JPH11349412A - Stable aqueous suspensionlike agrochemical formulation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous suspensionlike agrochemical formulation containing a herbicidally active ingredient stable in long-term preservation and comprising a specific compound. SOLUTION: This formulation is obtained by formulating [3-(2-chloro-4- methylsulfenylbenzoyl)-4-phenylthio]bicyclo[3.2.1]oct-3-en-2-one and a ligninsulfonate in a ratio of 1 pts.wt. to 0.05-15 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a herbicide active ingredient for paddy fields [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1].
The present invention relates to an aqueous pesticide suspension containing oct-3-en-2-one which is stable in long-term storage.

[0002]

2. Description of the Related Art [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] oct-3-en-2-one has a melting point of 1: 1.
A new compound of 85-187 ° C, water solubility 0.05 ppm, and yellow powder. It has a low dose and is higher than annual broadleaf weeds such as cyperaceae weeds such as fireflies, which are important weeds in paddy fields, and oaks. It is a component that is expected to be put to practical use as a paddy herbicide because it shows herbicidal effects and residual effects of the drug, has no phytotoxicity, has no toxicity and is environmentally safe.

On the other hand, a preparation in which a solid active ingredient insoluble or hardly soluble in water is pulverized into fine particles and dispersed or suspended in water using a dispersant is an aqueous suspension pesticide preparation or a flowable preparation. It has attracted attention as a preparation that improves powdering, solidification, inconvenient measurement, and the like, as seen in granules and wettable powders. In addition, recent herbicides for paddy fields have good diffusibility into paddy fields and can be treated uniformly, and can be sprayed with undiluted solution as it is, or can be directly treated at the inflow port (water port).
Flowable preparations that focus on ease of use are becoming mainstream.

In general, flowable preparations are liable to undergo chemical changes such as hydrolysis of the active ingredient during long-term storage, increase in the particle size of the pulverized particles, aggregation and sedimentation, and hard caking and gelation of the sedimented layer. Therefore, various techniques for preventing this and stabilizing the preparation have been developed. [3- (2-Chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] oct-3-en-2- using the flowable formulation technology developed so far.
In the case of using a flowable preparation, the increase in the particle size of the pulverized particles, aggregation and sedimentation, hard caking of the sedimented layer, gelation, and the like occurred, and it was difficult to produce a stable flowable preparation.

[0005] Prior art related to the present invention is as follows. A method of stabilizing a flowable preparation, characterized by dispersing and coexisting a lignin sulfonate as a dispersant with a specific active ingredient which is solid at room temperature and is poorly water-soluble or insoluble (JP-A-5-43401).
No., JP-A-10-87414). However, the active ingredients described therein are novel compounds [3-
(2-chloro-4-methylsulfenylbenzoyl)-
4-phenylthio] bicyclo [3.2.1] oct-3
-En-2-one is a compound having a completely different structure,
Even if a flowable preparation is produced based on the content of the above-mentioned publication, it is difficult to presume that a stable flowable preparation can be always obtained for the present compound.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2. 1] Oct-3-ene-2
An object of the present invention is to provide a flowable preparation which is stable in long-term storage without impairing the original excellent properties of the flowable preparation containing -on, that is, the herbicidal action of the active ingredient and the properties of the preparation itself.

[0007]

Means for Solving the Problems The inventors of the present invention have made various studies to solve the above problems, and as a result, have found that by dispersing and coexisting lignin sulfonate, a stable flowable preparation can be obtained over a long period of storage. Thus, the present invention has been completed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides: 1) [3- (2-chloro-4-) as an active ingredient, characterized by dispersing and coexisting lignin sulfonate.
Methylsulfenylbenzoyl) -4-phenylthio]
A stable aqueous suspension pesticide formulation containing bicyclo [3.2.1] oct-3-en-2-one, and 2) the amount of ligninsulfonate is the active ingredient [3-
(2-chloro-4-methylsulfenylbenzoyl)-
4-phenylthio] bicyclo [3.2.1] oct-3
The present invention provides the stable aqueous suspension pesticide preparation according to the above 1, which is 0.05 to 15 parts by weight per 1 part by weight of -en-2-one.

Hereinafter, the method of the present invention will be described in more detail. In the method of the present invention, [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] oct-3-ene-2 is used.
It is characterized in that -one and ligninsulfonate are dispersed and coexist.

