JPH1143403A - Production of agrochemical granule and agrochemical granule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve productivity, yield and pharmacodynamic effects of agrochemical granules by preparing empty ball through a process for carrying out extrusion molding of water-containing composition containing a specific carrier, a specific surfactant and water in a prescribed ratio. SOLUTION: A water-containing composition containing (A) 100 pts.wt. carrier which is calcium carbonate powder having 1,000-30,000 cm<2> /g specific surface area, 0.7-20 μm average particle diameter and <=0.2 wt.% water content, (B) 0.15 pts.wt. one or two or more surfactants selected from organic phosphates represented by the formula [R is a 1-18C hydrocarbon group; Y is a residue obtained by eliminating hydroxyl group from a polyoxyalkylene diol having 1-100 recurring numbers of oxyalkylene unit; M is H or a monovalent base; (m) and (n) are each 1 or 2 and (m+n)=3] and (C) 3-14 pts.wt. water is prepared and the hollow ball is prepared through a process for carrying out extrusion molding of the resultant water-containing composition and the agrochemical active component is impregnated into the hollow ball.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing pesticide granules and pesticide granules. Various pesticide preparations such as pesticide granules, pesticide dusts, pesticide emulsions and the like are used as herbicides, insecticides, fungicides, and the like. In particular, in recent years, the use of pesticide granules has been increasing in terms of workability and safety during spraying. Agrochemical granules are produced by roughly two methods. One of them is to prepare a water-containing composition containing a carrier, a surfactant and water, and more usually an excipient and a stabilizer. Then, the water-containing composition is extruded, and simultaneously or separately granulated, and the granulated wet product is dried to produce a vacancy containing no pesticide active ingredient. There is a method of impregnating the active ingredient. According to such a method for producing pesticide granules, 1) extrusion resistance at the time of extrusion molding is small, and therefore productivity is good. 2) A granulated wet product obtained by extrusion molding has sufficient strength, and And 3) that the pesticide active ingredient is quickly eluted into water from the produced pesticide granules, and that it has good medicinal properties. Requested. The present invention relates to a method for producing a pesticide granule and a pesticide granule that can simultaneously respond to such demands.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a pesticide granule through a process of preparing a water-containing composition as described above and extruding the water-containing composition, a water-containing composition containing a relatively large amount of water has been used. There is a method of preparing and a method of preparing a reduced water-containing composition containing a relatively small amount of water. However, when a water-containing composition containing a relatively large amount of water is prepared, drying of a granulated wet product obtained by extruding such a water-containing composition requires enormous energy, and cracks and Because of the susceptibility to breakage and thus poor yield, methods for preparing reduced water compositions containing relatively small amounts of water are now being practiced.

[0003] As a method for preparing the water-reduced composition as described above, 1) a mineral carrier such as talc, clay and bentonite is used as a carrier, and an alkyl phosphate ester salt is used as a surfactant. For preparing a water-containing composition with reduced water content (JP-A-58-10330)
2) 2) Mineral carriers such as kaolinite and pyrophyllite are used as carriers, and α is used as a surfactant.
A method of preparing a water-containing composition reduced in water by using a sulfo fatty acid ester salt (JP-A-3-74305); 3) water reduced by using calcium carbonate as a carrier and a dialkyl sulfosuccinate salt as a surfactant; (Japanese Patent Publication No. 63-45858, Japanese Patent Application Laid-Open No. 4-69302) have been proposed. However, when clay is used as the carrier, the extrusion resistance of the prepared water-containing composition at the time of extrusion molding is extremely large, and therefore, the productivity is extremely low. When talc or bentonite is used as a carrier, the extrusion resistance of the prepared water-containing composition at the time of extrusion molding is small, and therefore the productivity is good, but the pesticide active ingredient is hardly eluted from the obtained pesticide granule into water,
Therefore, its efficacy is low. Furthermore, when calcium carbonate was used as a carrier and a sulfonic acid type anionic surfactant such as α-sulfofatty acid ester salt or dialkyl sulfosuccinate salt was used as a surfactant, a surfactant was prepared in the same manner as when using the clay described above. Extrusion resistance during extrusion molding of the water-containing composition is large, and therefore productivity is low, and the strength of the granulated wet product obtained by extrusion-molding the water-containing composition is low. Deformation, breakage, etc. occur, and the yield is low.

