JP2002363005A - Stabilized agricultural aqueous suspension - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an excellent aqueous suspension comprising bensultap, capable of retaining long-term fluidity and having good suspension stability during dilution at a high concentration. SOLUTION: This aqueous suspension comprises the bensultap, a specific surfactant, urea or L-lysine hydrochloride and further polyethylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous agricultural suspension which does not cause solidification or caking during storage for a long period of time and has excellent suspension stability for a high-concentration diluent.

[0002]

2. Description of the Related Art Conventionally, as agricultural pesticides, mainly powders,
Granules have been used, but in recent years, high-concentration preparations that are easy to handle in small quantities are becoming mainstream. The high-concentration preparation has a high content of the pesticidal active ingredient and can be used by dispersing it in an appropriate amount of a suitable solvent such as water at the time of use. Examples thereof include emulsions and wettable powders. However, both types of formulations tend to be repelled in recent years because, for example, a large amount of an organic solvent is used for an emulsion, and powdering of a wettable powder at the time of preparation of a spray liquid is inevitable. Although the wettable powder obtained by granulating the wettable powder almost eliminates the disadvantages of the wettable powder, the dispersed particle size when diluted with water is more than 10 μm.
m and large. Therefore, for example, when a high-concentration chemical solution is sprayed in the air, problems such as clogging of the strainer occur. To avoid this problem, aqueous suspensions in which the pesticidal active ingredient is atomized and suspended in water are being developed.
However, depending on the type of the pesticidal active ingredient, solidification, crystal growth, caking, etc. occur due to melting and recrystallization of the pesticidal active ingredient during the production of the aqueous suspension and during long-term storage, and thus the physical properties of the pesticide formulation. Deterioration is easy to occur. The aqueous suspension containing bensultap tends to solidify due to the heat generated during the production, and the whole preparation hardens in a short period of time. Therefore, it has been difficult to obtain a stable aqueous suspension.

[0003]

It contains bensultap, is easy to handle, (1) maintains fluidity for a long period of time, does not cause a caking phenomenon due to settling of suspended particles, and (2) benzultap aqueous suspension A high aqueous concentration of bensultap even when diluted with water to a certain extent at the time of use and the concentration of bensultap is high (such dilution is hereinafter referred to as high concentration dilution); The purpose is to obtain a suspension.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that aqueous suspensions containing bensultap, a specific surfactant, urea or L-lysine hydrochloride are available. The turbidity agent does not solidify during production or storage at room temperature, maintains fluidity over a long period of time, and furthermore, by containing polyethylene glycol, does not generate sediment at the time of high concentration dilution and has excellent dilution stability. I found it to work.

JP-A-4-327502, JP-A-6-29
3607 and JP-A-4-89817 describe the use of urea as a deicing agent in aqueous suspensions as known. However, there is no description that suppresses caking or solidification of the aqueous suspension. In addition, Japanese Unexamined Patent Application Publication No.
Japanese Patent Application Laid-Open No. Hei 4-3275 discloses a method for solving the flow leaf phenomenon (a phenomenon in which when a liquid agent is sprayed on a seedling in a nursery box and then transplanted to Honda, the seedling is submerged and decay as it is).
No. 02 describes the use of polyethylene glycol in an aqueous suspension as a thickener. However, there is no description about suspension stability when an aqueous suspension is diluted at a high concentration.

That is, the present invention relates to (1) (i) bensultap, (ii) (i) a condensate of naphthalenesulfonic acid or a salt thereof with formaldehyde, (b) ligninsulfonic acid, and (c) polycarboxylic acid. Or (2) one or more surfactants selected from the group consisting of (2) polyoxyethylene styryl phenyl ether or a salt thereof, or a formaldehyde condensate thereof; (iii)
An aqueous suspension comprising urea or L-lysine hydrochloride, (iv) a water-soluble polymer, and (v) a suspension aid; (2) the water-soluble polymer is polyethylene glycol The aqueous suspension according to the above (1), which is characterized in that:
(3) The above (1), wherein the suspension aid is one or more suspension aids selected from the group consisting of montmorillonite, colloidal silicon oxide, colloidal silicon oxide-aluminum oxide mixture, and sepiolite. (4) The aqueous suspension according to (1) to (4), wherein the content of bensultap is 5 to 60% by weight based on the whole preparation.
(3) The aqueous suspension according to any of (3), (5) the content of the total formulation is 5 to 60% by weight of bensultap, 0.2 to 10% by weight of a surfactant, urea or L-lysine hydrochloride 0 0.5 to 15% by weight, polyethylene glycol 0.
The aqueous suspension according to any one of the above (1) to (4), wherein the aqueous suspension is 1 to 5% by weight and a suspension aid 0.05 to 10% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The content of bensultap in the aqueous suspension of the present invention is usually about 5 to 5
It is about 60% by weight, preferably about 10 to 50% by weight.

