JP2010095498A - Aqueous suspension formulation-packaged article having improved storage stability, and method for storing aqueous suspension formulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous suspension formulation-packaged article which suppresses or prevents permeation of a solvent in an aqueous suspension formulation from a package container, and enables using an inexpensive polyethylene package container as a storage container. <P>SOLUTION: The aqueous suspension formulation packaged article comprises a polyethylene package container (Z), and an aqueous suspension formulation filled in the container, the aqueous suspension formulation obtained by mixing an agrichemically active constituent (a), a protective colloid agent (b), a solvent (c) having a solubility parameter of 6-9 [cal/mL]<SP>1/2</SP>, and water so that the weight ratio of the solvent (c) to the protective colloid agent (b) becomes within the range of a value 1-20. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous suspension preparation package having improved storage stability and a method for preserving an aqueous suspension preparation. More specifically, the present invention includes an agrochemical active ingredient and a solvent, and a solvent from a packaging container. The present invention relates to an aqueous suspension preparation package in which a plastic container, particularly a polyethylene packaging container, is filled with an aqueous suspension preparation in which permeation is suppressed or prevented and agricultural chemicals and solvents do not come into contact with farm workers.

  Further, the present invention suppresses or prevents solvent permeation from a packaging container when an aqueous suspension preparation containing an agrochemical active ingredient and a solvent is filled and stored in a plastic container, particularly a polyethylene packaging container. Further, the present invention relates to a method for preserving an aqueous suspension preparation that prevents agricultural chemicals and solvents from coming into contact with farm workers.

  In recent years, with increasing demands for safety of human agricultural products and the surrounding environment of agricultural chemical formulations, the mainstream of agricultural chemical formulations applied to paddy fields is a form in which agricultural chemical active ingredients are dissolved using a solvent (especially oil-based solvent) as a bulking agent. The emulsion has shifted to an aqueous suspension preparation in which the agrochemical active ingredient is suspended and dispersed using water as a bulking agent.

Since this aqueous suspension preparation uses water as an extender, it has an advantage over the oil preparation in terms of safety to humans and the surrounding environment.
On the other hand, aqueous suspension preparations have problems related to long-term storage stability, such as aggregation, crystal precipitation, sedimentation, etc., of agricultural chemical active ingredients dispersed in the preparations, as well as against target organisms compared to oil preparations. There are problems such as poor effectiveness.

  Conventionally, in order to solve such problems relating to long-term storage stability and effects on target organisms, various studies have been conducted on aqueous suspension formulations using protective colloid agents and organic solvents.

  In JP-A-55-36458 (Patent Document 1), an agrochemical active ingredient that is solid at room temperature and has a solubility in water at 20 ° C. of 1% by weight or less, a surfactant having an HLB of 5 or less, polyvinyl alcohol, There has been proposed a stable aqueous suspension agricultural chemical composition that is finely dispersed in water with ethylene glycol and liquid paraffin as essential components. The aqueous suspension pesticide composition is described that particle growth is suppressed and suspension stability and active ingredient stability are improved.

  In JP-A-60-214701 (Patent Document 2), a labor-saving and stable improvement in herbicidal effect, suspended in water using a pyrazole compound, a surfactant, a protective colloid agent, and a solvent. Application-type suspension pesticide compositions have been proposed.

  In JP-A-61-180701 (Patent Document 3), a water-insoluble pesticidal active ingredient that is liquid at room temperature, a water-insoluble pesticidal active ingredient that is solid or pasty at room temperature, polyvinyl alcohol, a water-soluble thickener, a dispersant, Contains water as an essential component and has good emulsion stability and suspension stability, characterized by dispersing solid or pasty pesticidal active ingredients in a liquid polyvinyl alcohol emulsion of water-insoluble pesticidal active ingredients. An aqueous suspension biocide composition with a suppressed increase in viscosity has been proposed.

Japanese Patent Application Laid-Open No. 2-275803 (Patent Document 4) has a good immediate effect and residual effect characterized in that a poorly water-soluble pesticide is partially encapsulated and partially emulsified and dispersed. A pest control formulation with reduced toxicity has been proposed.

In JP-A-4-327503 (Patent Document 5), a water-insoluble pesticidal active ingredient (solid or liquid) having a particle size of 0.1 to 250 μm, an aliphatic hydrocarbon or a glyceride oil (2 to 2).
40 wt.%) Is co-suspended, and further surfactant (3-35 wt.%), Steric inhibitor (0.1 wt.
10% by weight), an antifoaming agent (0.1 to 5% by weight), and a suspending agent (0.1 to 5% by weight). Agrochemical compositions that have been stably suspended using a loaded solvent have been proposed.

  JP-A-10-7504 (Patent Document 6) contains an agrochemical active ingredient, a vegetable oil fatty acid alkyl ester, a water-soluble polymer compound, a surfactant, and water, and has a formulation viscosity of 100 to 1000 mPa · s at 25 ° C. An aqueous suspension pesticide having excellent suspension stability, discharge from a container, and redispersibility in water has been proposed.

  In JP-A-10-175806 (Patent Document 7), extremely broad-leaved weeds, which are dispersed in submerged paddy fields by hand shaking or mechanical spraying and in which a pyrazole compound is suspended in water with a surfactant, are extremely difficult. Suspended agricultural chemical compositions having a high weed effect have been proposed.

  In JP-A-10-182302 (Patent Document 8), an emulsion containing at least one selected from water, protein, polyvinyl alcohol, and a surfactant (0.1 to 20% by weight) and a liquid pesticidal active ingredient. And at least one selected from water, protein, polyvinyl alcohol and surfactant, and solid pesticidal active ingredients. An aqueous suspension agricultural chemical composition in which quality deterioration is suppressed has been proposed.

  Examples of the agricultural chemical active ingredient include imazosulfuron and benzulide. The aqueous suspension agricultural chemical composition contains an organic solvent, an inorganic salt, an organic acid, a phospholipid, an epoxidized vegetable oil, and a phthalic ester. It is stated that it may be.

  In JP-A-10-251107 (Patent Document 9), a sulfonylurea containing a sulfonylurea herbicidal active ingredient and / or a herbicidal ingredient having a herbicidal effect, a water-soluble cellulose ether, water, and a high-boiling-point solvent. Labor-saving water-based suspension formulation for flooded sewage paddy fields, which suppresses the degradation of herbicidal ingredients, has good diffusibility of herbicidal active ingredients in paddy water, has little phytotoxicity to rice, and has a high herbicidal effect Has been proposed.

In JP-A-10-279406 (Patent Document 10), cihalohop butyl, polyvinyl alcohol, (degree of saponification: 78 to 83 mol%, degree of polymerization: 1000 or less), high boiling point solvent (two kinds of specific branched alkylbenzenes, isoparaffin) A sulfonylurea herbicide component, which is characterized by containing at least one selected from an organic solvent, ditridecyl phthalate, and rice bran oil fatty acid methyl ester), and diffusibility of herbicidal active ingredients in paddy water is suppressed In addition, a labor-saving aqueous suspension formulation having a good herbicidal effect and low risk of ignition, ignition, toxicity and irritation has been proposed.

  In JP-A-10-287503 (Patent Document 11), a sulfonylurea herbicidal active ingredient and / or a herbicidal ingredient, polyvinyl alcohol, (degree of saponification: 69 to 90 mol%, degree of polymerization: 2000 or less), a high-boiling solvent, water Contained in water-saving water-borne suspension with good diffusibility of herbicidal active ingredients in paddy water, low phytotoxicity to rice, high herbicidal effect, low risk of ignition and ignition, toxicity and irritation Suspended preparations have been proposed.

  In JP-A-10-306001 (Patent Document 12), as an active ingredient, one or more selected from an insecticidal active ingredient, a bactericidal active ingredient or an antifungal active ingredient, a water-soluble cellulose ether, and a high boiling point solvent are contained. An aqueous suspension formulation with good suspension stability, no phytotoxicity derived from surfactants, high antibacterial effect, low risk of ignition and ignition, toxicity and irritation Has been.

  JP-A-10-310501 (Patent Document 13) contains an agrochemical active ingredient, a protective colloid agent, a thickener, water, a high-boiling solvent, and has a formulation viscosity of 200 to 1000 mPa · s at 20 ° C., SVI value. An aqueous suspension preparation having a water content of 2 to 10 is filled in a molded container made of water-impermeable paper, and the aqueous suspension preparation is sprayed directly on the flooded sewage paddy through the pores provided in the package. A low-toxicity and low-irritating, labor-saving, aqueous suspension formulation that has no deformation of the storage container, small change in viscosity, good discharge from the container, and easy-to-process packaging is proposed. ing.

