JP2853941B2 - Pesticide solid formulation composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for agrochemical solid preparation (hereinafter simply referred to as "composition"). Agrochemical formulations in various formulations have been put to practical use, and in particular, solid formulations having the property of being easily emulsified in water have recently attracted attention. The present invention relates to an improvement in a composition for obtaining such a solid preparation.

[0002]

2. Description of the Related Art Conventionally, a water-soluble polymer is added as a binder to a water-insoluble inorganic solid carrier such as talc, bentonite, gypsum or the like, or a water-insoluble organic solid carrier such as cork powder or cellulose powder. A material obtained by impregnating and adsorbing a bulk material, a surfactant and the like is used. Agrochemical solid preparations have been obtained by using such a composition and giving shape by various shaping means.

However, the above-mentioned conventional compositions have the following disadvantages due to the use of a water-insoluble solid carrier. 1) When the obtained pesticidal solid preparation is dispersed in water, an aggregate of a water-insoluble solid carrier is easily formed,
Difficult to spray. 2) After spraying the obtained pesticidal solid preparation, the water-insoluble solid carrier remains in the soil or on the crop for a long time. 3) The medicinal component is strongly adsorbed to the water-insoluble solid carrier, and the once-adsorbed medicinal component has a very slow release, so that the use efficiency of the medicinal component is poor and the medicinal component remains for a long period of time.

Therefore, in order to solve the drawbacks caused by using the water-insoluble solid carrier, a proposal has been made to use a water-soluble solid carrier instead of the water-insoluble solid carrier. For example, 1) Examples of using a water-soluble inorganic salt such as urea and thiourea as a water-soluble solid carrier (JP-A-2-108604);
2) Examples using saccharides such as dextrin, lactose and starch hydrolysis products (JP-A-3-47103, JP-A-57-10)
9702), 3) Examples using polyalkylene glycols which are solid at normal temperature (Japanese Patent Application Laid-Open No. 2-279604), and examples using a water-insoluble inorganic solid carrier in combination (Japanese Patent Application Laid-Open No. 2-2796).
03).

However, the conventional proposals using the above-mentioned water-soluble solid carriers have the following disadvantages. 1) In the case of a conventional example using a water-soluble inorganic salt such as urea and thiourea,
It is difficult to obtain a pesticidal solid formulation that can be stably emulsified in water. 2) In the case of conventional proposals using saccharides, the water-soluble solid carrier is liable to be deteriorated in a step of obtaining a solid pesticide formulation, such as a granulation step and a drying step, so that emulsion stability is deteriorated. 3) In the case of conventional proposals using polyalkylene glycols, the obtained agricultural chemical solid preparation is liable to fuse or stick during storage or transportation, and these are particularly remarkable in summer. Poor shape stability causes trouble in handling. If a water-insoluble inorganic solid carrier is used in combination to reduce such a defect, it is inevitable that the release of the medicinal component is slow as described above.

[0006]

The problem to be solved by the present invention is that a conventional composition using a water-insoluble solid carrier or a water-soluble solid carrier is difficult to dissolve in an agricultural chemical solid preparation obtained therefrom. It is time-consuming, poor in emulsion stability, and poor in shape stability.

[0007]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above-mentioned problems, a water-soluble solid carrier in which a specific aromatic compound and a water-soluble polymer compound are blended in a predetermined ratio as a solid carrier is used. It has been found that a composition comprising a substantially water-insoluble pesticide bulk in a proportion and a surfactant in a predetermined proportion to the pesticide bulk is respectively suitable.

That is, the present invention provides a solid form comprising an aromatic compound selected from 1) a salt of an aromatic carboxylic acid and 2) a mixture of an aromatic carboxylic acid and a salt of an aromatic carboxylic acid, and a water-soluble polymer compound. Containing 100 parts by weight or less of a substantially water-insoluble pesticidal active ingredient per 100 parts by weight of the carrier,
In addition, a surfactant is used in an amount of 5-1 to 100 parts by weight of the pesticide bulk material.
A composition containing the aromatic compound / the water-soluble polymer compound at a ratio of 99/1 by weight.
To 65/35 (weight ratio).