The surfactant used in the aqueous suspension of the present invention includes formaldehyde condensate of naphthalenesulfonic acid or a salt thereof, ligninsulfonic acid salt, polycarboxylic acid or a salt thereof, polyoxyethylenestyrylphenylether or a salt thereof. Salts or formaldehyde condensates thereof. Examples of the salt include a phosphate ester salt, a sulfate ester salt, a sulfonate, an amine salt and the like. These may be appropriately selected from known ones.

As the surfactant, there is no problem even if a commercially available surfactant is used.
Newcargen FS-4 (formaldehyde polycondensate of sodium naphthalene sulfonate: Takemoto Yushi Co., Ltd.)
New Calgen WG-4 (sodium lignin sulfonate: manufactured by Takemoto Yushi Co., Ltd.), New Cargen RX-
B (Sodium lignin sulfonate: Takemoto Yushi Co., Ltd.)
Demol EP (special polycarboxylic acid polymer: manufactured by Kao Corporation), Newcalgen FS-1 (polyoxyalkylene allyl phenyl ether: manufactured by Takemoto Yushi Co., Ltd.),
Newcalgen FS-12 (polyoxyalkylene allyl phenyl ether: manufactured by Takemoto Yushi Co., Ltd.), Newcalgen FS-11 (polyoxyethylene allyl phenyl ether formaldehyde condensate: manufactured by Takemoto Yushi Co., Ltd.),
Neugen EA-177 (polyoxyethylene distyryl phenyl ether: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Newcargen FS-7 (polyoxyalkylene allyl phenyl ether sulfate salt: manufactured by Takemoto Yushi Co., Ltd.), Newcargen FS- 3 (polyoxyethylene allyl phenyl ether phosphate amine salt: manufactured by Takemoto Yushi Co., Ltd.),
Solpol 3561 (polyoxyethylene styryl phenyl ether sulfate: manufactured by Toho Chemical Co., Ltd.), Solpol 7290-P (polyoxyethylene styryl phenyl ether sulfate: manufactured by Toho Chemical Co., Ltd.), Soprofol FL (polyoxyethylene tristyryl) Phenyl ether phosphate triethanolamine: manufactured by Rhone Poulin) and the like. Among them, Newcargen WG-4, Newcargen FS-7, Solpol 7290-P, Solpol 3561, Soprofol FL, and the like are preferable, and Newcalgen WG-4 and Newcargen FS-7 are particularly preferable.

The above surfactants can be used alone or in combination of two or more, preferably one to three. The content of the surfactant in the aqueous suspension of the present invention is usually about 0.2 to 10% by weight based on the whole preparation.
Degree, preferably about 0.5 to 8% by weight.

[0011] In the aqueous suspension of the present invention, one or more other surfactants, preferably 1 to 3 other than the above-mentioned surfactants,
Types can be combined. Examples of such a surfactant include sodium alkylbenzenesulfonate, sodium dialkylsulfosuccinate and the like. The content of such surfactants used in combination in the aqueous suspension of the present invention is generally about 0.1 to 10% by weight, preferably about 0.2 to 10% by weight, based on the whole preparation.
It is about 5% by weight.

The aqueous suspension of the present invention may further contain one or more, preferably 1-3, other pesticidal active ingredients in order to widen the application range of the preparation. As other pesticidal active ingredients, any pesticidal active ingredients such as insecticides, fungicides, herbicides, etc. may be used as long as they are solid at normal temperature. Examples of the pesticidal active ingredient corresponding to this are as follows, but are not limited to the following examples as long as the pesticidal active ingredient is in a solid state at normal temperature.