  In JP-A-11-35408 (Patent Document 14), an agrochemical active ingredient (preferably composed of one or more solids and one or more liquids), polyvinyl alcohol (0.1 to 2% by weight), surfactant, glycol (1-30% by weight), urea (1-30% by weight), bentonite, latex (1-30% by weight), and a polyvinyl alcohol emulsion of liquid agrochemical active ingredient (particle size) 1.5-10 μm), solid agrochemical active ingredient suspension (pH 2-6), latex, surfactant, mixed and prepared, creamed, particle size change even under high and low temperature conditions There has been proposed an aqueous emulsified suspension pesticide composition in which quality deterioration is suppressed.

  In JP-A-11-158006 (Patent Document 15), a herbicidal active ingredient having a water solubility of 1000 ppm or less at 20 ° C., a protective colloid agent (saponification degree: 69 to 90 mol%, polymerization degree: polyvinyl alcohol having a degree of polymerization of 2000 or less, water-soluble cellulose. Ether), high boiling point solvent, water, diffusibility and reachability of herbicidal active ingredients in paddy water, low phytotoxicity to rice, high herbicidal effect, danger against ignition and ignition Labor-saving application-type aqueous suspension formulations with low toxicity and irritation have been proposed.

  In JP 2001-89307 A (Patent Document 16), pyrazolate, a low melting point herbicidal active ingredient, a surfactant (polyoxyethylene alkyl ether phosphate ester, saponification degree: 60 to 90 mol%, polymerization degree: 50 to 2000). Suspension stability and surface, characterized by containing one or more selected from the group consisting of polyvinyl alcohol, phenylphenol phosphate ester and polyoxyethylene bisstyryl phenyl ether), organic acid ester and water Proposal of an aqueous suspension formulation for direct spraying of flooded sewage paddy fields with good diffusibility of herbicidal active ingredients in water and physicochemical stabilization of both high melting and low melting herbicidal active ingredients Has been.

  JP 2002-293702 A (Patent Document 17) contains modified polyvinyl alcohol (terminal alkyl group-modified type is preferred), herbicidal active ingredient (water solubility at 20 ° C. is preferably 100 ppm or less), high boiling point solvent, and water. It has a good suspension stability and freeze-restoration characteristics, has good diffusibility and reachability of herbicidal active ingredients in paddy water, has little phytotoxicity to rice, and has high herbicidal effect Labor-saving application-type aqueous suspension formulations with low risk of ignition, ignition, toxicity and irritation have been proposed.

JP-A 2007-145754 (Patent Document 18) contains imibenconazole, a naphthenic solvent, polyvinyl alcohol (degree of saponification: 85 mol% or more, degree of polymerization: preferably 1000 or less), sorbitan fatty acid ester, and 20 ° C. An aqueous suspension preparation having good suspension stability and excellent dischargeability from a container has been proposed, characterized in that the preparation viscosity is from 100 to 1000 mPa · s.

  However, when such an aqueous suspension preparation is stored, if a specific packaging container is used, there may be a problem that an organic solvent permeates (penetrates) the packaging container depending on the type of the solvent. For example, long-term storage stability is cited as a major problem.

More details are as follows.
Generally, a polyethylene container is used as a storage container for an aqueous suspension preparation because of its low cost for material and molding.

  On the other hand, hydrocarbon solvents, fatty acid ester solvents, vegetable oils, and the like are generally used as organic solvents added for the purpose of improving the physical characteristics of aqueous suspension preparations, effects on target organisms, and the like.

  However, when an aqueous suspension preparation containing these solvents is stored in a polyethylene packaging container, there are several serious problems associated with the problem that the organic solvent penetrates the packaging container. .

  For example, when a pesticide containing a pesticide active ingredient and a solvent permeates through the packaging container, the pesticide may come into contact with the worker or volatilize into the surrounding environment (vapor drift). For example, the permeated solvent may contaminate the label attached to the packaging container.

  Regarding the above problems, many studies have been made based on the viewpoint of selecting or setting the material and structure of the packaging container according to the solvent to be used, but such a solution has a large cost burden. There's a problem.

In addition, if there is no packaging material that is compatible with the solvent to be used (does not cause the above problem), formulation using the solvent becomes impossible.
Furthermore, there has been no technique for suppressing or preventing the permeation phenomenon that occurs when a solvent that permeates a polyethylene single-layer container is applied to an aqueous suspension preparation from the viewpoint of formulation formulation.

For this reason, there is a demand for the development of an aqueous suspension preparation in which permeation of the solvent from the packaging container is remarkably suppressed or prevented even if it contains a solvent that permeates the polyethylene packaging container.
In addition, Patent Document 1 describes an example in which an aqueous suspension agricultural chemical composition containing liquid paraffin, kerosene, or cottonseed oil was used, and the growth of dispersed particles was evaluated by storage for 2 years at room temperature.

  However, the aqueous suspension pesticide composition contains a surfactant having an HLB value of 5 or less, polyvinyl alcohol, ethylene glycol and liquid paraffin as essential components, and the number of types of essential components increases, resulting in cost reduction. It is disadvantageous.

  In addition, some of the essential ingredients are limited to substances such as polyvinyl alcohol, ethylene glycol, or liquid paraffin (limited in relation to specific dosage forms and types of agrochemical active ingredients). In particular, in view of the fact that liquid paraffin must be included as a solvent and that a specific surfactant is required, the aqueous suspension pesticide composition described in Patent Document 1 is never easy to use. There wasn't.

And in the said patent documents 2-18, long-term preservation | save of the agrochemical composition containing solvents, such as a hydrocarbon solvent, a fatty-acid ester solvent, a vegetable oil, in a specific packaging container like a polyethylene packaging container ( For example, there is no description about room temperature (usually 20 to 25 ° C. for 240 days).
JP-A-55-36458 JP 60-214701 A JP-A-61-180701 JP-A-2-275803 JP-A-4-327503 Japanese Patent Laid-Open No. 10-7504 JP-A-10-175806 JP-A-10-182302 JP-A-10-251107 JP-A-10-279406 JP-A-10-287503 JP-A-10-306001 JP-A-10-310501 JP-A-11-35408 Japanese Patent Laid-Open No. 11-158006 JP 2001-89307 A JP 2002-293702 A JP 2007-145754 A

  The object of the present invention is to suppress or prevent solvent permeation from the packaging container, thereby causing problems such as volatilization of the solvent (vapor drift) and contact of agricultural chemicals and solvents with agricultural workers due to solvent permeation. Furthermore, it is to provide an aqueous suspension preparation package using an inexpensive polyethylene packaging container as a storage container and having advantages in both environmental safety and health and cost.

  Further, the object of the present invention is to prevent the solvent from permeating through the packaging container even if an aqueous suspension preparation containing a solvent that would otherwise permeate through the packaging container is stored in the packaging container. Another object is to provide a storage method that enables storage for a period of time (for example, 240 days at room temperature (usually 20 to 25 ° C.)).

The present inventors diligently studied to solve the above problems.
As a result, the present inventors have found that any solvent that causes the above problems has a solubility parameter (SP value) of 6 to 9.

  Further, the present inventors have a relationship that the SP value of the solvent and the SP value of the packaging container material are relatively close between the solvent and the material of the packaging container through which the solvent permeates (made of plastic). It has been found that the above transmission phenomenon tends to occur when the above is established.

  Furthermore, even if the aqueous suspension preparation contains a solvent having an SP value of 6 to 9, if the protective colloid agent is contained in a specific amount with respect to the solvent, the above-mentioned permeation can be prevented. The present invention has been completed by finding that the phenomenon can be suppressed or prevented.

That is, the aqueous suspension preparation package of the present invention comprises an agrochemical active ingredient (a), a protective colloid agent (b), a solubility parameter (hereinafter referred to as “SP value”, the unit is [cal / mL] ^1/2 ) 6 ~ 9
An aqueous suspension preparation comprising the solvent (c) and water mixed together so that the weight ratio of the solvent (c) having an SP value of 6-9 to the protective colloid agent (b) is in the range of 1-20. In a polyethylene packaging container (Z).

  Furthermore, in the aqueous suspension preparation package, it is more effective that the protective colloid agent (b) is polyvinyl alcohol or water-soluble cellulose ethers to prevent the solvent from permeating the packaging container. It is preferable in terms of the point, and mixing the solvent so that the weight ratio of the solvent to the protective colloid agent (b) is in the range of 3 to 15 prevents or remarkably suppresses solvent permeation. Is preferred.

Moreover, the preservation | save method of the aqueous suspension which concerns on this invention is a pesticidal active ingredient (a), protective colloid agent (b), solvent (c) of SP value 6-9, and water with respect to protective colloid agent (b). The solvent (c) having an SP value of 6 to 9 is mixed so that the weight ratio is in the range of 1 to 20, and the obtained aqueous suspension preparation is filled in a polyethylene packaging container.

  Furthermore, in the method for preserving the aqueous suspension preparation, the protective colloid agent (b) is polyvinyl alcohol or water-soluble cellulose ethers, and the effect of preventing the solvent from passing through the packaging container is higher. In addition, it is preferable to mix the solvent so that the weight ratio of the solvent to the protective colloid agent (b) is in the range of 3 to 15 in order to prevent or remarkably suppress solvent permeation. preferable.