In the composition of the present invention, the solid carrier comprises an aromatic compound and a water-soluble polymer compound,
The aromatic compound is selected from 1) a salt of an aromatic carboxylic acid, 2) a mixture of an aromatic carboxylic acid and a salt of an aromatic carboxylic acid, and the above 1) and 2).

The aromatic compounds constituting the solid carrier include 1) salts of aromatic monocarboxylic acids such as benzoic acid, toluic acid and naphthalene monocarboxylic acid; 2) phthalic acid, isophthalic acid, terephthalic acid; Salts of aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid; 3) salts of aromatic tri- or tetracarboxylic acids such as trimellitic acid and pyromellitic acid; 4) salts and aromatics of aromatic carboxylic acids as exemplified above. And mixtures with aromatic carboxylic acids.

The salts of aromatic carboxylic acids as exemplified above include their fully neutralized salts and partially neutralized salts having a free carboxyl group. Such aromatic carboxylic acid salts include 1) alkali metal salts such as sodium, potassium and lithium, 2) calcium, magnesium,
Alkaline earth metal salts such as barium; and 3) organic salts such as alkanolamines and quaternary ammoniums.

When only the salt of an aromatic carboxylic acid is used as the aromatic compound constituting the solid carrier, sodium benzoate, sodium hydrogen phthalate, potassium hydrogen isophthalate, sodium dihydrogen trimellitate may be used. It is preferable to use an alkali metal salt of an aromatic carboxylic acid such as When a mixture of an alkali metal salt of an aromatic carboxylic acid and an aromatic carboxylic acid is used as the aromatic compound constituting the solid carrier, a carboxyl group involved in salt formation in the alkali metal salt of an aromatic carboxylic acid is used. Is n in one molecule, the ratio of both is alkali metal aromatic carboxylate / aromatic carboxylic acid = 1 / (2n−
It is preferable to use one having a range of 1) to 1 / (n-1) (molar ratio). Specifically, aromatic alkali carboxylic acid monoalkali metal salt / aromatic carboxylic acid ≧ 1/1 (molar ratio), aromatic carboxylic acid dialkali metal salt / aromatic carboxylic acid = 1/3 to 1/1 (molar ratio) ), Aromatic alkali carboxylic acid alkali metal salt / aromatic carboxylic acid = 1/5 to 1 /
It is preferable to use those which give 2 (molar ratio).

The water-soluble polymer compound constituting the solid carrier includes known compounds such as natural polymer compounds, modified natural polymer compounds, and synthetic polymer compounds.
Examples of such water-soluble polymer compounds include: 1) natural polymer compounds such as xanthan gum, gum arabic, and guar gum;
2) Modified natural polymer compounds such as hydroxyethylcellulose and carboxymethylcellulose 3) Polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylamide, poly (meth) acrylate, polyalkoxylated polyalkylenepolyamine, having 4 or more carbon atoms Synthetic polymer compounds such as a salt of a copolymer of olefin and maleic anhydride and a salt of a copolymer of styrene and maleic anhydride, among which polyvinyl alcohol,
Nonionic water-soluble polymer compounds which do not dissociate in water, such as partially saponified polyvinyl acetate and hydroxyethyl cellulose, are preferred.

In the composition of the present invention, the solid carrier is composed of the aromatic compound and the water-soluble polymer compound as described above, and the aromatic compound / the water-soluble polymer compound = It is composed of 99/1 to 65/35 (weight ratio), preferably 90/10 to 75/25 (weight ratio).

In the composition of the present invention, the pesticidal drug substance is substantially water-insoluble, and specifically has a solubility in water at room temperature of 1% or less, and there is no particular limitation on the type thereof. However, insecticides, fungicides and herbicides are advantageously applied.