Examples of the insecticide include pyridafenthion, dimethoate, PMP (O, O-dimethyl-S-phthalimidomethyldithiophosphate), CVMP (2
-Chloro-1- (2,4,5-trichlorophenyl) vinyldimethylphosphate), dimethylvinphos, acephate, salithion, DEP (dimethyl-2,2,2)
-Trichloro-1-hydroxyethylphosphonate),
NAC (1-naphthal-N-methyl carbamate), M
TMC, MIPC (2-isopropylphenyl-N-methylcarbamate), PHC (2-isopropoxyphenyl-N-methylcarbamate), MPMC, XMC
(3,5-xylyl-N-methylcarbamate), bentiocarb, pirimicarb, mesomil, oxamyl,
Thiodicarb, cypermethrin, cartap hydrochloride, thiocyclam, diflubenzuron, teflubenzuron, chlorfluazuron, buprofezin, hexthiazox, fenbutatin oxide, pyridaben, clofentezin, nitenpyram and the like.

Examples of fungicides include tyrium, captan, TPN, fusalide, tolclofosmethyl, fosetyl, thiophanatemethyl, benomyl, carbendazole, thiabendazole, dietofencarb, iprodione, vinclozolin, procymidone, fluoroimide, oxycarboxin, mepronil, flutranil,
Pencyclone, metalaxyl, oxadixyl, triadimefon, hexaconazole, triforine, blasticidin S, kasugamycin, polyoxin, validamycin A, mildiomycin, PCNB, hydroxyisoxazole, dazomet, dimethylimol, diclomedine, triazine, ferimzone, probenazole, isoprothiolane , Tricyclazole, pyroquilon, oxonic acid, diclosimet and the like.

Examples of herbicides include sulfonylureas (eg, imazosulfuron, bensulfuronmethyl, azimsulfuron, sulfosulfuron, pyrazosulfuronethyl, halosulfuronmethyl, etc.), triazines such as simethrin, and ureas such as dimuron; Acid amides (eg, propanil, mefenacet, etobenzanide, etc.),
Examples thereof include carbamates such as Swep, diazoles (eg, oxadiazon, pyrazolate, etc.), dinitroanilines such as prodiamine, and other compounds such as capfentrol and pentoxazone.

Urea or L-lysine hydrochloride used in the aqueous suspension of the present invention is a compound having the effect of breaking hydrogen bonds between water molecules, and urea is particularly preferred. The content of urea or L-lysine hydrochloride in the aqueous suspension of the present invention is usually about 0.5 to 15% by weight, preferably about 1 to 10% by weight, based on the whole preparation.

Polyethylene glycol is a water-soluble polymer having water retention, moisture retention, viscosity increase and the like. The polyethylene glycol used in the aqueous suspension of the present invention preferably has an average molecular weight of about 2,000 to 70,000. For example, PEG 4000N (average molecular weight 3,000: manufactured by Sanyo Chemical Co., Ltd.), PEG6000S
(Average molecular weight 8,300: manufactured by Sanyo Chemical Co., Ltd.), PEG
20,000 (average molecular weight: 20,000: Sanyo Chemical Co., Ltd.)
And PEG6000S is particularly preferred.
The content of polyethylene glycol in the aqueous suspension of the present invention is about 0.1 to 5% by weight, preferably about 0.1 to 3% by weight, based on the whole preparation.

In the aqueous suspension of the present invention, one or more, preferably one to three, other water-soluble polymers can be used in combination other than polyethylene glycol. For example, an adsorptive water-soluble polymer (eg, polyvinylpyrrolidone, alkylated vinylpyrrolidone copolymer, vinylpyrrolidone-styrene block copolymer, methylvinylether-maleic anhydride copolymer, polyvinyl alcohol, sodium polyacrylate, carboxymethylcellulose, etc.) And non-adsorbable water-soluble polymers such as polyol-based polymers and polysaccharides. Examples of the polysaccharide include gum arabic, gelatin, guar gum, xanthan gum, starch, and starch derivatives (eg, starch hydrolyzate, soluble starch, enzyme-modified starch, pregelatinized starch, dextrins such as dextrin and cyclodextrin) and the like. No.