  In the aqueous suspension preparation package of the present invention, a solvent that causes a permeation phenomenon (a solvent having an SP value of 6 to 9) is added to a plastic storage container, particularly a polyethylene packaging container. On the other hand, since a specific amount of the protective colloid agent is contained, the permeation phenomenon of the solvent does not occur even when stored for a long time in a polyethylene packaging container.

  For this reason, it is possible to avoid problems such as contact of the solvent containing the pesticide with the worker, volatilization to the surrounding environment (vapor drift), or contamination of the label with the solvent containing the pesticide, due to the permeation of the solvent into the packaging container. it can.

Further, it is not necessary to revise the packaging container material and structure according to the type of solvent, and there is an excellent effect of avoiding the problem of increased cost burden.
Furthermore, in the aqueous suspension preparation package of the present invention, as described above, a protective colloid agent is added to the aqueous suspension preparation filled in the packaging container, and the protective colloid agent in the aqueous suspension preparation and By controlling the weight ratio with the solvent, the permeation of the solvent is prevented or significantly suppressed, and thus components such as a surfactant are not necessarily required. For this reason, the aqueous suspension preparation package of this invention can be manufactured cheaply and simply.

  According to the method for preserving an aqueous suspension preparation of the present invention, even if the aqueous suspension preparation contains a solvent that can permeate a plastic storage container, particularly a polyethylene packaging container, the solvent is not contained in the aqueous suspension preparation. Not only can the aqueous suspension preparation be stored without causing a problem of permeation through the packaging container, but also has an effect that it can be stored for a long period of time (for example, 240 days at room temperature (usually 20 to 25 ° C.)). Can do.

  Furthermore, an inexpensive polyethylene packaging container should be used even in an aqueous suspension preparation containing the above-mentioned solvent that would normally permeate a polyethylene container or the like by the storage method of the aqueous suspension preparation of the present invention. In addition, there is no need to spend time and effort on searching for a material that does not permeate the solvent, so that the aqueous suspension preparation can be stored for a long period of time at a low cost. can get.

  In the method for preserving an aqueous suspension preparation of the present invention, as described above, a protective colloid agent is added to a conventional aqueous suspension preparation containing an agrochemical active ingredient and a container-permeable solvent, and the By controlling the weight ratio between the protective colloid agent and the solvent, the phenomenon that the solvent permeates the packaging container is prevented or markedly suppressed, whereby the aqueous suspension preparation is stored for a long time in the polyethylene packaging container. Therefore, the above-mentioned effects can be obtained with low cost and simple work.

Hereinafter, the method for preserving the aqueous suspension preparation package and the aqueous suspension preparation of the present invention will be specifically described.
<Aqueous suspension formulation package>
The aqueous suspension preparation package according to the present invention is formed by filling an aqueous suspension preparation into a plastic container, particularly a polyethylene packaging container.
This aqueous suspension preparation is obtained by mixing (a) an agrochemical active ingredient, (b) a protective colloid agent, (c) a solvent having a solubility parameter of 6 to 9 [cal / mL] ^1/2 and water.

Moreover, in this aqueous suspension preparation, the weight ratio [(c) / (b)] of the solvent (c) to the protective colloid agent (b) is 1-20, preferably 3-15. It is desirable that the amount is contained so that solvent permeation can be prevented or significantly suppressed.
(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, etc. If it is used as a component, it will not specifically limit, As such a pesticidal active ingredient (a), the following are mentioned.

  For example, organophosphorus (such as 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-dichlorovinyl) ) -2,2-dimethylcyclopropanecarboxylate), etc.), benzoyl hydrazide, neonicotinoid, triazine, thiourea, oxadiazine, phenylpyrazole, nereistoxin and benzoylphenylurea insecticides Agent, insect growth regulator (buprofezin (2-tert-butylimino-3- An isopropyl-5-phenyl-1,3,5-l, 2,6] thiadiazinan-4-one), etc.) natural insecticides, biopesticides, like acaricides and nematicides.

Examples of the disinfectant include inorganic coppers, organic coppers, inorganic sulfur agents, organic sulfur agents, organophosphorus, benzimidazole, dicarboximide, acid amide, triazole (tetraconazole ((± ) -2- (2,4-Dichlorophenyl) -3- (1H-1,2,4-
Triazol-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, anilinopyrimidine, dithiolane, quinoxaline, aminopyrimidine, Phenylpyrrole-based, triazine-based, cyanoacetamide-based, guanidine-based, phthalide-based (fusalides (4,5,6,7-tetrachlorophthalide), etc.) germicides, antibiotic-based germicides (kasugamycin ([5-amino -2-methyl-6- (2,3,4,5,6-pentahydroxy-cyclohex Siloxy) tetrahydropyran-3-yl] amino-α-iminoacetic acid)), natural product fungicides and biological pesticides.

  As herbicides, for example, phenoxy acid type (MCPA thioethyl (S-ethyl = 2- (4-chloro-2-methylphenoxy) thioacetate etc.)), carbamate type, acid amide type (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-sulfonate )), Bipyridylium, dinitroaniline, aromatic carboxylic acid, imidazolinone, fatty acid, organic phosphorus, amino acid, diphenyl ether (biphenox (5- (2,4-dichlorophenoxy) -2-nitro Methyl benzoate)))), nitrile, cyclohexanedione, phenylphthalimide, cineol, indandione, benzofuran, triazolopyrimidine, oxazinone, allyltriazolinone, isourazole, pyrimidinylthiophthalide System, triazolinone series, inorganic herbicide, biological pesticide and the like.

Examples of plant growth regulators include ethylene, auxin, cytokinin, and gibberellin.
The said pesticidal active ingredient (a) may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, specific pesticide active ingredients contained in these include, for example, “Agricultural Chemicals Handbook 2005 Edition” (Japan Plant Protection Association, issued on October 11, 2005), “SHIBUYA INDEX 9th Edition” (SHIBUYA INDEX) Research Group, issued on December 15, 2001), “The Pesticide Manual Evention Edition” (published by British Crop Protection Council), and the like.

  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 agrochemical active ingredient (a) is usually added (contained) in an amount of 0.01 to 60% by weight, preferably 0.1 to 50% by weight, in the total amount of 100% by weight of the aqueous suspension preparation. Is desirable.
(B) Protective colloid agent In the present invention, when preparing an aqueous suspension preparation, the protective colloid agent (b) functions as an emulsifying and dispersing agent for a solvent, such as a protective colloid agent for oil droplet particles comprising an agrochemical solution. It is functioning as well.

  When the protective colloid agent is added, the periphery of the oil droplet particles made of the (agrochemical solution or) solvent is protected by the protective colloid agent molecules, and contact between the oil droplet particles and the inner wall of the polyethylene container is prevented. Thereby, it can prevent that a solvent permeate | transmits a polyethylene container.

  On the other hand, when the protective colloid agent is not used, and when emulsified and dispersed using a surfactant or the like, the oil droplet particles are dispersed due to the dispersion effect of the surfactant or the like, but the oil droplet particles are dispersed in polyethylene. The action of protecting [preventing] from contact with the wall surface of the packaging container does not work, and the solvent permeates the polyethylene packaging container.

Examples of the protective colloid agent (b) used in the present invention include polyvinyl alcohol,
In addition to gum arabic, gelatin, and albumin, water-soluble cellulose ethers, water-soluble soybean polysaccharides (trade name “Soya Five”, manufactured by Fuji Oil Co., Ltd.), sodium alginate, and the like are exemplified, but not limited thereto.

  Among the protective colloid agents, polyvinyl alcohol and water-soluble cellulose ethers have a higher effect of preventing the solvent from permeating through the packaging container, and better dischargeability of the aqueous suspension preparation from the packaging container. This is preferable.

Dischargeability is determined by filling the container with an aqueous suspension preparation (filling amount: Xg) and then removing the aqueous suspension preparation from the container by tilting the container (discharge amount: Yg). (Y / X) x 100%, the larger the value, the smaller the amount of aqueous suspension formulation that remains or adheres to the container. It means that the discharge is good.

  Examples of the polyvinyl alcohol include Kuraray Poval PVA-405 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 500, saponification degree 80 to 83 mol%), Kuraray Poval PVA-210 (trade name, manufactured by Kuraray Co., Ltd., Average polymerization degree 1000, saponification degree 87-89 mol%), Kuraray Poval PVA-420 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 2000, saponification degree 78-81 mol%), Kuraray Poval L-8 (trade name, stock) Manufactured by Kuraray Co., Ltd., average polymerization degree 1000 or less, saponification degree 69.5-72.5 mol%).