As such insecticides, 1) O, O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) thiophosphate (diazinone), O, O-
Dimethyl-O- (4-methylthio-m-tolyl) thiophosphate (MPP), O, O-dimethyl-O- (4-
Nitro-m-tolyl) thiophosphate (MEP),
O, O-dipropyl-O- (4-methylthiophenyl)
Organophosphate insecticides such as phosphate (propaphos), S-α-ethoxycarbonylbenzyl-O, O-dimethylphosphorodithioate (Elsan), 2) 2
-(4-ethoxyphenyl) -2-methoxypropyl-
3-phenoxybenzyl ether (trebon), (R
S) -α-cyano-phenoxybenzyl (RS) -α-
Pyrethroids such as isopropyl-4-chlorophenylacetate (Sumicidin), (RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate (cyclosal) And 3) carbamate insecticides such as O-sec-butylphenylmethyl carbamate (BPMC).

The fungicides include: 1) an organic sulfur-based fungicide such as diisopropyl-1,3-dithiolan-2-ylidenemalonate (isoprothiolane); 2) S-benzyl-O, O-diisopropyl phosphorothioate ( I
BP) and organic phosphoric acid ester fungicides such as O-ethyl-S, S-diphenylphosphorodithioate (Hinozan).

Further, as herbicides, 1) S-4-chlorobenzyldiethylthiocarbamate (Saturn), S-
Carbamate herbicides such as ethyl perhydroazepine-1-carbothioate (molinate), S-1-methyl-1-phenylethylpiperidine-1-carbothioate (dimepiperate), 2) 2-chloro-2 ′, 6'-
Diethyl-N- (butoxymethyl) acetanilide (butachlor), 2-chloro-2 ′, 6′-diethyl-N
-(Methoxymethyl) acetanilide (arachlor), 2-chloro-2 ', 6'-diethyl-N- (2-
Acid amide herbicides such as propoxyethyl) acetanilide (pretilachlor); 3) 2,4-dichlorophenoxyacetate (2,4PA); S-ethyl-4-chloro-2-methylphenoxythioacetate (phenothiol); Phenoxyacetic acid herbicide 4) α, α, α
-Trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine (trifluralin), N-butyl-
Dinitroaniline herbicides such as N-ethyl-α, α, α-trifluoro-2,6-dinitro-p-toluidine (vesulosin);

In the composition of the present invention, the surfactant is
Although the type is not particularly limited, a nonionic surfactant, an anionic surfactant or a combination thereof can be advantageously used.

As such nonionic surfactants, 1)
POA phenyl ethers having a substituent on a phenyl group such as polyoxyalkylene (hereinafter simply referred to as POA) styryl phenyl ether, POA benzyl phenyl ether, and POA alkyl phenyl ether; 2) having a substituent on the phenyl group of the above 1) Formalin condensates of POA phenyl ethers, 3) polyhydric alcohol fatty acid partial esters such as sorbitan fatty acid partial ester, glycerin fatty acid partial ester, sucrose fatty acid partial ester, etc. 4) polyhydric alcohol fatty acid partial esters of the above 3) POA polyhydric alcohol fatty acid partial ester obtained by adding an alkylene oxide; 5) blocked polyoxyethylene / polyoxypropylene glycol; In any case, examples of the alkylene oxide that forms the POA include ethylene oxide, propylene oxide, and a mixture of ethylene oxide and propylene oxide, and those in which the number of moles of the alkylene oxide added is in the range of 5 to 50 mol. preferable. The molecular weight of the blocked polyoxyethylene / polyoxypropylene glycol is 2,000 to 2,000.
It is preferably 20000 and oxyethylene / oxypropylene = 50/50 to 90/10 (molar ratio).

Examples of the anionic surfactant include 1) sulfate or phosphate of POA phenyl ethers having a substituent on the phenyl group, and 2) alkylbenzene sulfonate and alkylnaphthalene sulfonate. Alkyl allyl sulfonates, 3) lignin sulfonates, and 4) dialkyl sulfosuccinates, of which 1) is preferred.