[0004]

The problem to be solved by the present invention is to prepare a reduced water-containing composition containing a relatively small amount of water and then to extrude the water-containing composition. According to the above-mentioned conventional method of producing a vacant ball containing no pesticidal active ingredient through the above process and then impregnating the vacant beads with the pesticidal active ingredient, 1) improvement in productivity by reducing extrusion resistance during extrusion molding 2) Improving the yield by giving the granulated wet product obtained by extrusion molding a sufficient strength. 3) Improving the medicinal effect by facilitating the active dissolution of the pesticide active ingredient from the produced pesticide granules into water quickly. Improvement is that the above 1) to 3) cannot be simultaneously satisfied.

[0005]

Means for Solving the Problems Thus, the present inventors have
As a result of studying to solve the above problems, a specific carrier is used as a carrier, and a specific surfactant is used as a surfactant. It has been found that it is correct and suitable to prepare a water-containing composition through the step of preparing a water-containing composition containing the water-containing composition and extruding the water-containing composition.

That is, the present invention provides a water-containing composition containing a carrier, a surfactant and water, and extrudes the water-containing composition to produce vacant beads. In the method of producing pesticide granules by impregnating
The following carrier A was used as the carrier, and the following surfactant B was used as the surfactant, and 0.1 to 5 parts by weight of the surfactant B and 3 to 10 parts by weight of water per 100 parts by weight of the carrier A.
The present invention relates to a method for producing pesticide granules, comprising preparing a water-containing composition containing 14 parts by weight.

Carrier A: specific surface area of 1,000 to 30,000
a cm ² / g, an average particle diameter of 0.7～20Myuemu, calcium carbonate water is less than 0.2 wt% powder

Surfactant B: One or more selected from organophosphates represented by the following formula 1:

[0009]

(Equation 1)

In the formula 1, R: a hydrocarbon group having 1 to 18 carbon atoms Y: a residue obtained by removing a hydroxyl group from a polyoxyalkylene diol having 1 to 100 repeating oxyalkylene units M: H or a monovalent base m , N: 1 or 2 and an integer satisfying m + n = 3

The carrier A used in the present invention has a specific surface area of 10
The average particle diameter is from 0.7 to 30,000 cm ² / g.
It is a calcium carbonate powder having a particle size of 20 μm and a water content of not more than 0.2% by weight.
8000 cm ² / g, and the average particle size is 2.5 to 15
Calcium carbonate powder of μm is preferred. The bulk density of the calcium carbonate powder used as the carrier A is not particularly limited, but is preferably in the range of 0.50 to 0.95 g / ml. In the present invention, the bulk density means the bulk density specified in JIS-K5101.

The surfactant B used in the present invention is one or more selected from the organic phosphoric esters represented by the formula (1). The organic phosphoric acid ester represented by the formula 1 includes an acidic phosphoric acid ester of a polyoxyalkylene diol having one end blocked with a hydrocarbon group, and a phosphoric acid obtained by neutralizing the acidic phosphoric acid ester with a monovalent basic compound. And ester salts.

In the formula 1, Y is a residue obtained by removing a hydroxyl group from polyoxyalkylene diol. Examples of such polyoxyalkylene diols include polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, and polyoxyalkylene diols composed of two or more different oxyalkylene units. Such polyoxyalkylene diol is
The number of repeating oxyalkylene units is 1 to 100, preferably 1 to 50, and more preferably 2 to 10
More preferably, Among them, a polyoxyethylene diol in which the oxyalkylene unit is an oxyethylene unit and the number of repetitions is 2 to 10 is particularly preferred.

