JPH0959105A - Aqueous suspension formulation composition - Google Patents

Abstract

(57) [Summary] [Structure] In an aqueous suspension preparation containing 2,3-dicyano-1,4-dithiaanthraquinone, a polyhydric alcohol is used as an anti-aggregation agent in an amount of 8% by weight or more based on the total amount of the preparation. An aqueous suspension preparation composition, characterized by containing less than or equal to wt%. [Effect] During long-term storage, it prevents aggregation of active ingredient particles and caking, and guarantees stable formulation properties for a long period of time.

Description

Detailed Description of the Invention

[0001]

The present invention relates to 2,3-dicyano-1,
The present invention relates to an agricultural fungicide composition containing 4-dithiaanthraquinone (generic name: dithianon). More specifically, it relates to an improved aqueous suspension formulation composition containing dithianon (hereinafter referred to as "flowable agent").

[0002]

BACKGROUND OF THE INVENTION Dithianon is mainly used for citrus black spot, scab, anthracnose, pear black spot, scab, ring spot, etc., for peach, persimmon, grape, plum, apple, strawberry, konjac. ,
It is a fungicide that is highly effective against diseases such as tea, and its mechanism of action is thought to act on the protoplasm of pathogenic bacteria, enzymes, and thiol groups of proteins. And the bactericidal effect is superior to the preventive effect rather than the therapeutic effect.

Conventionally, dithianon has been used mainly in the form of a wettable powder in Japan, and in the form of powder in a very limited field, but it becomes more economical. , A suspension formulation (flowable formulation) was developed in which the dithianon drug substance was wet peptized using a bead mill or the like to have an average particle size of about 1 μm. Since this product can enhance the efficacy by reducing the particle size, a lower content of the flowable agent can be used at the same dilution ratio as compared with the wettable powder, and the dithianone drug substance can be saved accordingly. Specifically, a flowable agent containing 40% of dithianon is commercially available.

[0004]

However, this dithianon flowable agent has poor physical storage stability, and liquid separation and caking, which are considered to be caused by agglomeration of active ingredients, occur during storage, resulting in formulation from a container. Occasionally, problems such as hard to come out or not at all occurred. It was found that this decrease in physical properties was caused not only by freezing, which is often seen in flowable formulations when the formulation was placed below freezing, but also when stored at temperatures above freezing. This is thought to be due to the unique physicochemical properties of the dithianon particles in the formulation, but the details are unknown.

[0005]

Means for Solving the Problems In the dithianon flowable agent, the present inventors have used a polyhydric alcohol such as ethylene glycol or propylene glycol as an anticoagulant in an amount of 8% by weight or more, preferably 10% by weight, based on the total amount of the preparation. It was found that the physical storage stability can be improved by adding at least 0.1%, and the present invention was completed.

That is, the present invention provides a dithianon flowable agent which contains a polyhydric alcohol as an anti-agglomeration agent and is unlikely to undergo physical changes such as separation of liquid during storage, caking or gelation.

In the flowable agent of the present invention, the content of dithianon with respect to the total amount of the preparation is about 10 to 70% by weight, which is determined in consideration of manufacturability, cost, usability and the like. In Japan, 40% by weight is used.

In the present invention, an agrochemical component other than dithianone can be added as necessary to enhance the bactericidal effect, broaden the spectrum, or impart an insecticidal effect. As a preferable mixed component, cupric hydroxide, 8-hydroxyquinoline copper, a copper agent such as basic copper chloride, thiophanate methyl, benzimidazole-based agents such as thiabendazole, iprodione, vinclozolin, dicarboximide-based agents such as procymidone, Examples include EBI agents such as triflumizole and phenalimol, dithiocarbamate compounds such as zineb, manneb and thiuram, metalaxyl, captan, streptomycin and the like. In these mixed flowables, care should be taken as the physicochemical properties may be greatly influenced by the properties of the mixed raw materials.

Examples of the polyhydric alcohol used as an anticoagulant in the present invention include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and butylene glycol, or condensates thereof, glycerin, Examples thereof include diglycerin, glycerin monoether, and glycerin monoester. Of these, ethylene glycol and propylene glycol are preferable in terms of cost and effect.

The amount added is 8% by weight or more, preferably 10% by weight, based on the flowable agent. This is because if the amount is less than this, the effect of preventing aggregation is small. If the amount of these polyhydric alcohols added is too large, the amount of water added will be reduced, the cost will be high, and other physical properties of the preparation will be prone to problems, so the amount should be kept at 20% by weight at most. When using ethylene glycol, the amount added is 8
It is preferably not less than 10% by weight, and in the case of propylene glycol, not less than 10% by weight is preferable.

A flowable agent is a dispersion of solid drug substance particles in water. Generally, a surfactant, a thickener, an antifreezing agent, an antiseptic agent, an antifoaming agent, etc. are used in addition to the drug substance and water. Be compounded. These auxiliaries are also blended in the flowable agent of the present invention, if necessary.

The surfactant used in the composition of the present invention is not particularly limited, and various anionic surfactants, nonionic surfactants and the like which have been conventionally used in the field of agrochemical formulation can be used.