Further, as a combined use of a nonionic surfactant and an anionic surfactant, a combined use of the above-mentioned POA phenyl ether having a substituent on the phenyl group and the above-mentioned alkylbenzene sulfonate is preferable. In the present invention, selection of a surfactant can be performed by applying a known technique relating to a surfactant for agricultural chemicals.

The composition of the present invention contains a solid carrier, a pesticidal drug substance and a surfactant as described above.
The pesticidal active ingredient is contained in an amount of 100 parts by weight or less, preferably 100 to 20 parts by weight, based on 100 parts by weight of the solid carrier, and the surfactant is 5 to 100 parts by weight of the pesticidal active ingredient. 100 parts by weight, preferably 10-70
It is contained in parts by weight.

The method for preparing the composition of the present invention is not particularly limited, and known methods can be applied. As such a preparation method, 1) a solid carrier preliminarily shaped into a desired shape is prepared using an aromatic compound and a water-soluble polymer compound, and a mixture of the pesticide drug substance and a surfactant is added thereto. A method of directly impregnating and adsorbing, or impregnating and adsorbing an aqueous emulsified dispersion obtained by emulsifying or dispersing the pesticidal drug substance with a surfactant, followed by drying if necessary;
A method in which water is added to a surfactant and a water-soluble polymer compound to prepare an emulsified or suspended aqueous liquid, which is sprayed on a powdery or granular aromatic compound and dried, A) a method of preparing an emulsified or suspended aqueous composition by adding water to an agrochemical, a surfactant, an aromatic compound, and a water-soluble polymer compound, and spray-drying the composition. .

In preparing the composition of the present invention, when a liquid pesticide having a melting point of about 70 ° C. or less, particularly at room temperature or less, the above-mentioned preparation method is applied as it is, but the melting point is 70 ° C. When the above-mentioned solid pesticidal drug substance is used, a solution in which the solid pesticidal drug substance is dissolved in an organic solvent can be used. As such an organic solvent, those capable of dissolving the solid pesticidal drug substance and having a boiling point of 150 ° C. or higher and having no hindrance such as evaporation or odor in the preparation step are preferable.
Further, it is preferable that the solid carrier does not dissolve or swell, that is, does not inhibit the shape stability of the solid carrier. Specific examples include mineral oils, vegetable oils, higher fatty acid esters, aromatic hydrocarbon solvents, and the like. These organic solvents are present in a proportion of 100 parts by weight or less based on 100 parts by weight of the solid pesticide raw material. Used for

Hereinafter, the structure and effects of the present invention will be more specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples. In the following Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”.

[0027]

【Example】

Test Category 1 (Preparation of Composition) Examples 1-3 and Comparative Examples 1-3 73 parts of Saturn, 5.5 parts of polyoxyethylene (15 mol) distyrylphenyl ether, 3.5 parts of sodium dodecylbenzenesulfonate And 150 parts of a 10% aqueous solution of polyvinyl alcohol (Kuraray Povar 217 VF-N, manufactured by Kuraray Co., Ltd.), taken through a homogenizer,
A homogeneous emulsion was prepared. Separately sodium benzoate 8
A solution was prepared by dissolving 5 parts in 200 parts of warm water at 50 ° C. The two liquids prepared here were mixed to obtain an aqueous liquid. This aqueous liquid was dried using a hot-air spray dryer at a hot-air inlet temperature of 120 ° C. and an outlet temperature of 65 ° C. to obtain a powder-shaped composition (Example 1). In the same manner as above, powder-shaped compositions (Examples 2, 3 and Comparative Examples 1 to 3) having the composition shown in Table 1 or Table 2 were obtained.

Examples 4 to 6 and Comparative Examples 4 to 6 Diethylbenzene solution 50 containing 50% of trifluralin
Parts, 17 parts of polyoxyethylene (15 mol) distyryl phenyl ether sulfate ammonium and 170 parts of a 10% aqueous solution of hydroxyethyl cellulose.
Through a homogenizer, a homogeneous emulsion was prepared. This emulsion was sprayed evenly on 83 parts of sodium benzoate powder (average particle size: 100 mesh) in a fluidized bed apparatus. Then, this was dried at 50 to 55 ° C. for 2 hours in a fluidized bed drier to obtain a composition (Example 4) which was formed into granules having a water content of 1% or less. In the same manner, granulated compositions (Examples 5, 6 and Comparative Examples 4 to 6) having the composition shown in Table 1 or Table 2 were obtained.