In addition to these polyvinyl alcohols, the following modified polyvinyl alcohols may be mentioned.
For example, as the terminal alkyl group-modified polyvinyl alcohol, Kuraray Poval MP-203 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 300, saponification degree 86.5-89.5 mol%), Kuraray Poval MP-103 (product) Name, Kuraray Co., Ltd., average polymerization degree 300, saponification degree 98.0-99.0 mol%), side chain alkyl group-modified polyvinyl alcohol, Shin-Etsu Poval COTP-2000 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) As a carboxyl group-modified polyvinyl alcohol, Kuraray Poval PVA KL-506 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 600, saponification degree 74.0)
80.0 mol%), as a cation-modified polyvinyl alcohol, Kuraray Poval PVA C-506 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 600, saponification degree 74.0-8)
0.0 mol%), Kuraraypoval as silicon-containing modified polyvinyl alcohol
R-2105 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 500, saponification degree 98.0 to 99.0 mol%), and sulfonic acid group-modified polyvinyl alcohol, Goseilan L-0301 (trade name, Nippon Synthetic Chemical Co., Ltd.) As an acetoacetyl group-modified polyvinyl alcohol, Goseifamer Z-200 (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree of 99.0 mol% or more) and the like can be mentioned. It is not limited.

  Moreover, as said water-soluble cellulose ether, two of three OH groups in one glucose residue contained in a cellulose are substituted by a methoxy group, and methoxy group is 27-32 in the molecule | numerator. Examples thereof include methylcellulose containing 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, “Marporose M” (trade name, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., methoxy group substitution rate 27.5-31.5%, thermal gelation temperature 50-55 ° C.), “Metroses SM” (Product) Name, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group substitution rate 27.5-31.5%, thermal gelation temperature about 52 ° C.), etc., as hydroxypropyl methylcellulose, “Marporose 60MP” (trade name, Matsumoto Yushi) Manufactured by Pharmaceutical Co., Ltd., methoxy group substitution rate 28-30%, hydroxypropoxy group substitution rate 7-12%, thermal gelation temperature 58-64 ° C.), “
“Marporose 65MP” (trade name, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., methoxy group substitution rate 27-30%, hydroxypropoxy group substitution rate 4-7.5%, thermal gelation temperature 62-68 ° C.), “Marporose 90MP” ( Product name, Matsumoto Yushi Seiyaku Co., Ltd., methoxy group substitution rate 19-25%, hydroxypropoxy group substitution rate 4-12%, thermal gelation temperature 70-90 ° C., “Marporose MP” (trade name, Matsumoto Yushi Seiyaku Co., Ltd.) And a methoxy group substitution rate of 16.5 to 20%, a hydroxypropoxy group substitution rate of 60 to 70%, and a thermal gelation temperature of 60 to 70 ° C.).

Moreover, the following are mentioned as water-soluble cellulose ethers other than these.
For example, hydroxyethyl cellulose obtained by reacting cellulose with ethylene oxide, hydroxypropyl cellulose obtained by reacting cellulose with propylene oxide, and monochloroacetic acid reacted with alkali cellulose obtained by reacting cellulose with caustic soda. For example, carboxymethyl cellulose in which a part of the hydroxyl group is substituted with a carboxyl group.

These water-soluble cellulose ethers are commercially available. For example, the following commercially available products may be used.
Examples of hydroxyethyl cellulose include HEC Daicel (trade name, manufactured by Daicel Chemical Industries, Ltd.), Fuji Heck (trade name, manufactured by Fuji Chemical Co., Ltd.), NATROSOL (trade name, manufactured by Nissho Iwai Corporation), and the like. Examples of propyl cellulose include Nisso HPC (trade name, manufactured by Nippon Soda Co., Ltd.), and examples of carboxymethyl cellulose include Sunrose (trade name, manufactured by Nippon Paper Industries Co., Ltd.), CMC Nippon (trade name, Nippon CMC Co., Ltd.). Manufactured), serogen (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), CMC Daicel (trade name, manufactured by Daicel Chemical Industries, Ltd.), and the like, but are not limited thereto.

These protective colloid agents (b) may be used alone or in combination of two or more.
The protective colloid agent (b) is desirably contained in the aqueous suspension preparation in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight.
(C) Solvent In the present invention, the solvent (c) used for the preparation of the aqueous suspension preparation is for the purpose of emulsifying the agrochemical active ingredient, preventing crystal precipitation, and improving the biological effect and spreadability in paddy fields. Solvents that are used and usually have an SP value of 6-9 are used.

  In addition, the solvent used in the present invention has an SP value of usually 6 to 9, and has a property of permeating through a polyethylene container. Therefore, the solvent is emulsified and dispersed with the protective colloid agent (b), and the protective colloid agent ( By protecting with b), it is necessary to prevent direct contact with the surface of the polyethylene container and to prevent permeation from the container.

  In addition, the reason why the SP value of the solvent used in the present invention is usually 6 to 9 is that the SP value of the solvent that permeates the polyethylene container is usually 6 to 9, and the SP value is less than 6 and 9. This is because the excess solvent usually does not substantially permeate the polyethylene container, and therefore it is not necessary to apply the technique of the present invention to obtain the effects of the present invention.

  The SP value of the solvent used in the present invention is R.D. F. Fedors, Polym. Eng. Sci. , 14, 147 (1974).

Specifically, the cohesive energy is E _coh [cal / mol], and the molar volume is V [mL / m.
ol], and the sum of the cohesive energies E _coh of all the groups contained in the compound (that is, the solvent to which the present invention is applied) for which the SP value is calculated is ΣE _co
and is _h, if the sum of the molar volume V of all groups contained in the compound [sigma] v, SP value .delta.v [
cal / mL] ^1/2 is calculated from the following equation.

Further, specific values of the cohesive energy E _coh and the molar volume V of the group contained in the compound to be calculated are known documents (for example, Van Krevelen, DW “Cohesive Properties and Solidity”; In Proper
ties of Polymers, Elsevier Scientific Publishing, Netherlands, Chapter 7 (1997), etc.) can be used.

Examples of the solvent having an SP value of 6 to 9 that can be used in the present invention include xylene (SP value 8.7), alkene L (SP value 7.6), alkene 200P (SP value 7.3) (all above Aromatic hydrocarbon solvents such as trade name, manufactured by Nippon Petrochemical Co., Ltd.
Paraffinic solvents such as IP solvent 2028 (SP value 7.0), IP solvent 2835 (SP value 6.2) (all are trade names, manufactured by Idemitsu Kosan Co., Ltd.);
Naphthenic solvents such as Naphthezol 160 (SP value 7.7) and Naphthezol 220 (SP value 8.0) (all are trade names, manufactured by Nippon Petrochemical Co., Ltd.);
Ditridecyl phthalate (SP value 9.0), diisobutyl adipate (SP value 8.7), isopropyl palmitate (SP value 8.4), isotridecyl stearate (SP value 7.8), isopropyl myristate (SP value) 8.1), fatty acid ester solvents such as triisodecyl trimellitic acid (SP value 8.3);
Vegetable oil fatty acid esters such as methyl oleate (SP value 7.6), rice bran oil fatty acid methyl ester (SP value 8.1);
Vegetable oils such as oleic acid (SP value 8.5), linoleic acid (SP value 9.0);
However, it is not limited to these, and any solvent that falls within the range of SP values of 6 to 9 can be used without any limitation.

Moreover, these solvents may be used alone or in combination of two or more.
The solvent (c) having an SP value of 6 to 9 is desirably contained in the aqueous suspension preparation in an amount of 1 to 60% by weight, preferably 5 to 50% by weight.

In addition, water can be mix | blended in arbitrary amounts, for example, it is often contained in the amount of about 40 to 95 weight% in the aqueous suspension formulation.
(D) Mixing ratio (weight ratio) of protective colloid agent and solvent
The mixing ratio of the solvent having an SP value of 6 to 9 to the protective colloid agent in the aqueous suspension preparation package of the present invention must be in the range of 1 to 20 by weight.

When a solvent having an SP value of 6 to 9 is added at a ratio lower than 1 with respect to the protective colloid agent, the solvent permeation prevention action not only tends to peak, but also costs are disadvantageous. Furthermore, the dischargeability of the aqueous suspension preparation from the packaging container is significantly reduced.

  On the other hand, when a solvent having an SP value of 6 to 9 is added at a weight ratio exceeding 20 with respect to the protective colloid agent, the emulsion stability is lowered, and prevention of solvent permeation due to the protective colloid effect cannot be expected.

Furthermore, when taking into consideration the effect of preventing solvent permeation and the cost derived from the added amount of the protective colloid agent and the ability to discharge the aqueous suspension preparation from the packaging container, the preferred addition ratio of the solvent having an SP value of 6 to 9 is the protective colloid. It is 3-15 times with respect to an agent.
(Z) Packaging container In the present invention, a packaging container made of a solvent having an SP value of 6 to 9 and a material that can permeate the solvent (generally a polymer compound having an SP value close to the SP value of the solvent, etc. )) Can be used to prevent the solvent from permeating from the packaging container, and the effect of remarkably suppressing can be obtained, but more preferable packaging containers are as follows.