The hydrocarbon group blocking one end of the polyoxyalkylene diol exemplified above has 1 to 1 carbon atoms.
8 hydrocarbon groups. Such hydrocarbon groups include
1) methyl group, ethyl group, isopropyl group, butyl group,
Alkyl groups such as hexyl group, octyl group, lauryl group and stearyl group; 2) monocyclic saturated hydrocarbon groups such as cyclopentyl group and cyclohexyl group; 3) aromatic groups such as phenyl group and naphthyl group; 4) octylphenyl group And a substituted phenyl group substituted with an alkyl group such as a nonylphenyl group. Among these, an alkyl group having 8 to 12 carbon atoms, particularly a straight-chain alkyl group, is preferred.

The method for producing the polyoxyalkylene diol having one end blocked with a hydrocarbon group is not particularly limited, and a known method can be applied thereto. For example, a method of obtaining a polyoxyalkylene diol having one end blocked with an alkyl group or a phenyl group by successively adding a predetermined number of moles of 1,2-alkylene oxide to one mole of alcohol or phenol in the presence of a basic catalyst. Is mentioned.

The organic phosphoric acid ester used as the surfactant B includes an acidic phosphoric acid monoester in which 1 mol of a polyoxyalkylenediol having one end blocked is ester-bonded to phosphoric acid, and 2 mol of a polyoxyalkylenediol having one end blocked. Acid phosphate diester ester-bound to phosphoric acid and phosphate ester salts obtained by neutralizing these acid phosphate esters with a monovalent basic compound are included. A mixture with an acidic phosphoric acid diester or a mixture of a phosphoric acid monoester salt and a phosphoric acid diester salt obtained by neutralizing these with a monovalent basic compound is preferred. The method for producing such an organic phosphate is not particularly limited, and a known method can be applied thereto.
For example, 1) a method of obtaining 2 mol of acidic phosphoric acid monoester by reacting 2 mol of polyoxyalkylene diol with one end blocked, 1 mol of water, and 1 mol of phosphorus pentoxide, 2) polyoxyalkylene diol with one end blocked Reaction of 3 moles of alkylene diol with 1 mole of phosphorus pentoxide to form acidic phosphoric acid monoester 1
To obtain 1 mol of acid phosphoric acid diester and 1 mol of acidic phosphoric acid diester, 3)
There is a method of reacting 2 mol of polyoxyalkylene diol having one end blocked with 1 mol of phosphorus oxychloride, followed by hydrolysis to obtain 1 mol of acidic phosphoric diester. The phosphoric acid ester salt can be obtained by neutralizing such an acidic phosphoric acid monoester or acidic phosphoric acid diester with a monovalent basic compound.

The monovalent basic compound used for neutralization includes:
1) Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. 2) Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, etc. 3) Methyldiethanolamine, ethyl Monoethanolamine,
N-alkyl-substituted alkanolamines such as butyldiethanolamine; 4) alkylamines having 1 to 4 carbon atoms such as trimethylamine, triethylamine and tributylamine; and 5) cyclic amines such as morpholine and pyridine. Oxides are preferred, and potassium hydroxide and sodium hydroxide are particularly preferred as alkali metal hydroxides.

In the present invention, a water-containing composition containing the above-described carrier A, surfactant B and water is prepared. The water-containing composition contains 0.1 to 5 parts by weight of surfactant B and 3 to 14 parts by weight of water per 100 parts by weight of carrier A. It is preferable to contain 4 parts by weight and 5 to 10 parts by weight of water.

In the present invention, the water-containing composition, and those containing water in a proportion of 3 to 15% by volume based on the void specific volume V _E (ml / g) of carrier A obtained by Equation 2 below Is particularly preferred.

[0020]

(Equation 2)

In the formula 2, ρ: true density of the carrier A ρa: bulk density of the carrier A ｛0.50 ≦ ρa ≦ 0.9
5 (g / ml)｝

The specific void volume V _E (ml /
As the carrier A having g), a calcium carbonate powder having a bulk density of 0.50 to 0.95 g / ml is used as described above, and among these, the bulk density is such that the specific surface area is 1500. ~8000cm a ² / g, the average particle diameter thereof is preferably used calcium carbonate powder is 2.5～15Myuemu.

