxon Chemical Co., Ltd.), Purified methylnaphthalene (manufactured by Sumitomo Chemical Co., Ltd.), alkylnaphthalene solvents such as diisopropylnaphthalene, paraffin solvents such as isoparaffin, liquid paraffin, and n-paraffin, naphthesol (manufactured by Nippon Petrochemical Co., Ltd.), Exssol (Exxon Chemical Co., Ltd.) Trade name), ether solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether;
Alcohol solvents such as methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, and 3-methyl-1,3-butanediol; alkyls such as N-methylpyrrolidone, n-octylpyrrolidone, and n-dodecylpyrrolidone A pyrrolidone solvent, DuPont DBE (manufactured by DuPont), ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, didecyl phthalate, dialkyl phthalate (C10-C12), trinormal alkyl trimellitate (C8-C10),
Polybasic ester solvents such as tri-2-ethylhexyl trimellitate, trialkyl trimellitate (C9), triisodecyl trimellitate, dioleyl adipate, isobutyl oleate, methyl cocoate, methyl laurate, methyl methyl palmate Fatty acid esters such as isopropyl palmitate, isotridecyl stearate, 2-ethylhexyl stearate, methyl oleate, octyl oleate, lauryl oleate, decyl oleate, Hisol SAS-296, Hisol SAS-LH (Nippon Petrochemical Co., Ltd.) Company), etc.
Vegetable oil fatty acid esters such as rice bran oil fatty acid methyl ester, soybean oil fatty acid methyl ester, rapeseed oil, soybean oil, castor oil, cottonseed oil, and vegetable oils such as corn oil, but are not limited thereto. There is no problem even if one or more of these are used in combination. The content of the high boiling solvent in the preparation is 1 to 60% by weight, preferably 5 to 50% by weight.

The package of the aqueous suspension preparation of the present invention can be used irrespective of the water depth, as long as the paddy field after the sublimation operation is in a flooded state. In other words, from the state where a slight water layer exists on the soil surface, such as when planting rice, to the state where a water depth of 5 to 3 cm is spread over the entire paddy field, it is possible to spray unless the soil surface is completely dry. It can also be used at the time of irrigation water input. It may be under low water conditions at the time of rice planting, such as dropping treatment at the same time as rice planting, and if treated, the pesticide active ingredient diffuses to some extent, becomes more uniform by subsequent water entry, and exhibits a sufficient herbicidal effect be able to.

The package of the aqueous suspension preparation of the present invention can be sprayed at any time before transplanting, at the time of transplanting, or after transplanting, and can be applied to directly flooded rice.

Spraying with the aqueous suspension preparation package of the present invention is used without diluting the undiluted solution into more water, but it is not necessary to spray uniformly over the entire paddy field as in the case of granules. Spraying may be performed by shaking the aqueous suspension formulation package of the present invention from the ridge as it is, or by inverting the package and holding the pores downward to drop the package. Further, when the irrigation water flows, the inflow water may be dropped at the water intake (water mouth) of the paddy field, and may be poured into the paddy field together with the inflow water.

[0030]

EXAMPLES Next, examples of the aqueous suspension preparation package for direct application of a flooded sewage paddy field of the present invention will be described, but the present invention is not limited thereto. In addition, all the parts in an Example show a weight%.

Example 1 An average degree of polymerization of 500 and a degree of saponification of 80 in 70.4 parts of water.
0 to 83.0 mol% of polyvinyl alcohol (trade name "Kuraray Poval PVA-405" Kuraray Co., Ltd.) 2
And 3 parts of propylene glycol, and 12 parts of the oxadiazon drug substance, 0.1 part of p-chloro-metaxylenol and 0.5 part of colloidal hydrous aluminum silicate were added thereto.
A. (Bachofen AG) so that the average particle diameter of the pulverized liquid was 2 μm.

The crushing medium has a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. 12 parts of a 2% aqueous xanthan gum solution was added to the pulverized liquid, and the mixture was uniformly mixed using a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation. Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. Impermeable paper made by laminating polyethylene film, paper, polyethylene film, aluminum foil, polyethylene terephthalate film, and polyethylene film in this order is molded into a cube of 5 x 6 x 18 cm, and six pores with a diameter of 2.5 mm are formed on the upper surface. This container is filled with 500 ml of the above aqueous suspension preparation, and this part is covered with a peelable sealing material in which a polyethylene film and an aluminum foil are laminated.
The container was sealed to obtain an aqueous suspension formulation package.

Example 2 2 parts of Marpolose M-25 (methyl cellulose having a methoxy group substitution rate of 27.5 to 31.5%, trade name of Matsumoto Yushi Seiyaku Co., Ltd.) and 3 parts of propylene glycol were dissolved in 70.1 parts of water. And 12 parts of the oxadiazon drug substance, p
0.1 parts of -chloro-metaxylenol and 0.3 parts of colloidal hydrous magnesium silicate were added, and the mixture was finely pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid was 2 µm.