Examples of the packaging container (Z) for the aqueous suspension preparation package of the present invention include polyethylene packaging containers.
More specifically, it is made of polyethylene, is not easily deformed by external pressure and temperature conditions, is non-specific in shape, has low molding costs, and is suitable for spraying and transferring aqueous suspension preparations from packaging containers. If it is a packaging container of a different form, it does not matter.

Examples of the packaging container satisfying such conditions include a high-density polyethylene single layer container.
(E) Other components In the aqueous suspension preparation package of the present invention, the following components may be added as auxiliary agents in addition to the above-described essential components as long as the effects of the present invention are not lost. .

  For example, (e-1) surfactants (excluding those corresponding to the protective colloid agent (b)) include nonionic surfactants, anionic surfactants, and cationic surfactants. And amphoteric surfactants.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, etc.
Examples of the anionic surfactants include alkyl aryl sulfonates, lignin sulfonates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and lauryl sulfates.
Examples of cationic surfactants include alkyl trimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts, and the like.
Examples of amphoteric surfactants include dialkylaminoethyl betaine and alkyldimethylbenzyl betaine.

  However, the nonionic surfactant is limited to those exceeding HLB5. When the HLB is 5 or less, the suspension stability of the aqueous suspension preparation of the present invention is significantly deteriorated with respect to long-term storage, and the dispersed particles are agglomerated and coalesced, resulting in practical problems.

  In the present invention, since the protective colloid agent (b) has an emulsifying and dispersing action, a sufficient effect can be obtained without blending a surfactant, and therefore a surfactant is not necessarily required (aqueous suspension). Surfactant may not be included in the formulation).

Thus, when a surfactant is not used (the aqueous suspension preparation does not contain a surfactant), the aqueous suspension preparation of the present invention can be produced inexpensively and easily.
The surfactant that can be used in the present invention is not limited to these examples,
These surfactants may be used alone or in combination of two or more.

The content of the surfactant in the aqueous suspension preparation is preferably 0 to 20% by weight, and more preferably 0.1 to 20% by weight.
(E-2) Thickeners (excluding those corresponding to protective colloid agents (b)) include, for example, heteropolysaccharides such as xanthan gum, welan gum, and lambzan gum, dextrin, starch derivatives such as phosphate starch, tragacanth gum, and casein , Colloidal hydrous aluminum silicate, colloidal hydrous magnesium silicate, colloidal hydrous aluminum silicate / magnesium, silicon dioxide, and the like, but are not limited thereto.

Moreover, these thickeners may be used individually by 1 type, and may be used in combination of 2 or more types.
The content of the thickener in the aqueous suspension preparation is preferably 0.1 to 10% by weight.
(E-3) Examples of antifoaming agents include silicone-based and fatty acid-based substances,
(E-4) Antifreezing agents include ethylene glycol, propylene glycol, glycerin and the like,
(E-5) Examples of antiseptic and antibacterial agents include potassium sorbate, p-chloro-m-xylenol, butyl p-oxybenzoate, and the like.
(E-6) Examples of pH adjusters include citric acid, phosphoric acid, magnesium carbonate,
(E-7) Stabilizers for pesticidal active ingredients include antioxidants, UV inhibitors, crystal precipitation inhibitors, and the like.

In the present invention, these optional components (adjuvants) may be appropriately added, but are not limited to the auxiliary agents exemplified here.
The above adjuvant may be used alone or in combination of two or more of (e-1) to (e-7), and the adjuvant belonging to any one of them is used alone, or Two or more kinds may be used in combination.

<Method for preparing aqueous suspension preparation package>
Although the preparation method of the aqueous suspension formulation package of this invention is not specifically limited, For example, it can prepare by the following method.
(Preparation stage of aqueous suspension formulation)
After adding the protective colloid agent (b) and other auxiliary agent (e) as necessary to water, the solvent (c) having an SP value of 6 to 9 is added to obtain an emulsion (i).

If necessary, a premix product obtained by dissolving an agrochemical active ingredient (a) in a solvent (c) having an SP value of 6 to 9 may be used after emulsifying with a protective colloid agent (b) (emulsion (ii)). .
The emulsified liquid (i) or (ii) is mixed with an agrochemical active ingredient (a
) And other adjuvants (e) are dissolved or dispersed to prepare an aqueous suspension formulation;
(Note that when this emulsion (ii) is used, an aqueous suspension preparation can be prepared by mixing this emulsion (ii), other auxiliary agent (e), if necessary, water and the like. Good.)
Or
In the emulsified liquid (i) or (ii), the pesticidal active ingredient (a) and other auxiliary agents (e
) Is added to water and then wet pulverized using glass beads or the like; or an agrochemical active ingredient (a) and other auxiliary (e) as required are added to water. Thereafter, a method of preparing an aqueous suspension preparation by mixing a dispersion that has been wet-ground using glass beads or the like and an emulsion (i) or (ii) prepared in advance;
Any of these may be adopted.
(Preparation stage of aqueous suspension preparation package)
Next, in the present invention, the aqueous suspension preparation prepared as described above is filled into a (synthetic) resin container, particularly a polyethylene packaging container (Z) that is desirable in terms of low cost and high versatility. An aqueous suspension formulation package of the invention is prepared.

The dimensions and shape of the container are not particularly limited.
In the present invention, a polyethylene (PE) container is suitable as a container for containing (filling) the aqueous suspension preparation, but the container is not limited to this, and is made of a material through which a solvent having an SP value of 6 to 9 permeates. It can also be applied to containers, and polypropylene (PP), polystyrene (PS), natural rubber, polydimethylsiloxane, or the like may be used.
<Usage form (use method) of aqueous suspension preparation>
The aqueous suspension preparation prepared by the above method is, for example, a raw solution, or a method of diluting about 1.5 to 5 times with water and spraying directly on a paddy field, or
The raw solution or a solution diluted about 50 to 5000 times with water is sprayed onto crops and weeds using a sprayer or the like, or helicopter is used from the air. Although it can be applied to weeding, insecticidal and the like by a method of diluting to 2 to 100 times and spraying, it is not limited thereto.
<Preservation method of aqueous suspension preparation package>
In the present invention, the agrochemical active ingredient (a), the protective colloid agent (b), the solubility parameter (hereinafter referred to as “SP value”, the unit is [cal / mL] ^1/2 ) is 6 to 9 [cal / mL] ^{1. / 2} solvent (c) and water are mixed so that the weight ratio [(c) / (b)] of the solvent (c) to the protective colloid agent (b) is in the range of 1-20. The aqueous suspension preparation is stored by filling the resulting aqueous suspension preparation in an arbitrary amount into a polyethylene packaging container (Z).

Thus, the aqueous suspension preparation according to the present invention contains the protective colloid agent (b) as an essential component, and the solvent (c) having an SP value of 6 to 9 is added to the protective colloid agent (b). In contrast, a solvent having an SP value of 6 to 9 that permeates through a polyethylene packaging container is an aqueous suspension because it is blended so as to have a weight ratio of 1 to 20, preferably 3 to 15. Although the solvent (c) is protected by the protective colloid agent (b) in the present invention even though it is contained in the suspension, the solvent (c) is applied to the wall surface of the polyethylene packaging container (Z). Contact can be prevented or significantly suppressed.

As a result, even if a synthetic resin container, particularly a polyethylene packaging container (Z) is used, the solvent (
The aqueous suspension preparation containing c) can be stored for a long time. In addition, the aqueous suspension preparation stored in such a container is excellent in discharging properties from the packaging container (Z).

  The term “long-term storage” in the present invention refers to a storage temperature exceeding 40 ° C. and not more than 50 ° C., for example, at room temperature (usually 20 to 25 ° C.) to 40 ° C. Below, for example, a cycle condition (cycle 1 cycle) that reciprocates between a high temperature (50 ° C.) and a low temperature (−10 ° C.) for a period of at least 90 days (corresponding to three years of room temperature storage) (preferably at least 120 days). In the case of storage at 50 ° C. for 7 days and then −10 ° C. for 7 days), the solvent (c) is contained in the packaging for a period of 6 cycles (equivalent to 3 years of room temperature storage) (preferably at least 8 cycles). It means that it can be stored without penetrating the container and without impairing the discharge after storage.

  In the following, preferred embodiments of the present invention will be described in detail with reference to examples of aqueous suspension preparation packages in which solvent permeation from the packaging container of the present invention is suppressed or prevented and methods for preserving aqueous suspension preparations in polyethylene packaging containers. However, the present invention is not limited to these examples.

In the examples and comparative examples, “parts” means all parts by weight.
[Example 1]
2 parts of hydroxypropylmethylcellulose was dissolved in 44.9 parts of water.