A water-containing composition as described above,
The water-containing composition containing water at a ratio of 3 to 15% by volume with respect to the void specific volume V _E (ml / g) of the carrier A determined by
It has excellent viscoelastic properties, that is, high flow properties and yield properties, has low extrusion resistance during extrusion, and therefore has high productivity, and the strength of the granulated wet product obtained by extrusion molding on it is high. It is high and does not cause deformation, breakage, or the like during drying or transport, and therefore has a high yield and is more suitable.

The present invention does not particularly limit the method for preparing the water-containing composition. For example, the method includes dissolving a predetermined amount of surfactant B in a predetermined amount of water, and adding this to a predetermined amount of carrier A. And a method of preparing a water-containing composition by kneading. As the kneading machine used for preparing the water-containing composition, a known kneading machine can be appropriately used. Examples thereof include a ribbon mixer type mixer, a V-type mixer, a rotary mixer, a conical mixer, and a high-speed fluidizer. Mold mixer, continuous kneader and the like.

In the water-containing composition used in the present invention, excipients, stabilizers and the like can be appropriately selected and contained as solid components other than the carrier A and the surfactant B. Examples of such an excipient include a known natural or synthetic water-soluble polymer, and examples of the stabilizer include a known pH buffer.

According to the present invention, the water-containing composition thus prepared is extruded to produce empty beads, and the empty beads are impregnated with the pesticidal active ingredient to produce pesticide granules. The extruded product is granulated separately, the granulated wet product is usually dried, and then, if necessary, an empty ball is produced by sizing.However, extrusion molding and granulation can be performed simultaneously. it can.
For extrusion molding, screw molding machines, roll molding machines,
A known extrusion molding machine such as a blade molding machine can be used, but in any case, when applying the method of the present invention, the properties of the water-containing composition, the type of the extrusion molding machine, and the requirements for the granulated wet product are required. It goes without saying that the operating conditions of the extruder, such as the extrusion pressure and speed, are appropriately selected depending on the mechanical properties and the like to be performed.

In the present invention, the pesticide produced as described above is impregnated with the pesticidal active ingredient to produce pesticide granules. The pesticidal active ingredient to be impregnated into the vacant beads is not particularly limited, but as the water solubility index, 1) the octanol / water partition coefficient is 10 ⁴ or more.
It is preferably 10 ⁸ or 2) those having a water solubility at 20 ° C. of 1 to 0.001 ppm. Agrochemical active ingredients having such a water solubility index are substantially water-insoluble and include insecticides, fungicides, and herbicides as described below. As insecticides, 2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl = ether (ethofenprox), (RS) -α
-Cyano-3-phenoxybenzyl = (RS) -2,2
-Dichloro-1-1 (4-ethoxyphenyl) cyclopropanecarboxylate (cycloprotoline), Nt
tert-butyl-N '-(4-ethylbenzoyl)-
3,5-dimethylbenzohydrazide (tebufenozide), 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H
-1,3,5-thiadiazin-4-one (buprofezin), 1- [4- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-fluorophenyl]-
3- (2,6-difluorobenzoyl) urea (flufenoxuron) and the like.

As fungicides, 1- (4-chlorobenzyl) -1-cyclobentyl-3-phenylurea (pencyclone), 6- (3,5-dichloro-4-methylphenyl) -3 (2H)- Pyridazinone (dicromedin)
And the like.