The crushing medium has a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. 12.5 parts of a 2% welan gum aqueous solution was added to the pulverized liquid, and the mixture was uniformly mixed using a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation. The viscosity of this aqueous suspension formulation, SVI
The values are shown in Table 1. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Example 3 In 72.4 parts of water, Marpolose 65MP-400 (hydroxypropyl methylcellulose having a methoxy group substitution rate of 27 to 30% and a hydroxypropoxy group substitution rate of 4 to 7.5%) was used.
2 parts of Matsumoto Yushi Pharmaceutical Co., Ltd.) and 3 parts of propylene glycol are dissolved, and oxadiazon drug substance 1
2 parts, 0.1 part of p-chloro-metaxylenol and 0.5 part of silicon dioxide were added, and the mixture was pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid was 2 μm.

The media for crushing had a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. 10 parts of a 2% aqueous ramzan gum solution was added to the pulverized liquid, and the mixture was uniformly mixed using a three-one motor to obtain an aqueous suspension preparation. Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. Example 1
Fill the same paper container with 500 ml of the above aqueous suspension formulation,
The container was sealed to obtain an aqueous suspension formulation package.

Example 4 Polyvinyl alcohol having a saponification degree of 87.0 to 89.0 mol% (trade name "Kurarepovar PVA") was added to 60.4 parts of water.
-210 "Kuraray Co., Ltd.) 1 part and propylene glycol 3 parts are dissolved therein,
0.1 part of p-chloro-metaxylenol and 0.5 part of colloidal hydrous aluminum / magnesium silicate were added, and the mixture was finely pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid was 2 μm.

The crushing medium has a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. A 2% aqueous solution of carboxymethylcellulose (trade name “CMC Daicel 1170”, Daicel Chemical Industries, Ltd.) 3
0 parts were added and uniformly mixed using a three-one motor to obtain an aqueous suspension formulation. The viscosity of this aqueous suspension formulation, SVI
The values are shown in Table 1. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Example 5 Marporose 60MP-50 (hydroxypropyl methylcellulose having a methoxy group substitution ratio of 28 to 30% and a hydroxypropoxy group substitution ratio of 7 to 12%, trade name of Matsumoto Yushi Seiyaku Co., Ltd.) in 66.7 parts of water 3 And 3 parts of propylene glycol were dissolved, and a solution of 4.2 parts of a phenothiol drug substance dissolved in 20 parts of alkylbenzene (trade name: “Solvesso 150” manufactured by Exxon Chemical Co., Ltd.) in advance was mixed with p-chloro-metaxylenol. 0.1 part and 3 parts of colloidal hydrous magnesium silicate were added, and finely pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid became 3 μm, to obtain a uniform aqueous suspension preparation.

The crushing medium has a diameter of 1.5.
Hard glass beads of ２．０2.0 mm were used. Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Example 6 The average degree of polymerization was 500 and the degree of saponification was 72.
5 to 74.5 mol% of polyvinyl alcohol (trade name “Kuraray Poval PVA-505” Kuraray Co., Ltd.) 2
And 3 parts of propylene glycol were dissolved, 5 parts of the raw material of terenylchlor, 0.1 part of p-chloro-metaxylenol and 8 parts of liquid paraffin were added, and the average particle diameter of the pulverized liquid was 2 μm using Dynomill KDL type. Was finely ground.

The crushing medium has a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. To this pulverized liquid, 25 parts of a 10% aqueous starch phosphate solution was added and uniformly mixed using a three-one motor to obtain an aqueous suspension preparation.
Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

COMPARATIVE EXAMPLE 1 Using 57.9 parts of water of Example 6, and replacing 25 parts of a 10% aqueous starch phosphate solution with 24 parts of an aqueous solution of 5% carboxymethylcellulose (trade name "CMC Daicel 1590", Daicel Chemical Industries, Ltd.) An aqueous suspension preparation was obtained by the same composition and operation as in Example 6 except that Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Comparative Example 2 In 79.9 parts of water, Marpolose 65MP-400 (hydroxypropyl methylcellulose having a methoxy group substitution rate of 27 to 30% and a hydroxypropoxy group substitution rate of 4 to 7.5%) was used.
2 parts of Matsumoto Yushi Pharmaceutical Co., Ltd.) and 3 parts of propylene glycol are dissolved, and oxadiazon drug substance 1
2 parts, 0.1 part of p-chloro-meta-xylenol and 3 parts of colloidal hydrous magnesium silicate are added, and finely pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid becomes 3 μm, and a uniform aqueous suspension is added. A cloudy formulation was obtained.

The media for crushing has a diameter of 1.5.
Hard glass beads of ２．０2.0 mm were used. Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Comparative Example 3 An aqueous suspension preparation was obtained by the same composition and operation as in Example 2 except that 57.6 parts of water and 25 parts of 12.5 parts of a 2% welan gum aqueous solution were used. Table 1 shows the viscosity and SVI value of this aqueous suspension preparation. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Comparative Example 4 Polyvinyl alcohol having a saponification degree of 87.0 to 89.0 mol% (trade name “Kuraray Poval PVA”) was added to 75.7 parts of water.
-210 "Kuraray Co., Ltd.) and 1 part of propylene glycol were dissolved, and 5 parts of the original terenylchlor, 0.1 part of p-chloro-metaxylenol and 0.2 part of colloidal hydrous aluminum silicate were added. The pulverized liquid was finely pulverized using a Dynomill KDL type so that the average particle diameter of the pulverized liquid was 2 μm.