In this solution,
Kasugamycin drug substance (antibiotic fungicide) 0.6 parts,
5 parts propylene glycol,
A premix in which 25 parts of MEP drug substance (organophosphorus insecticide) and 12 parts of methyl oleate (SP value 7.6) are mixed and dissolved,
10 parts of a fusaride base (phthalide fungicide) finely pulverized to an average particle size of 3.0 μm using Jet-O-mizer (manufactured by Seishin Enterprise Co., Ltd.),
Add 0.3 parts of colloidal hydrous aluminum silicate,
The mixture was stirred and mixed at 5000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).

Subsequently, 0.2 part of xanthan gum was added to the mixture, and the mixture was uniformly mixed with a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation.
450 mL of this aqueous suspension preparation is filled into a high-density polyethylene single layer container (500 mL capacity) specified in the agrochemical packaging labeling guidelines of the agricultural chemical packaging material specification table, and the container is sealed to obtain an aqueous suspension preparation package. It was.
[Example 2]
In Example 1, the formulation composition was 0.6 parts of kasugamycin drug substance (antibiotic fungicide), 10 parts of fusalide drug substance (phthalide fungicide), 25 parts of MEP drug substance (organophosphorus insecticide), Kuraray Poval PVA-405 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 500, saponification degree 80 to 83 mol%) 1 part, methyl laurate (SP value 8.2) 16 parts, hydrous aluminum silicate 0.3 part, xanthan gum An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 0.2 part, 5 parts of propylene glycol and 41.9 parts of water were used.
[Example 3]
Dissolve 0.55 parts of sodium alginate in 63.95 parts of water, and in this, 5 parts of propylene glycol, 10 parts of alkene L (SP value 7.6) (trade name, manufactured by Nippon Petrochemical Co., Ltd.), buprofezin raw material (Insect growth control agent) 20 parts and colloidal hydrous aluminum silicate 0.3 part are added, and the average particle size of the pulverized liquid is 2.5 μm with Dynomill KDL type (Willy A. Bachofen AG). Finely pulverized.

The pulverized liquid here refers to a liquid in which pulverized particles of an agrochemical active ingredient and emulsified particles of a solvent are combined, and the average particle size refers to the average particle size of a mixture of pulverized particles and emulsified particles.
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.

To this pulverized liquid, 0.2 part of xanthan gum was added and mixed uniformly with a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation.
450 mL of this aqueous suspension preparation is filled into a high-density polyethylene single layer container (500 mL capacity) specified in the agrochemical packaging labeling guidelines of the agricultural chemical packaging material specification table, and the container is sealed to obtain an aqueous suspension preparation package. It was.
[Example 4]
In Example 3, the formulation composition was 20 parts of buprofezin active ingredient (insect growth regulator), Kuraray Poval L-8 (trade name of Kuraray Co., Ltd., average polymerization degree 1000 or less, saponification degree 69.5-72.5 mol%) 4 parts, methyl oleate (SP value 7.6) 10 parts, colloidal hydrous aluminum silicate 0.3 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, water 6
An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that the amount was 0.5 parts.
[Example 5]
In 55.9 parts of water, 1.5 parts of gum arabic is dissolved. In this, 5 parts of propylene glycol, 12 parts of rice bran oil fatty acid methyl ester (SP value 8.1), and BPMC active ingredient (carbamate insecticide) 10 And a premix prepared by mixing and dissolving 15 parts of MEP active ingredient (organophosphorus insecticide) and 0.4 part of colloidal hydrous aluminum silicate, and adding 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) And stirred for 10 minutes.