Further, as a herbicide, 6-methyl-3 [1
-Methyl-1- (3,5-dichlorophenyl) ethyl]
-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one, (RS) -2- (2,4-dichloro-m-tolyloxy) propionanilide (chromeprop), 5- (2 , 4-Dichlorophenoxy) -2-
Methyl nitrobenzoate (bifenox), O-3-t
tert-butylphenyl = 6-methoxy-2-pyridyl (methyl) thiocarbamate (pyributicarb), 5-
tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one (oxadiazon), 4- (2,4-dichlorobenzoyl) -1, 3-dimethyl-5-pyrazolyl-
p-toluenesulfonate (pyrazolate), 2- [4
-(2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy] -4'-methylacetophenone (benzophenap).

In the present invention, the content ratio of the pesticide active ingredient to be impregnated into the vacant beads is not particularly limited, and the proportion can be arbitrarily selected depending on the kind and physical properties of the pesticide active ingredient.
Usually 0.1 to 25 per 100 parts by weight of carrier A in empty beads
Impregnated so as to have a ratio of 5 parts by weight, preferably 5 to 15
Impregnate so as to be in parts by weight.

The present invention does not particularly limit the method for impregnating the pesticide into the vacant beads. Examples of the method include: 1) When the pesticidal active ingredient is liquid at room temperature, such a liquid pesticidal active ingredient is used. And impregnating by mixing an empty ball with a universal mixer. 2) When the pesticidal active ingredient is solid at room temperature, the solid pesticidal active ingredient is heated and melted. Or a method of dissolving it in an organic solvent to form a liquid, and impregnating the liquid by mixing it with an empty ball by using a universal mixer. As the organic solvent used in the above 2), those having a boiling point of 150 ° C. or more and having no trouble such as evaporation or odor in the preparation step are preferable, and furthermore, they do not dissolve or swell the carrier in the vacant beads. Those which do not hinder the shape retention of are preferred. Specific examples of such organic solvents include mineral oils, vegetable oils, higher fatty acid esters, aromatic hydrocarbon solvents, and the like. These organic solvents usually have a content of 300 parts by weight or less based on 100 parts by weight of the pesticidal active ingredient. Use in proportion.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the method for producing pesticide granules according to the present invention include the following 1) to 8). 1) The carrier A has a specific surface area of 3000 cm ² / g,
The average particle size is 7.4 μm and the water content is 0.2% by weight.
Calcium carbonate powder (T-1) and di [octyloxy polyoxyethylene diol (m = 4, m is the number of repeating oxyethylene units, the same applies hereinafter)] surfactant hydrogen / Mono [octyloxy / polyoxyethylene diol (m =
4)] An organic phosphate ester (P-1) obtained by neutralizing a mixture of dihydrogen phosphate = 1/1 (molar ratio) with potassium hydroxide by 90% by weight, and further adding water, an excipient and a stabilizer. A water-containing composition containing 2 parts by weight of the organic phosphate (P-1) and 7 parts by weight of water per 100 parts by weight of the calcium carbonate powder (T-1) was prepared,
A method for producing a pesticide through the step of extrusion-molding the water-containing composition, and then impregnating the pesticide with the pesticidal active ingredient.

2) Instead of the organic phosphate (P-1), di [lauryloxy polyoxyethylene diol (m = 8)] monohydrogen phosphate / mono [lauryloxy polyoxyethylene diol (m = 8)
8)] The above 1) except that an organic phosphate (P-2) obtained by neutralizing a mixture of dihydrogen phosphate = 1/1 (molar ratio) with 50% by weight of sodium hydroxide was used.
Calcium carbonate powder (T-1) 1
A method for preparing a water-containing composition containing 3 parts by weight of an organic phosphate (P-2) and 6 parts by weight of water per 00 parts by weight, and producing a pesticide granule in the same manner as in 1) above. .

3) Instead of the organic phosphate (P-1), di [octyloxy poly (oxyethylene / oxypropylene) diol (m = 6, n = 2, n is the number of repeating oxypropylene units; The same)] monohydrogen phosphate / mono [octyloxy poly (oxyethylene / oxypropylene) diol (m =
6, n = 2)] dihydrogen phosphate = 1 /
Calcium carbonate powder (T-) was prepared using the same organic phosphate (P-3) except that the mixture of 1 (molar ratio) was neutralized with potassium hydroxide by 90% by weight and the organic phosphate (P-3) was used.
1) Organic phosphoric acid ester (P-3) per 100 parts by weight
Of a water-containing composition containing 1 part by weight of water and 8 parts by weight of water, and then producing a pesticide granule in the same manner as in 1) above.