[0029]

[Table 1]

[0030]

[Table 2]

In Tables 1 and 2, numerical values in the tables: parts A-1: sodium benzoate A-2: sodium benzoate / benzoic acid = 4/1 (weight ratio) mixture A-3: hydrogen phthalate Sodium salt B-1: Polyvinyl alcohol B-2: Hydroxyethyl cellulose C-1: Saturn C-2: Elsan C-3: Trifluralin D-1: Polyoxyethylene (15 mol) distyryl phenyl ether D-2: Dodecylbenzene Sodium sulfonate D-3: Polyoxyethylene (25 mol) distyryl phenyl ether formalin condensate D-4: Polyoxyethylene (15 mol) distyryl phenyl ether sulfate ammonium E-1: Diethyl benzene

Comparative Example 7 To 21 parts of Saturn, 6 parts of polyoxyethylene (15 mol) distyrylphenyl ether and 4 parts of sodium dodecylbenzenesulfonate were added and mixed, and then 35 parts of powdered thiourea and 24 parts of sodium sulfate were added. Was added and mixed uniformly.
To this, a 20% aqueous solution of carboxymethyl cellulose 12
And kneaded again. This was granulated using a basket-type extrusion granulator (screen hole diameter 0.6 mm),
After drying in a fluidized bed dryer at ~ 55 ° C for 2 hours, 1
A composition (Comparative Example 7) sized to a length of about 2 mm and shaped into granules was obtained.

Comparative Example 8 Polyethylene glycol (molecular weight: 40) was added to 10 parts of Saturn.
00) and mixed by heating to 80 ° C.
3 parts of polyoxyethylene (25 mol) distyryl phenyl ether formalin condensate and diatomaceous earth 77
Then, the mixture was mixed well with a juice mixer, and then cooled to room temperature. This was pulverized using a pulverizer to obtain a composition (Comparative Example 8) shaped into powder.

Comparative Example 9 Polyethylene glycol (molecular weight: 40) was added to 30 parts of Saturn.
00) and mixed by heating and melting at 80 ° C.
This was flowed on a rotating drum and cooled and solidified into a plate shape. This was crushed, sized to 1000 to 300 μm, and a granulated composition (Comparative Example 9) was obtained.

Comparative Example 10 70 parts of polyethylene glycol (molecular weight: 4000)
A granulated composition (Comparative Example 10) in the same manner as in Comparative Example 9 except that 5 parts of polyoxyethylene (25 mol) distyrylphenyl ether formalin condensate was used instead of 5 parts I got

Comparative Example 11 20 parts of trifluralin and 40 parts of diethylbenzene were taken and dissolved by heating at 50 ° C. Separately, 35 parts of dextrin was added to and dissolved in 200 parts of water at 50 ° C. Mix both solutions,
An aqueous emulsion was obtained through a homogenizer. This aqueous emulsion was dried at a hot air inlet temperature of 150 ° C. and an outlet temperature of 60 to 70 ° C. using a hot air cocurrent spray dryer to obtain a powder-shaped composition (Comparative Example 11). .

Comparative Example 12 20 parts of Saturn, 5 parts of polyoxyethylene (15 mol) distyrylphenyl ether and 5 parts of sodium dodecylbenzenesulfonate were taken and dissolved. Separately, 70 parts of carboxymethyl cellulose was added to and dissolved in 400 parts of water at 50 ° C. The two liquids were mixed to obtain a powdery composition (Comparative Example 12) in the same manner as in Comparative Example 11 below. Table 3 summarizes the compositions of these compositions (Comparative Examples 7 to 12).