Furthermore, 0.2 part of xanthan gum was added and mixed uniformly with a three-one motor (manufactured by HEIDON) to obtain an aqueous suspension preparation.
450 mL of this aqueous suspension preparation is filled into a high-density polyethylene single layer container (500 mL capacity) specified in the agrochemical packaging labeling guidelines of the agricultural chemical packaging material specification table, and the container is sealed to obtain an aqueous suspension preparation package. It was.
[Example 6]
In Example 5, the formulation composition was 10 parts BPMC active ingredient (carbamate insecticide), 15 parts MEP active substance (organophosphorus insecticide), 2 parts carboxymethylcellulose, 18 parts isobutyl adipate (SP value 8.7) An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that 0.3 parts of colloidal hydrous aluminum silicate, 0.25 parts of xanthan gum, 5 parts of propylene glycol and 49.45 parts of water were used.
[Example 7]
In Example 5, the formulation composition was 10 parts permethrin drug substance (pyrethroid insecticide), 5 parts gum arabic, 10 parts naphthesol 220 (SP value 8.0) (trade name, manufactured by Nippon Petrochemical Co., Ltd.), colloidal An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that 0.2 part of hydrous aluminum silicate, 0.2 part of xanthan gum, 5 parts of propylene glycol, and 69.6 parts of water were used.
[Example 8]
In Example 3, the formulation composition was 12 parts of tetraconazole base (triazole fungicide), 7 parts of hydroxyethyl cellulose, 10 parts of IP solvent 2835 (SP value 6.2) (trade name, manufactured by Idemitsu Kosan Co., Ltd.), An aqueous suspension preparation package was obtained in the same manner as in Example 3, except that 0.3 parts of colloidal hydrous aluminum silicate, 0.2 parts of xanthan gum, 5 parts of propylene glycol, and 65.5 parts of water were used.
[Example 9]
In Example 3, the formulation composition was 12 parts of tetraconazole base (triazole fungicide), Kuraray Poval MP-203 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 300, saponification degree 86.5 to 89.5 mol). %) 1.7 parts, triisodecyl trimellitic acid (SP value 8.3) 24 parts, colloidal hydrous aluminum silicate 0.3 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, water 56.8 parts. Except for the above, an aqueous suspension preparation package was obtained in the same manner as in Example 3.
[Example 10]
In Example 1, the formulation composition was 1.2 parts of kasugamycin active substance (antibiotic fungicide), 15 parts of fusalide active substance (phthalide fungicide), 1.2 parts of gum arabic, linoleic acid (SP value 9.0) ) An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 15 parts, colloidal hydrous aluminum silicate 0.3 parts, xanthan gum 0.25 parts, propylene glycol 5 parts and water 62.05 parts were used. It was.
[Example 11]
In Example 1, the formulation composition was 10 parts imibenconazole base (triazole fungicide), 1.7 parts methylcellulose, 30 parts isotridecyl stearate (SP value 7.8), colloidal hydrous aluminum silicate 0.25. Parts suspension, xanthan gum 0.2 parts, propylene glycol 5 parts, water 52.85 parts were obtained in the same manner as in Example 1 to obtain an aqueous suspension preparation package.
[Example 12]
In Example 1, the formulation composition is 10 parts of imibenconazole active substance (triazole fungicide), Kuraray Poval PVA-205 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 500, saponification degree 87 to 89 mol%). 5 parts, rice bran oil fatty acid methyl ester (SP value 8.1) 16 parts, colloidal hydrous magnesium silicate 0.4 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, water 63.9 parts An aqueous suspension preparation package was obtained in the same manner as in Example 1.
[Example 13]
In Example 3, the formulation composition was 5 parts of tenyl chlor drug substance (acid amide herbicide), 6 parts of gum arabic, 7.5 parts of triisodecyl trimellitic acid (SP value 8.3), colloidal hydrous aluminum silicate An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that 3 parts, 0.2 parts of xanthan gum, 5 parts of propylene glycol, and 76 parts of water were used.
[Example 14]
In Example 3, the formulation composition was 5 parts of tenyl chlor drug substance (acid amide herbicide), 5 parts of Kuraray Poval PVA-210 (trade name of Kuraray Co., Ltd., average polymerization degree 1000, saponification degree 87-89 mol%), IP Solvent 2028 (SP value 7.0) (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 14 parts, colloidal hydrous aluminum silicate 0.3 parts, welan gum 0.3 parts, propylene glycol 5 parts, water 70.4 parts Except that, an aqueous suspension preparation package was obtained in the same manner as in Example 3.
[Example 15]
Formulation composition is 5 parts of cimetrine active substance (triazine herbicide), 4 parts of sodium alginate, 14 parts of isopropyl myristate (SP value 8.1), 0.2 part of colloidal hydrous aluminum silicate, 0.3 part of xanthan gum, An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 5 parts of propylene glycol and 71.5 parts of water were used.
[Example 16]
In Example 1, the formulation composition was 5 parts of cimetrin active ingredient (triazine herbicide), 0.8 parts of gum arabic, IP solvent 2835 (SP value 6.2) (trade name, manufactured by Idemitsu Kosan Co., Ltd.), 13 parts, An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 0.2 parts of colloidal hydrous aluminum silicate, 0.3 parts of xanthan gum, 5 parts of propylene glycol, and 75.7 parts of water were used.
[Example 17]
In Example 5, the formulation composition was 12 parts of butachlor drug substance (acid amide herbicide), 5 parts of sodium alginate, 14 parts of isobutyl adipate (SP value 8.7), 0.4 part of colloidal hydrous magnesium silicate, An aqueous suspension preparation package was obtained in the same manner as in Example 5, except that 0.2 part of xanthan gum, 5 parts of propylene glycol, and 63.4 parts of water were used.
[Example 18]
In Example 5, the formulation composition was 12 parts of butacrol base (acid amide herbicide), Kuraray Poval PVA-420 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 2000, saponification degree 80 to 83 mol%) 1.5 Parts, IP solvent 2028 (SP value 7.0) (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 28.5 parts, colloidal hydrous magnesium silicate 0.4 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, water An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that the amount was 52.4 parts.
[Comparative Example 1]
In Example 5, the formulation composition was 10 parts BPMC drug substance (carbamate insecticide), 15 parts MEP drug substance (organophosphorus insecticide), 0.4 part sodium alginate, rice bran oil fatty acid methyl ester (SP value 8) 0.1) An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that 20 parts, hydrous aluminum silicate 0.3 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, and water 49.1 parts were used. It was.
[Comparative Example 2]
In Example 5, the formulation composition was 10 parts BPMC drug substance (carbamate insecticide), MEP
Active ingredient (organophosphorus insecticide) 15 parts, polyoxyethylene styryl phenyl ether 15 parts, methyl oleate (SP value 7.6) 10 parts, hydrous aluminum silicate 0.3 part, xanthan gum 0.2 part, propylene An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that 5 parts of glycol and 44.5 parts of water were used.
[Comparative Example 3]
In Example 3, the formulation composition was 20 parts buprofezin base (insect growth regulator), 5 parts polyoxyethylene styryl phenyl ether, 10 parts triisodecyl trimellitic acid (SP value 8.3), colloidal hydrous aluminum silicate 0 An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that the content was .3 parts, xanthan gum 0.2 parts, propylene glycol 5 parts and water 59.5 parts.
[Comparative Example 4]
In Example 3, the formulation composition was 20 parts of buprofezin active ingredient (insect growth regulator), 12 parts of polyoxyethylene styryl phenyl ether sulfate, 20 parts of oleic acid (SP value 8.5), 0. 1 colloidal hydrous aluminum silicate. An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that 2 parts, 0.3 parts of welan gum, 5 parts of propylene glycol, and 42.5 parts of water were used.
[Comparative Example 5]
In Example 5, the formulation composition was 10 parts permethrin drug substance (pyrethroid insecticide), 0.5 part hydroxypropyl methylcellulose, IP solvent 2028 (SP value 7.0) (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 15 parts. An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that colloidal hydrous magnesium silicate 0.4 part, xanthan gum 0.2 part, propylene glycol 5 part and water 68.9 parts were used.
[Comparative Example 6]
In Example 3, the formulation composition was 12 parts tetraconazole base (triazole fungicide), 8.3 parts gum arabic, 5 parts decahydronaphthalene (SP value 8.3), colloidal hydrous aluminum silicate 0. An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that 3 parts, 0.3 parts of welan gum, 5 parts of propylene glycol, and 69.1 parts of water were used.
[Comparative Example 7]
In Example 1, the formulation composition was 1.2 parts of kasugamycin drug substance (antibiotic fungicide), 15 parts of fusalide drug substance (phthalide fungicide), Kuraray Poval PVA-420 (trade name, manufactured by Kuraray Co., Ltd., average) Polymerization degree 2000, saponification degree 80-83 mol%) 0.8 part, rice bran oil fatty acid methyl ester (SP value 8.1) 30 part, colloidal hydrous aluminum silicate 0.3 part, xanthan gum 0.3 part, propylene An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 5 parts of glycol and 47.4 parts of water were used.
[Comparative Example 8]
In Example 1, the formulation composition was 10 parts of imibenconazole base (triazole fungicide), 8 parts of hydroxyethyl cellulose, 4 parts of alkene L (SP value 7.6) (trade name, manufactured by Idemitsu Kosan Co., Ltd.), colloid An aqueous suspension preparation package was obtained in the same manner as in Example 1 except that 0.4 part of the aqueous hydrous magnesium silicate, 0.2 part of xanthan gum, 5 parts of propylene glycol, and 72.4 parts of water were used.
[Comparative Example 9]
In Example 3, the formulation composition was 5 parts of a tenyl chlor drug substance (acid amide herbicide), 0.5 part of methyl cellulose, 20 parts of methyl laurate (SP value 8.2), 0.4 part of colloidal hydrous magnesium silicate. An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that 0.2 parts of xanthan gum, 5 parts of propylene glycol, and 68.9 parts of water were used.
[Comparative Example 10]
In Example 3, the formulation composition was ten parts of tenyl chlor drug substance (acid amide herbicide), 12.5 parts of carboxymethyl cellulose, 10 parts of rice bran oil fatty acid methyl ester (SP value 8.1), colloidal hydrous magnesium silicate An aqueous suspension preparation package was obtained in the same manner as in Example 3 except that 0.4 part, 0.2 part of xanthan gum, 5 parts of propylene glycol, and 66.9 parts of water were used.
[Comparative Example 11]
In Example 1, the formulation composition was 5 parts of cimetrin active ingredient (triazine herbicide), 10 parts of Kuraray Poval PVA-210 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 1000, saponification degree 87-89 mol%), adipine Example 1 except that 5 parts of isobutyl acid (SP value 8.7), 0.3 parts of colloidal hydrous aluminum silicate, 0.3 parts of welan gum, 5 parts of propylene glycol and 74.4 parts of water were used. An aqueous suspension formulation package was obtained.
[Comparative Example 12]
In Example 1, the formulation composition was 5 parts of cimetrin active ingredient (triazine herbicide), 9 parts of Kuraray Poval PVA-210 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 1000, saponification degree 87 to 89 mol%), naphthesol 220 (SP value 8.0) (trade name, manufactured by Nippon Petrochemical Co., Ltd.) 8 parts, colloidal hydrous aluminum silicate 0.3 parts, xanthan gum 0.3 parts, propylene glycol 5 parts, water 72.4 parts Except that, an aqueous suspension preparation package was obtained in the same manner as in Example 1.
[Comparative Example 13]
In Example 5, the formulation composition was 12 parts of butachlor drug substance (acid amide herbicide), 4 parts of polyoxyethylene styryl phenyl ether sulfate, IP solvent 2835 (SP value 6.2) (trade name, manufactured by Idemitsu Kosan Co., Ltd.) ) 15 parts, colloidal hydrous magnesium silicate 0.4 parts, xanthan gum 0.2 parts, propylene glycol 5 parts and water 63.4 parts It was.
[Comparative Example 14]
In Example 5, the formulation composition was 12 parts of butacrol bulk (acid amide herbicide), Kuraray Poval MP-203 (trade name, manufactured by Kuraray Co., Ltd., average polymerization degree 300, saponification degree 86.5-89.5 mol%). ) 1.2 parts, 2-ethylhexyl stearate (SP value 7.6) 30 parts, colloidal hydrous aluminum silicate 0.3 parts, xanthan gum 0.2 parts, propylene glycol 5 parts, water 51.3 parts An aqueous suspension preparation package was obtained in the same manner as in Example 5 except that.
[Test Example 1 (permeability test)]
In the packaging container with a label formed by pasting the label on the single layer container (500 mL capacity) made of high-density polyethylene specified in the agrochemical packaging material display guideline of the agricultural chemical packaging material specification table, the above-mentioned Examples and Comparative Examples immediately after preparation The aqueous suspension preparation was filled with 450 mL, and the resulting aqueous suspension preparation package was left to stand at 20 ° C. for 240 days, at 40 ° C. for 90 days, and at 50 ° C. for 90 days. The presence or absence and degree of solvent adhesion to the label were evaluated.

Further, the aqueous suspension preparation package obtained in the same manner as described above was stored stationary under conditions of 6 cycles (1 cycle is stored at 50 ° C. for 7 days and then stored at −10 ° C. for 7 days).
Thereafter, the stored sample was taken out, and the presence or absence and degree of solvent adhesion to the container and the label were evaluated in the same manner as described above.

The evaluation criteria are as follows.
“−”: No transmission.
“±”: A slight amount of permeation is recognized (no problem in practical use).
“+”: Clear transmission is recognized (problem in practical use).
“++”: There is a risk of adhesion to the surroundings (practical problem).

The results are shown in Tables 1 and 2.
[Test Example 2 (Emission Test)]
The high-density polyethylene single layer container (500 mL capacity) specified in the agrochemical packaging material specification table of the agricultural chemical packaging material specification table is filled with 450 mL of the aqueous suspension preparation just prepared in each of the above Examples and Comparative Examples, and at 25 ° C. After standing for 1 day, the container was inverted 20 times, and then the container was inverted to discharge the aqueous suspension preparation.