These surfactants function as a wetting agent or a dispersant for wetting the dithianon drug substance particles or the other active ingredient drug substance particles to be mixed with water and stabilizing the dispersion in water. , Selected from the following surfactants:

As the anionic surfactant, for example,
Alkyl sulfonic acid, alpha olefin sulfonic acid,
Sulfonic acid type surfactants such as ligninsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, naphthalenesulfonic acid formalin condensate, dialkylsulfosuccinate and salts thereof, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl allyl ether Sulfates, polyoxyethylene styryl phenyl ether sulphates, polyoxyethylene phenyl alkyl allyl ether sulphates, polyoxyalkylene glycol sulphates, higher alcohol sulphates, fatty acid ester sulphates, phenylphenol (EO) sulphates, etc. Salt, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl Phosphate surfactants such as sulfates, phenylphenol (EO) phosphate salts, polyoxyethylene phenylalkyl allyl ether phosphates, higher alcohol phosphates, polyoxyethylene tribenzylphenol phosphate and salts thereof, higher fatty acid salts, polycarboxylic acids Examples thereof include acid type surfactants and salts thereof. The salts of the above surfactants include sodium,
Potassium, magnesium, calcium, ammonium,
It includes salts of ethanolamine, diethanolamine, triethanolamine and various amines.

Examples of the nonionic surfactant include, for example,
Polyoxyethylene alkyl allyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene phenyl alkyl allyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol, polyoxyethylene alkyl ester, polyoxyethylene poly Examples thereof include oxypropylene block copolymer, polyoxyalkylene glycol, alkynediol (acetylene glycol), alkynylene polyoxyethylene diol, sorbitan fatty acid ester, and alkylaryl ether formalin condensate.

These surfactants are used alone or as a mixture of two or more, and the addition amount thereof is selected within the range of 0.1 to 10% by weight.

An inorganic thickener and / or a water-soluble polymer is used as the thickener. Inorganic thickeners include smectite-based clay minerals and colloidal silica, and smectite-based clay minerals include bee gum, banger (above,
Vanderbilt), Laponite (Laporte),
Examples include bentonite, and examples of colloidal silica include Aerosil (manufactured by Degussa).

As the water-soluble polymer, various natural products, synthetic products or semi-synthetic products can be used. For example, guar gum, locust bean gum, quince seed gum, tara gum, tragacanth gum, karaya gum, xanthan gum (xanthan gum), Various gums such as heteropolysaccharides such as welan gum, rumzan gum, carrageenan and gum arabic, alginic acid derivatives such as sodium alginate, ammonium alginate, propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methacrylate, polyethylene oxide, polyacrylic Synthetic organic water-soluble polymer compounds such as acid, sodium polyacrylate, polyacrylamide, dextrin, pectin, gelatin, casein,
Natural water-soluble polymer compounds such as glue, albumin, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose,
Cellulose derivatives such as hydroxypropyl cellulose,
Examples thereof include starch derivatives such as sodium carboxymethyl starch and hydroxyethyl starch.

These thickeners can be used alone or in combination of two or more, and the addition amount thereof is determined in the range of 0.01 to 10% by weight to give an appropriate viscosity. By the addition of this thickener, the original particles are uniformly dispersed and stabilized in the flowable preparation and settling is prevented, but in the dithianon flowable agent of the present invention, a polyhydric alcohol is further used as an anticoagulant. It is added.

Usually, in a flowable agent, an antifreezing agent is added to prevent freezing in the cold season, but in the flowable agent of the present invention, the polyhydric alcohol added as an anticoagulant functions. Therefore, it is not necessary to add it.

In the present invention, various other components such as a defoaming agent such as silicone emulsion, an antibacterial and antifungal agent, or a coloring agent may be further added. As the antibacterial / antifungal agent, various substances can be used, for example, sorbic acid and its salts, benzoic acid and its salts, dehydroacetic acid and its salts, paraoxybenzoic acid esters, thiabendazole, BIT, thiazolone, BNPK. , Neoplatinth (manufactured by Ueno Pharmaceutical Co., Ltd.), Hoxite LX-2 (manufactured by Hokuko Chemical Co., Ltd.), Dell Top, Dell Top 33
(Above, Takeda Pharmaceutical Co., Ltd.), Biocide 800
A, Biocide 800S (above, Taisho Co., Ltd.), Proxel CRL, Proxel GXL, Proxel XL-
2. Examples include Proxel TN (above manufactured by Zeneca), Biotac, Bioace, Biohove (above manufactured by Kei AI Kasei Co., Ltd.). In addition to these, various antibacterial and antifungal agents can be appropriately selected and used. Further, the amount of addition when added to the composition of the present invention can be freely selected.

[0022]

In the present invention, the storage stability of the dithianon flowable agent can be improved by adding 8% by weight or more of the polyhydric alcohol. Although the reason for this is not clear, it is considered that, for example, dithianone particles dispersed in water adsorb these polyhydric alcohols on the surface, which prevents aggregation between particles.

[0023]

EXAMPLES The present invention will now be described with reference to examples.