4) Instead of the calcium carbonate powder (T-1), a calcium carbonate powder having a specific surface area of 1500 cm ² / g, an average particle diameter of 14.8 μm and a water content of 0.2% by weight. Compound (T-2) and di [hexyloxy / polyoxyethylene diol (m = 14)] monohydrogen phosphate / mono [hexyloxy / polyoxyethylene instead of the organic phosphate (P-1) Diol (m = 14)]. Dihydrogen phosphate = 1/1 (molar ratio), except that an organic phosphate (P-4) obtained by neutralizing 70% by weight with potassium hydroxide was used. A method for producing pesticide granules in the same manner as described above.

5) Instead of calcium carbonate powder (T-1), calcium carbonate powder having a specific surface area of 5000 cm ² / g, an average particle diameter of 4.4 μm and a water content of 0.2% by weight The compound (T-3) was replaced with di [stearyloxyoxyethylenediol (m = 1)]. Monohydrogen phosphate / mono [stearyloxyoxyethylenediol (P-1) instead of the organic phosphate (P-1). m = 1)] · dihydrogen phosphate =
A method for producing pesticide granules in the same manner as in the above 1) except that an organic phosphate (P-5) obtained by neutralizing a 1/1 (molar ratio) mixture with sodium hydroxide by 70% by weight is used.

6) Instead of the organic phosphate (P-1), di [cyclohexyloxy / polyoxyethylene diol (m = 18)] monohydrogen phosphate / mono [cyclohexyloxy / polyoxyethylene diol (m = 18) 18)] The mixture of dihydrogen phosphate = 1/1 (molar ratio) is mixed with potassium hydroxide for 90 hours.
A method for producing pesticide granules in the same manner as in the above 1) except that the organic phosphoric acid ester (P-6) neutralized by weight% is used.

7) Instead of the organic phosphate (P-1), di [phenyloxy polyoxyethylene diol (m = 25)] monohydrogen phosphate / mono [phenyloxy polyoxyethylene (m = 2)
5)] In the same manner as in the above 1) except that an organic phosphate (P-7) obtained by neutralizing a mixture of dihydrogen phosphate = 1/1 (molar ratio) with 70% by weight of butylethanolamine was used. A method for producing pesticide granules.

8) Instead of the organic phosphate (P-1), di [nonylphenyloxy polyoxyethylene diol (m = 8)] monohydrogen phosphate / mono [nonylphenyloxy polyoxyethylene diol ( m = 8)] · dihydrogen phosphate =
A method for producing pesticide granules in the same manner as in the above 1) except that an organic phosphate (P-8) obtained by neutralizing a 1/1 (molar ratio) mixture with dibutylamine at 70% by weight is used.

Preferred examples of the pesticide granule according to the present invention include the following 9). 9) The water-containing composition of any of the above 1) to 8) is extrusion-molded, granulated, and the granulated wet product is dried to produce empty beads. A pesticide granule obtained by mixing a liquid material and impregnating the empty beads with the pesticidal active ingredient.

Hereinafter, the structure and effects of the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts mean parts by weight and% means% by weight unless otherwise specified.