[0038]

[Table 3]

In Table 3, F-1: thiourea F-2: Glauber's salt F-3: dextrin F-4: carboxymethylcellulose F-5: polyethylene glycol (molecular weight 4000) F-6: diatomaceous earth E-2: diethylbenzene

Test Category 2 (Evaluation of Composition) For each of the compositions obtained in Test Category 1, the dissolution rate was measured by the following method 1, and the emulsification stability was determined by the following methods 1, 2, and 3 and the shape stability was further evaluated by the following method 4. The results are summarized in Table 4.

Method 1 Take 100 ml of 3rd degree hard water at 20 ° C. into a stoppered cylinder,
1 g of the shaped composition was added thereto. Immediately after the introduction, the cylinder was turned over, and thereafter, the cylinder was repeatedly turned over at intervals of 2 seconds, so that a total of 10 turns were performed. In the course of this operation, the number of times of inversion until the composition completely collapsed was measured, and this was used as an index of the dissolution rate. The less the number of falls,
This indicates that the dissolution rate is high. Further, a total of 10 inversions were performed, and the emulsified and dispersed state of the aqueous liquid in the cylinder was visually observed, and the emulsion stability was evaluated according to the following criteria. ：: almost no undispersed particles, separated products, precipitates, etc. △: slight undispersed particles, separated products, precipitates, etc. ×: many undispersed particles, separated products, precipitates, etc.

Method 2 Take 100 ml of 3 degree hard water at 20 ° C. in a cylinder with a stopper and
1 g of the shaped composition was added thereto. After standing for 5 minutes, the cylinder was turned over. Immediately, the aqueous liquid in the cylinder was visually observed for the emulsified and dispersed state, and the emulsion stability was evaluated based on the same criteria as in Method 1.

Method 3 In a container equipped with a stirrer, take 1000 ml of 3 degree hard water at 20 ° C., stir the mixture at a rotation speed of 150 rpm, and immediately add 10 g of the shaped composition into the container. Stirring was continued for minutes. Immediately, the aqueous liquid in the cylinder was visually observed for the emulsified and dispersed state, and the emulsion stability was evaluated based on the same criteria as in Method 1.

Method 4 Agglomerates of the shaped composition are crushed in advance, and 1 kg of the
The equivalent was taken in a polyethylene bag, sealed and packed. This was housed in a mold having a bottom area of 10 × 10 cm, and was placed in a thermostat at 40 ° C. so that a weight of 5 kg was directly applied to the package. Twenty-four hours later, the package was opened, the composition was taken out, the degree of occurrence of the aggregate was visually observed, and the shape stability was evaluated based on the following criteria. ：: Almost no agglomerates △: Little agglomerates observed ×: Many agglomerates

[0045]

[Table 4]

[0046]

As is clear from the above, the present invention as described above has an effect that a composition using a solid carrier has a high dissolution rate of a medicinal ingredient and good emulsion stability and shape stability. .

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI A01N 47/12 A01N 47/12 A (58) Investigated field (Int.Cl. ⁶ , DB name) A01N 25/08-25 / 30 A01N 33/18 A01N 47/12 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. A solid carrier consisting of 1) a salt of an aromatic carboxylic acid and 2) an aromatic compound selected from a mixture of an aromatic carboxylic acid and a salt of an aromatic carboxylic acid, and a water-soluble polymer compound, and 100 wt. Parts of the pesticidal material substantially insoluble in water at a ratio of 100 parts by weight or less.
A composition for an agricultural chemical solid preparation containing a surfactant in an amount of 5 to 100 parts by weight with respect to 00 parts by weight, wherein the solid carrier is the aromatic compound / the water-soluble polymer compound = 99/1. ~
A composition for a pesticidal solid preparation, comprising a ratio of 65/35 (weight ratio). 2. The pesticidal solid preparation according to claim 1, wherein the pesticidal drug substance is soluble in 100 parts by weight of the pesticidal drug substance and contains 100 parts by weight or less of an organic solvent having a boiling point of 150 ° C. or higher. Composition.