The crushing medium has a diameter of 0.7.
Hard glass beads of １．２1.2 mm were used. A 2% aqueous solution of carboxymethylcellulose (trade name “CMC Daicel 1170”, Daicel Chemical Industries, Ltd.) 1
Five parts were added and mixed uniformly using a three-one motor to obtain an aqueous suspension formulation. The viscosity of this aqueous suspension formulation, SVI
The values are shown in Table 1. The same paper container as in Example 1 was filled with 500 ml of the above aqueous suspension preparation, and the container was sealed to obtain an aqueous suspension preparation package.

Comparative Examples 5 to 10 500 ml of the aqueous suspension preparation obtained in Examples 1 to 6
It was placed in a 1-volume polyethylene bottle (weight 40 g). The bottle was provided with a polyethylene inner plug provided with six 2 mm-diameter pores, sealed with a screw-in cap, and sealed.

[0050]

[Effects of the Invention] By implementing the aqueous suspension preparation package for direct spraying of flooded sewage paddy fields according to the present invention, the following effects can be obtained. First, there is no deformation of the container after storage.
Secondly, the change in viscosity is small even after storage, the dischargeability is good even after storage, and uniform drop spraying is possible. Third, since the container is mainly composed of paper, disposal of the container after spraying is easy. Fourth, because the preparation is a dispersion medium using water,
There are few dangers such as flammability and flammability, and there is no environmental health problem due to irritation to human body and odor. Fifth, it can be sprayed at any time after the scraping work, and it is sufficient to drop the medicine in the container without diluting it with water from the ridge, or simply drop it into the water mouth at the time of water entry and pour it with the inflow water. In addition, labor for spraying the medicine can be saved.

Next, the usefulness of the packaged aqueous suspension preparation of the present invention will be shown by test examples.

The viscosity and SVI value of the aqueous suspension preparation prepared according to the examples were measured by the following methods. Further, a storage test and a discharge property test of the preparation were performed by the following methods.

[0053]

[Test Example] Viscosity measurement Type B viscometer (manufactured by Tokimec Co., Ltd., spindle No.
1 or No. 2), the spindle rotation speed is 12r.
p. m, and the liquid temperature was measured at 20 ° C. The results are shown in Tables 1 and 2.
Shown in

Measurement of SVI value The aqueous suspension was placed in a measurement system MS-0 or MS-125 on a stress detection type rheometer Rheomat 115 (manufactured by Contrabass Corporation) and allowed to stand at 20 ° C. for 20 minutes. The shear rate (D) is continuously and linearly changed from 0 sec ^-1 to 33.3 sec ^-1 over 120 seconds, and then the shear rate (D) is 33.3 over 120 seconds.
It was measured during this period of viscosity (eta) continuously and linearly changed to 0 sec ^-1 from sec ^-1. The viscosity (η) was plotted against the shear rate (D) for plotting to obtain a viscosity curve of the aqueous suspension preparation. Shear speed (D) from 0 sec ^-1 to 3
The viscosity (η1) at a shear rate of 3 sec ^{-1 and} the viscosity (η2) at a shear rate of 33 sec ^-1 when the pressure was increased to 3.3 sec ^-1 were determined from a viscosity curve, and the SVI value was determined by the following equation. The results are shown in Tables 1 and 2.

[0055]

(Equation 1)

Storage test The aqueous suspension preparation package obtained according to the Examples and Comparative Examples was
After storage in a 0 ° C. incubator for 60 days, the package was visually inspected for deformation. Further, the aqueous suspension preparation after storage was taken out and its viscosity was measured. The results are shown in Tables 1 and 2.

Dischargeability test The aqueous suspension preparation package before storage obtained according to the Examples and Comparative Examples and the aqueous suspension preparation package after storage for 60 days in a 40 ° C incubator were put in a sprayable state. The aqueous suspension formulation was discharged by shaking the package 50 times, and the discharged weight was measured every 10 shakes, and the average value and standard deviation were obtained. The average value and the standard deviation were shown by the following equation using the coefficient of variation (CV). The results are shown in Tables 1 and 2.

[0058]

(Equation 2)

[0059]

[Table 1]

[0060]

[Table 2]

Claims (3)

[Claims] 1. A composition comprising a pesticidal active ingredient, a protective colloid agent, a thickener and water and having a viscosity at 20 ° C. of 200 to 10.
A package of an aqueous suspension preparation, characterized in that an aqueous suspension preparation having a water viscosity of 00 mPa · s and an SVI value of 2 to 10 is filled in a molded container made of water-impermeable paper. 2. A package of an aqueous suspension preparation, characterized in that a high boiling point solvent is added to the aqueous suspension preparation of claim 1. 3. A spraying method, characterized by dropping an aqueous suspension formulation directly into a flooded sewage paddy field through pores provided in the package according to claim 1 or 2.