In the present invention, there is no problem even if a commercially available water-soluble polymer is used, and among the commercially available products, Agrimer 30 (polyvinylpyrrolidone: manufactured by IS Corporation) and Agrimer AL-10 (alkyl Vinylpyrrolidone copolymer: manufactured by ISP Corporation, Agrimer ST (vinylpyrrolidone-styrene block copolymer: manufactured by ISP Corporation), Agrimer VEM
AH-240 (methyl vinyl ether-maleic anhydride copolymer: manufactured by ASP Co., Ltd.), Stabilose MKK100 (starch), and Road Pole 23 (xanthan gum: manufactured by Rhone Poulin Co., Ltd.) are preferred. The content of the water-soluble polymer in the aqueous suspension of the present invention is about 0.01 to 5% by weight based on the whole preparation.

The suspending aid is a water-insoluble additive such as Kunipia F (montmorillonite: Kunimine Kogyo KK)
), Laponite (manufactured by Nissin Kasei Co., Ltd.), for example, Aerosil such as Aerosil 200 (colloidal silicon oxide: manufactured by Nippon Aerosil Co., Ltd.), and a colloidal silicon oxide-aluminum oxide mixture (eg, Aerosil COK84: Si)
O2 / Al2O0 = 82-86 (%) / 14-18
(%): Nippon Aerosil Co., Ltd.), Adeplus ML
70DS (Sepiolite: manufactured by Mizusawa Chemical Industry Co., Ltd.) and the like. Among them, a colloidal silicon oxide-aluminum oxide mixture is preferred. When a suspension aid is used,
The content of the water-insoluble additive is usually about 0.5 to the whole preparation.
About 05 to 10% by weight, preferably about 0.1 to 3% by weight
It is about. Additives such as water-soluble polymers and suspension aids may be used alone or in combination of two or more.

In the aqueous suspension of the present invention, other additives used in ordinary aqueous suspensions can be used. For example, a pH adjuster, an antifreezing agent, an antifoaming agent, a preservative and the like can be used freely, and these may be selected according to the content of the pesticidal active ingredient used. As the pH adjuster, for example, citric acid monohydrate is used. Examples of the antifreeze include ethylene glycol, diethylene glycol, glycerin, propylene glycol and the like. As the defoaming agent, for example, a silicon-based defoaming agent (eg, Anti-Home E-20: manufactured by Kao Corporation) or the like is used. As a preservative, for example, butyl paraben (n
-Butyl parahydroxybenzoate), potassium sorbate, sorbic acid and the like.

When a pH adjuster is used, it is used in an amount of usually about 0.01 to 5% by weight, preferably about 0.05 to 3% by weight, based on the whole preparation. When a cryoprotectant is used, it is usually about 1 to the whole preparation.
-20% by weight, preferably about 3-10% by weight. When an antifoaming agent is used, it is used in an amount of usually about 0.05 to 0.5% by weight, preferably about 0.05 to 0.3% by weight, based on the whole preparation. When a preservative is used, it is generally about 0.01 to 3% by weight, preferably about 0.01 to 0.01% by weight based on the whole preparation.
It is used in the range of 1.5% by weight.

The aqueous suspension of the present invention can be prepared by (i) bensultap, (ii) a surfactant, (iii) urea or L-lysine hydrochloride and (iv) polyethylene glycol according to a method known per se or a method analogous thereto. Etc., and if desired, other components can be suspended in water. For example, a method in which all components to be used are sufficiently stirred and mixed by a high-speed stirrer for about 20 to 60 minutes and then finely pulverized and dispersed by a wet pulverizer such as a dyno mill or a microfluidizer (manufacturing method 1), A method in which the raw powder of the active ingredient is finely pulverized by a dry pulverizer such as a jet mizer, and the other components are mixed and dispersed by a high-speed stirrer for about 30 to 90 minutes (Production method 2). As will be understood from the above-mentioned production method, the active ingredient of the aqueous suspension of the present invention is in the form of fine particles in the preparation and is dispersed in water. When other fine powder components are used, they are similarly dispersed in water. The average particle size of the fine particles is about 10 μm or less, preferably about 0.1 to 6 μm.
It is about.