The lignin sulfonate used in the present invention is a water-soluble polymer sulfonate obtained by sulfonating lignin, which is a main component of wood, and neutralizing it with an alkali such as sodium hydroxide. Lignin is a major component of wood, together with cellulose and hemicellulose.
It is an amorphous polymer substance containing 0 to 30%, and is a substance in which phenylpropane-based structural units are condensed in a complicated manner. In the paper and pulp industries, wood is digested with alkali (alkali method), sodium sulfate (kraft method), calcium acid sulfite (sulfite method), etc. to separate only fibrous material as purely as possible, The components become soluble and are by-produced. Lignin sulfonate is produced using this cooking eluate as a raw material.
Lignin sulfonate molecular weight in the high molecular compound that millions hundreds shows dispersing ability as a surfactant having a hydrophobic backbone and a sulfonic group of C ₆ -C _3, other hydrophilic groups at the same time.

In the present invention, [3- (2-chloro-4)
A process for producing a flowable formulation containing -methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] oct-3-en-2-one is known as a general process for producing agrochemical flowable formulation. Method is applied. That is, the present compound and other active ingredients are pulverized together with a dispersing agent, a wetting agent, an antifreezing agent, an antifoaming agent, a thickening agent, an antifungal agent (preservative) and the like by pulverization by a wet method or a dry method. You.

[3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.
2.1] Other active ingredients used with oct-3-en-2-one include, for example, imazsulfuron (generic name of agricultural chemical; the same applies hereinafter), pyrazosulfuron-ethyl, benzulfuron-methyl, azimsulfuron, ethoxysulfuron MY-100 (test name) , The same applies hereinafter), and one or a mixture of two or more with NBA-061 or the like, but is not limited thereto.

[3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.
2.1] The content of oct-3-en-2-one is not particularly limited, but is about 1 to 60% by weight, usually 2 to 60% by weight.
About 40% by weight, when mixed with other active ingredients,
The mixing ratio of the other active ingredients is 0.1 part by weight with respect to 1 part by weight of the present compound.
It is about 01 to 20 parts by weight.

The compounding amount of the lignin sulfonate used in the present invention is 0.1 to 20% by weight. If the amount is too small, it is difficult to expect a sufficient effect. On the other hand, if the amount is used in an excessively large amount, the suppression effect can be obtained as it is, but there is a possibility that a problem may occur in the original characteristics of the agricultural chemical formulation. Usually, 1 to 1
A practically sufficient effect can be obtained in the range of 0% by weight.

In the present invention, components other than lignin sulfonate can be used as long as they are compounds generally used in agricultural chemicals. Other components, for example, antifreeze, wetting agent, antifoaming agent,
Thickeners, fungicides (preservatives), pH regulators and the like are used. Specific examples of the antifreezing agent include, for example, ethylene glycol, propylene glycol, and glycerin. The wetting agent is not particularly limited as long as it is a surfactant having a surface tension lowering ability. Specific examples of the thickener (anti-settling agent) include gum arabic, guar gum, xanthan gum, sodium alginate, polyvinyl alcohol, carboxymethyl cellulose, and a hydrophilic inorganic thickener. As the antifungal agent (preservative), specifically, for example, sodium benzoate, 1,2-benzisothiazolin-3-one (BI
T) and the like. Specific examples of the antifoaming agent include a silicone compound and an acetylene derivative. Examples of the pH adjuster include various inorganic acids and organic acids such as phosphoric acid, sulfuric acid, sulfonic acid, and carboxylic acid, and salts and esters thereof. Specifically, for example, acidic phosphate, citric acid, maleic acid, sorbic acid, lactic acid, tartaric acid and the like are exemplified. In addition, citric acid-disodium hydrogen phosphate, potassium dihydrogen phosphate-disodium hydrogen phosphate and the like can be mentioned.

[0016]

[Production method] In the case of wet pulverization generally adopted, the active ingredient [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] is used.
Octo-3-en-2-one, lignin sulfonate,
The antifreezing agent, the wetting agent, the defoaming agent, the pH adjuster, and water are mixed and dispersed using a polytron homogenizer or the like of a mixer, and then pulverized, preferably, pulverized using a dyno mill or the like of a wet pulverizer. Particle size is 0.5-5 μm, preferably 3 μm
m. The wet pulverizer is not limited to the above-mentioned dyno mill, but may be a wet pulverizer such as an attritor, a sand grinder, a pearl mill, an apex mill, a biscomil, and an ultraviscomill. Next, a thickener and an antifungal agent (preservative) are added to the obtained pulverized liquid, followed by stirring and mixing to obtain a flowable preparation. Further, a flowable preparation according to the present invention can be obtained by the dry pulverization method as described below. That is, the present compound is pulverized into a fine powder having the above-mentioned particle size by a dry pulverizer such as a jet mill, a hammer mill, and a pin mill, and the obtained pulverized product is subjected to lignin sulfonate, an antifreezing agent, a wetting agent, and a defoaming agent. Agent, p
It may be added to a liquid in which an H regulator, a thickener, a fungicide (preservative) and the like are dispersed.