[0024]

[Formulation Example 1] Newcargen FS- in a stainless steel container
7 (Takemoto Yushi Co., Ltd. anionic surfactant) 5.6
Parts by weight, 11.1 parts by weight of ethylene glycol, water 33.
1 part by weight and 0.2 part by weight of Pronal EX-300 (an antifoaming agent manufactured by Toho Chemical Industry Co., Ltd.) are mixed and dissolved. To this, 50 parts by weight of dithianon drug substance (93.0%) was added little by little, and when uniform, glass beads (φ1 mm) were added in substantially the same volume, and the mixture was stirred at high speed with a wheel-shaped stirring blade for 4 hours to deflocculate. . For 90 parts by weight of this peptized liquid, Kelzan S (US K
xanthan gum manufactured by elco) 1% + Proxel GXL
(Preservative manufactured by Zeneca Corporation) 10 parts by weight of a 2% aqueous solution were mixed to obtain 40% flowable. The content of dithianon in this flowable agent was 41.8% by weight. The average particle size measured by the laser diffraction particle size distribution measuring device is 0.8.
7 μm, viscosity (20 ° C., 12 rpm) is 1330
Initial physical properties such as cps, suspending property, fineness, dispersibility were also good.

[0025]

[Formulation Examples 2 to 7] In the same manner as in Formulation Example 1, flowable agents were obtained according to the formulations shown in Table 1. In the table, Solpol 3078 is a blend of anionic and nonionic surfactants manufactured by Toho Chemical Industry Co., Ltd., and Veegum R is a smectite inorganic thickener manufactured by Vanderbilt.

[0026]

[Table 1]

[0027]

[Comparative Examples 1 to 5] In the same manner as in Formulation Example 1, flowable agents were obtained according to the formulations shown in Table 2. Raw materials represented by products in the table are the same as above.

[0028]

[Table 2]

[0029]

[Test Example 1] The samples of Formulation Examples 1 to 5 and Comparative Examples 1 to 5 were tightly stoppered in glass bottles, preserved in abusive condition at 40 ° C., taken out after 3 months, and the decomposition rate of active ingredient (dithianone) and suspension (total) were measured. Agricultural method, 600-fold dilution), pH (5-fold dilution), and viscosity (B-type viscometer 12 rpm, 20 ° C.) were examined. The results are shown in Table 3.

[0030]

[Table 3]

[0031]

[Test Example 2] 250 g of a wide-mouth plastic bottle (caliber: 25) of 250 g of the flowable agent of Formulation Examples 1-5 and Comparative Examples 1-5
mm) for 3 days at -5 ° C, 1 day at room temperature, 3 ° C at 40 ° C.
An abuse cycle test was conducted in which 0 cycles were repeated at room temperature for 1 day, and 3 cycles were repeated. These samples are
No external freezing was observed during storage at 5 ° C. After the completion of 3 cycles, the following items were examined. (1) Container discharge rate (%): The bottle was tilted and the amount of the content liquid discharged in 10 minutes was examined. (2) Caking: It was investigated whether or not there was solidified contents in the bottle. ×: Large, Δ: Little, ○: Almost (3) Aggregation: The remaining content liquid was collected and examined by an optical microscope for the presence or absence of aggregates in the flowable preparation (600 times). The results are shown in Table 4.

[0032]

[Table 4]

[0033]

[Test Example 3] The flowable agents of Examples 1 and 2 and Comparative Examples 1 and 5 were filled in a plastic bottle of 500 cc and stored in a wooden warehouse (without air conditioning). After 18 months, the same test as in Test Example 2 was performed. The temperature of the warehouse during this period was 41 ° C at the highest and 2 ° C at the lowest, and the temperature did not fall below freezing. Table 5 shows the results.

[0034]

[Table 5]

[0035]

The flowable agent of the present invention has good physical properties as shown in Table 3, and a polyhydric alcohol such as ethylene glycol or propylene glycol is used as an anticoagulant.
By adding at least wt%, as shown in Test Examples 2 and 3, it is possible to prevent aggregation and caking of dithianon particles due to long-term storage. Agglomeration and caking cannot be prevented by a urea or ammonium chloride addition formulation which has been conventionally used as an antifreeze formulation of a flowable agent, or an ethylene glycol or propylene addition formulation of less than 8% by weight.

Claims (4)

[Claims] 1. An aqueous suspension preparation containing 2,3-dicyano-1,4-dithiaanthraquinone, which is used as an anticoagulant in an amount of 8% by weight or more and 20% by weight or more based on the total amount of the preparation.
An aqueous suspension preparation composition comprising the following polyhydric alcohol. 2. The polyhydric alcohol is ethylene glycol,
The aqueous suspension preparation composition according to claim 1, which is one kind or two or more kinds selected from propylene glycol and glycerin. 3. The polyhydric alcohol is ethylene glycol, and its content relative to the total amount of the preparation is 8% by weight to 2%.
It is 0% by weight, and the aqueous suspension preparation composition according to claim 1 or 2. 4. The aqueous suspension preparation composition according to claim 1 or 2, wherein the polyhydric alcohol is propylene glycol, and its content relative to the total amount of the preparation is 10% by weight to 20% by weight.