The pesticide preparation of the present invention thus produced is used as it is according to a known method or diluted at the time of use with an appropriate solvent such as water, if necessary, about 0 to 20 times by weight. The aqueous suspension of the invention obtained in use thus obtained contains high concentrations of bensultap. The method of using the pesticide preparation of the present invention varies depending on the place of use, etc.
It can be sprayed or immersed in a paddy field, a field, an orchard, a turf or a non-agricultural land by spraying or dripping. It can also be used for aerial application, soil treatment, foliage application, nursery box treatment, side application, seed treatment, floor soil admixture, insect application, paddy field underwater application, and the like. The amount of the aqueous suspension agent of the present invention varies depending on the content of the pesticidal active ingredient and the like, but cannot be specified unconditionally, but is usually about 1 to 1,000 g, preferably about 1 to 1,000 g, per 10 ares.
It is about 500 g.

[0025]

The present invention will be described more specifically with reference to the following examples, comparative examples and test examples, but the present invention is not limited to these examples. Further, the parts or percentages used herein indicate parts by weight or percentage by weight unless otherwise specified.

[0026] After mixing the above raw materials for 40 minutes using a high-speed stirrer,
Dynomill (Shinmaru Enterprises, 1.0m
Wet pulverization (1 pass) using m glass beads, a filling rate of 80%, and a peripheral speed of 15 m / s) to obtain an aqueous suspension containing 40% of bensultap.

[0027] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

[0028] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

[0029] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

[0030] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

[0031] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

[0032] By operating in the same manner as in Example 1, an aqueous suspension containing 40% of bensultap was obtained from the above raw materials.

Test Example 1 Examples 1 and 2 and Comparative Example 1
Regarding the aqueous suspension of No. 2, the viscosity, the presence or absence of caking, and the average particle diameter were examined by the methods described below. (1) Viscosity For each preparation, immediately after production and at room temperature (temperature 20
(25 ° C., humidity 40 to 65%) After standing for 3 years, the viscosity was measured at 25 ° C. using a B-type viscometer. (2) Presence or absence of caking After the preparations were manufactured, they were allowed to stand at room temperature (temperature: 20 to 25 ° C., humidity: 40 to 65%) for three years, and then the presence or absence of caking at the bottom was examined.

[Table 1] Table 1 shows that the aqueous suspension of the present invention is excellent in long-term storage stability.

Test Example 2 With respect to the aqueous suspensions of Examples 2, 3 and Comparative Example 3, the stability of an 8-fold dilution was examined by the method described below. (1) Stability of 8-fold diluted solution 217 mL of water and 31 mL of flowable (diluted suspension) were placed in a 250-mL measuring cylinder, and the mixture was turned down 10 times. 2
After hours, the presence or absence of precipitation was investigated.

[Table 2] Table 2 shows that the aqueous suspension of the present invention is excellent in suspension stability at high concentration dilution.

[0035]

According to the present invention, (i) bensultap, (ii) a surfactant, (iii) urea or L-lysine hydrochloride and (i)
v) The aqueous suspension containing polyethylene glycol has good suspension stability at the time of high concentration dilution, and maintains fluidity for a long period of time, and does not cause caking due to sedimentation of suspended particles. It can be advantageously used as an aqueous suspension having excellent properties.

Claims (5)

[Claims] (I) bensultap, (ii) (i) a condensate of naphthalenesulfonic acid or a salt thereof with formaldehyde, (b) ligninsulfonic acid salt, (c) polycarboxylic acid or a salt thereof, and (d) One or more surfactants selected from the group consisting of polyoxyethylene styrylphenyl ether or a salt thereof, or a formaldehyde condensate thereof, (iii) urea or L-lysine hydrochloride, (iv) a water-soluble polymer, and ( v) An aqueous suspension comprising a suspension aid. 2. The aqueous suspension according to claim 1, wherein the water-soluble polymer is polyethylene glycol. 3. The suspension aid according to claim 1, wherein the suspension aid is at least one suspension aid selected from the group consisting of montmorillonite, colloidal silicon oxide, colloidal silicon oxide-aluminum oxide mixture, and sepiolite. 2. The aqueous suspension according to 1. 4. The composition according to claim 1, wherein the content of bensultap is 5 to 60% by weight based on the whole preparation.
4. The aqueous suspension according to any one of 3. 5. Content of the whole preparation is 5 to 60% by weight of bensultap, 0.2 to 10% by weight of a surfactant, 0.5 to 15% by weight of urea or L-lysine hydrochloride, and 0.1 to 0.1% of polyethylene glycol. -5% by weight, and a suspension aid 0.
5 to 10% by weight.
The aqueous suspension according to any one of the above.