[0017]

EXAMPLES The method of the present invention will be described in more detail with reference to representative examples. However, these are merely examples for explanation, and therefore, the present invention is not limited only to these examples. In the following examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 6 parts of [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] oct-3-en-2-one, sun extract P- 252
(Lignin sulfonic acid salt: Nippon Paper Industries Co., Ltd.) 3 parts, propylene glycol 10 parts, Antihome E-20 (silicone emulsion: Kao Corporation) 0.2 parts, Kunipia F (Montmorillonite: Kunimine Industry Co., Ltd.) ) 1.5
Part, Proxel GXL (antifungal agent: Zeneca Corporation) 0.1
The resulting mixture was mixed and pulverized with a polytron homogenizer, and then pulverized with a wet pulverizer Dynomill to obtain a 6% flowable preparation of the present compound. After leaving this flowable product in a recycling room at −5 ° C. and 50 ° C. every 24 hours for 3 weeks, measure the average particle size in the flowable product using a laser diffraction particle size distribution analyzer (JEOL Ltd.). And compared with the average particle diameter at the time of production. As a result, the average particle diameter at the time of production and after 3 weeks were the same, and no change in appearance was observed.

Example 2 In place of Sun Extract P-252 of Example 1, 3 parts of Vanillex N (ligninsulfonate: Nippon Paper Industries Co., Ltd.) was added. Compound 6
% Flowable formulation was obtained. This flowable formulation is left in a recycling room at −5 ° C. and 50 ° C. every 24 hours for 3 weeks, and then a laser diffraction particle size distribution analyzer (JEOL Ltd.)
Was used to measure the average particle diameter in the flowable preparation, and compared with the average particle diameter at the time of production. As a result, the average particle diameter at the time of production and after 3 weeks were the same, and no change in appearance was observed.

Comparative Example 1 In place of Sun Extract P-252 of Example 1, 3 parts of Newcalgen Fs-7 (polyoxyalkylene phenyl ether sulfate salt: Takemoto Yushi Co., Ltd.) was added, and the other conditions were the same as in Example 1. By performing various operations, a 6% flowable preparation of the present compound was obtained. This flowable formulation is -5 ℃ and 50 ℃ 24
After being left in the recycling room every hour for 3 weeks, the average particle diameter in the flowable preparation was measured using a laser diffraction particle size distribution analyzer (JEOL Ltd.) and compared with the average particle diameter at the time of production. As a result, the average particle diameter after three weeks was increased by 30% from the average particle diameter at the time of production, and a state in which two layers were separated from the appearance was confirmed.

Comparative Example 2 In place of Sun Extract P-252 of Example 1, Solpol 7290-P (polyoxyethylene phenylalkyl allyl ether sulfate salt: Toho Chemical Industry Co., Ltd.) 3
The same procedures as in Example 1 were carried out except for the above, to obtain a 6% flowable preparation of the present compound. This flowable formulation is -5
After standing for 3 weeks in a recycling room at 24 ° C. and 50 ° C. every 24 hours, the average particle size in the flowable preparation was measured using a laser diffraction type particle size distribution analyzer (JEOL Ltd.) It was compared with the diameter. As a result, the average particle diameter after three weeks was increased by 30% from the average particle diameter at the time of production, and a state in which two layers were separated from the appearance was confirmed.

[3-] in the flowable of Examples 1 and 2
(2-chloro-4-methylsulfenylbenzoyl)-
4-phenylthio] bicyclo [3.2.1] oct-3
No increase in particle size was observed for -en-2-one, but the increase in particle size was confirmed for those of Comparative Examples 1 and 2, and two-layer separation was also performed. The condition was found to be impaired.

[0023]

According to the present invention, by dispersing and coexisting lignin sulfonate, [3-
(2-chloro-4-methylsulfenylbenzoyl)-
4-phenylthio] bicyclo [3.2.1] oct-3
-Excellent characteristics inherent to a flowable preparation containing en-2-one can be maintained. That is, a sufficient herbicidal action as a herbicide for paddy fields can be exhibited, and the finely divided active ingredient can be maintained in a stable suspension state during long-term storage.

Claims (2)

[Claims] [1] [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1] as an active ingredient, characterized by dispersing and coexisting a lignin sulfonate. ] Oct-3-ene-2
A stable aqueous suspension pesticide formulation containing -one. 2. The amount of the lignin sulfonate depends on the amount of the active ingredient [3- (2-chloro-4-methylsulfenylbenzoyl) -4-phenylthio] bicyclo [3.2.1].
0.05 to 1 part by weight of oct-3-en-2-one
The aqueous pesticidal suspension according to claim 1, wherein the amount is from 15 to 15 parts by weight.