The end point was when the drop interval of the drug from the mouth of the container was 10 seconds or more.
The weight of the drug discharged at this time was measured, and the ratio with respect to the weight of the drug filled in the container was evaluated as the discharge property (%).

  The calculation formula for emission is as follows.

It can be evaluated that the handleability of the aqueous suspension preparation is better as the value of the dischargeability (%) is larger.
The results are shown in Tables 1 and 2.

[Description of table]
The test results described in Tables 1 and 2 are as follows. Examples 1 to 18 are Comparative Examples 1 to 20 in terms of solvent permeability and dischargeability from a packaging container at 20 ° C., 40 ° C., 50 ° C. This suggests that it is clearly superior to 14.

Examples 1 to 18 showed good results in both the permeability test and the discharge test.
Focusing on the examples in which the aqueous suspension preparation contains polyvinyl alcohol or water-soluble cellulose ethers as a protective colloid agent, the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in a weight ratio with respect to the protective colloid agent. For Examples 1, 6, 9, and 12 contained in an amount in the range of 3 to 15, excellent results of completely preventing solvent permeation under various temperature conditions while maintaining very good dischargeability. showed that.

  For Examples 4, 8, and 14 in which the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in an amount in the range of 1 to 3 by weight with respect to the protective colloid agent, although the dischargeability is slightly reduced. The amount of the protective colloid agent added to the solvent particles was sufficient, and the results showed that the solvent permeation was prevented under various temperature conditions.

  Examples 2, 11 and 18 in which the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in an amount ranging from 15 to 20 by weight with respect to the protective colloid agent, exhibits very good dischargeability. As shown, the protective effect of the protective colloid agent on the solvent particles was slightly weak, and a slight amount of permeation was confirmed at 50 ° C., but it was at a level of no practical problem.

  Further, when attention is focused on Examples in which the aqueous suspension preparation contains a protective colloid agent other than polyvinyl alcohol or water-soluble cellulose ethers, the aqueous suspension preparation uses a solvent having an SP value of 6 to 9 against the protective colloid agent. For Examples 5, 10, and 15 contained in an amount ranging from 3 to 15 by weight, the solvent permeation was completely completed at 20 ° C., 40 ° C., and 50 ° C. while maintaining very good dischargeability. However, a slight amount of permeation was confirmed for the cycle conditions that go back and forth between the high temperature and the freezing conditions.

  Although Examples 7, 13, and 17 in which the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in an amount in the range of 1 to 3 by weight with respect to the protective colloid agent, the dischargeability is slightly reduced. Solvent permeation was completely prevented under the conditions of 20 ° C., 40 ° C., and 50 ° C., and a slight amount of permeation was confirmed under the cycle conditions.

  While Examples 3 and 16 in which the aqueous suspension preparation contained a solvent having an SP value of 6 to 9 in an amount in the range of 15 to 20 by weight with respect to the protective colloid agent, very good discharge properties were exhibited. Thus, the protective action of the solvent particles by the protective colloid agent was slightly weak, and a slight permeation was confirmed under the condition of 50 ° C., but it was at a level of no practical problem.

  In addition, the permeability test results of Examples 2, 4, 9, 12, 14, and 18 using polyvinyl alcohol as the protective colloid agent show that the factor contributing to the solvent permeability is that of the protective colloid agent and the SP value of 6-9. It is a mixing ratio of the solvent, suggesting that it is not affected by the saponification degree and polymerization degree of polyvinyl alcohol.

  Similarly, the permeability test results of Examples 1, 6, 8, and 11 in which the aqueous suspension preparation used water-soluble cellulose ethers as the protective colloid agent also showed that the factors contributing to the solvent permeability were the protective colloid agent and SP. It is a mixing ratio of solvents having a value of 6 to 9, suggesting that it is not affected by the type of water-soluble cellulose ethers.

  In addition, when the mixing ratio of the solvent having the SP value of 6 to 9 and the protective colloid agent is about the same, when the protective colloid agent is polyvinyl alcohol, water-soluble cellulose ethers and other cases, the solvent permeation suppression under cycle conditions In terms of effects, polyvinyl alcohol and water-soluble cellulose ethers completely prevent solvent permeation, suggesting that these two protective colloid agents have an effect of preventing permeation, particularly under a wide range of temperature conditions.

On the other hand, Comparative Examples 1 to 14 showed results that were significantly inferior to Examples in both the permeability test and the discharge test.
For Comparative Examples 2, 3, 4, and 13 in which the aqueous suspension preparation does not contain a protective colloid agent, the type and addition amount of the surfactant used for emulsification dispersion with respect to the solvent having an SP value of 6 to 9 may be changed. Although the excretion was good, the solvent permeation was remarkably permeated under all storage conditions, resulting in a very problematic formulation for practical use.

  Further, when attention is focused on a comparative example in which the aqueous suspension preparation contains polyvinyl alcohol or water-soluble cellulose ethers as a protective colloid agent, the aqueous suspension preparation has a weight of a solvent having an SP value of 6 to 9 with respect to the protective colloid agent. For Comparative Examples 8, 10, 11, and 12 contained in amounts in the range of less than 1, the solvent permeation was prevented under various temperature conditions, but the discharge from the packaging container was around 70% and around 80%. It was a very bad and practically problematic level.

  On the other hand, Comparative Examples 5, 7, 9, and 14 in which the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in an amount in a range exceeding 20 by weight with respect to the protective colloid agent is very good discharge. Although the protective effect of the solvent particles by the protective colloid agent was weak and there was no practical problem at 20 ° C, the solvent permeation was clear at 40 ° C, and the surroundings were affected under conditions of 50 ° C and cycle storage. The solvent permeation was confirmed, and overall, it was a very problematic level for practical use.

  Further, when focusing attention on examples in which the aqueous suspension preparation contains a protective colloid agent other than polyvinyl alcohol or water-soluble cellulose ethers, the solvent having an SP value of 6 to 9 is less than 1 by weight with respect to the protective colloid agent. For Comparative Example 6 contained in an amount in the range of 20 ° C., 40 ° C., 50 ° C., the solvent permeation was prevented, and the cycle conditions were practically no problem, but the discharge from the packaging container The property was very bad at 69%, which was a very problematic level for practical use.

  On the other hand, Comparative Example 1 in which the aqueous suspension preparation contains a solvent having an SP value of 6 to 9 in an amount in a range exceeding 20 by weight with respect to the protective colloid agent showed very good dischargeability. The protective action of the protective colloid agent on solvent particles is weak, and clear solvent permeation is confirmed under 20 ° C conditions, and permeation of the solvent to the extent that it permeates the surroundings is confirmed under 40 ° C, 50 ° C, and cyclic storage conditions. It was a certain formulation.

  The test results of Test Examples 1 and 2 in the above Examples and Comparative Examples show that when an aqueous suspension preparation containing a solvent having an SP value of 6 to 9 is stored in a polyethylene container, the permeation and prevention of the solvent permeation are reduced. It is an essential condition that (1) the protective colloid agent is contained, (2) the mixing ratio of the solvent having an SP value of 6 to 9 with respect to the protective colloid agent is in the range of 1 to 20 by weight, and (3 It is more effective that the protective colloid agent is polyvinyl alcohol or water-soluble cellulose ethers, and (4) the mixing ratio of the solvent having an SP value of 6 to 9 with respect to the protective colloid agent is in the range of 3 to 15 by weight. This suggests that the conditions prevent solvent permeation.

Claims (6)

(A) an agrochemical active ingredient, (b) a protective colloid agent, (c) a solvent having a solubility parameter (SP value) of 6 to 9 [cal / mL] ^1/2 and water,
The weight ratio [(c) / (b)] of the solvent (c) to the protective colloid agent (b) is 1-2.
An aqueous suspension formulation, mixed to an amount in the range of 0,
(Z) An aqueous suspension preparation package characterized by being filled in a polyethylene packaging container.   2. The aqueous suspension preparation package according to claim 1, wherein the protective colloid agent (b) is polyvinyl alcohol or water-soluble cellulose ethers. 3. The aqueous suspension according to claim 1 or 2, wherein the solvent (c) with respect to the protective colloid agent (b) is mixed so that the weight ratio is in the range of 3-15. Pharmaceutical packaging. (A) an agrochemical active ingredient, (b) a protective colloid agent, (c) a solvent having a solubility parameter of 6 to 9 [cal / mL] ^1/2 and water, the solvent (c) for the protective colloid agent (b) So that the weight ratio is in the range of 1-20,
A method for preserving an aqueous suspension preparation, wherein the obtained aqueous suspension preparation is filled in a polyethylene packaging container.   The method for preserving an aqueous suspension preparation according to claim 4, wherein the protective colloid agent (b) is polyvinyl alcohol or water-soluble cellulose ethers.   6. The aqueous suspension according to claim 4, wherein the solvent (c) is mixed so that the weight ratio of the solvent (c) to the protective colloid agent (b) is in the range of 3-15. Storage method of the preparation.