[0042]

【Example】

Test Category 1 (Manufacture of pesticide granule) Manufacture of pesticide granule (H-1) Carrier A has a specific surface area of 3000 cm ² / g, an average particle diameter of 7.4 μm and a water content of 0.2%. 2,000 parts of calcium carbonate powder and 50 parts of sodium tripolyphosphate were taken as a stabilizer and mixed uniformly. As the surfactant B, an organic phosphate ester (P-
44 parts of an aqueous liquid containing 90% of 1) (40 parts of solid content),
80 parts of gum arabic (g-1) and water 13 as excipients
A mixed aqueous solution composed of 6 parts was added and kneaded until the mixture became uniform to prepare a water-containing composition (C-1). 2040 parts of this water-containing composition (C-1) was mounted on a screw-type extruder equipped with a screen having a diameter of 1.0 mm (DG manufactured by Fuji Paudal)
-L1 type) and the motor inverter frequency 20
The mixture was extruded into a noodle shape at a frequency of 32 Hz and a shaft rotation speed of 32 rpm. The noodle-like extruded product was cut to a length of 2 to 4 mm, and the cut granulated wet product was immediately supplied to a fluidized-bed dryer (Model MDA-200 manufactured by Fuji Paudal Company) at a temperature of 50 ° C. for 15 minutes. After drying for a minute, an empty ball (h-1) was obtained. 1000 parts of this vacant ball (h-1) are put into a universal mixer (Dalton Co., Ltd.), and 80 parts of cycloprothrin having an octanol / water partition coefficient of 1.55 × 10 ⁴ as an agrochemical active ingredient are 240 parts of methylnaphthalene. Was added and then mixed for 15 minutes to impregnate with cycloprothrin to obtain 1320 parts of pesticide granule (H-1).

Pesticide granules (H-2) to (H-8), (HR
-1) to (HR-3) Production of pesticide granules (H-1) in the same manner as production of pesticide granules (H-1)
-2) to (H-8) and (HR-1) to (HR-3).

Production of Pesticide Granule (HR-4) Except not using the organic phosphate (P-1), the same procedure as in the case of the water-containing composition (C-1) was carried out.
4) was prepared. Using this water-containing composition (CR-4),
In the same manner as in the production of the pesticide granule (H-1), the pesticide granule (H
R-4) was produced.

Production of pesticide granule (HR-5) A water-containing composition (C-1) was used except that dioctyl sulfosuccinate sodium salt (r-1) was used instead of the organic phosphate (P-1). Similarly, a water-containing composition (CR
-5) was prepared. Using this water-containing composition (CR-5), a pesticide granule (HR-5) was produced in the same manner as in the production of the pesticide granule (H-1).

Production of pesticide granule (HR-6) A water-containing composition (C-1) except that α-sulforauric acid methyl sodium salt (r-2) was used in place of the organic phosphate (P-1). ) In the same manner as in the aqueous composition (CR-
6) was prepared. Using this water-containing composition (CR-6),
In the same manner as in the production of the pesticide granule (H-1), the pesticide granule (H
R-6) was prepared.

Production of pesticide granule (HR-7) A water-containing composition (C-1) was used except that a naphthalenesulfonic acid sodium salt formalin condensate (r-3) was used instead of the organic phosphate (P-1). ), A water-containing composition (CR-7) was prepared. This water-containing composition (CR-
7), in the same manner as in the production of the pesticide granule (H-1),
A pesticide granule (HR-7) was produced. Table 1 summarizes the contents of the organic phosphoric acid ester when used in the production of each pesticide granule, and Table 2 summarizes the contents of each pesticide granule.

[0048]

[Table 1]

In Table 1, oxyalkylene unit of P-3: random bond M-1: butylethanolamine M-2: dibutylamine

[0050]

[Table 2]

[0051] In Table 2, H-1~H-8: usage pesticidal granules according to the present invention: Part WP: filling ratio of water to the above-described V _E of the formula 2 (volume%) T-1: specific surface area 3000 cm ² / g, average particle size 7.4
μm, moisture 0.2%, ρ = 2.71 g / cm ³ , ρa = 0.
_{^{83g / cm 3, V E =}} 0.836cm 3 / g and a calcium carbonate powder (however, [rho, .rho.a and V _E correspond to each of Formula 2 described above, hereinafter the same) T-2: the specific surface area 1500cm ² / g, average particle size 14.
8 μm, moisture 0.2%, ρ = 2.71 g / cm ³ , ρa =
_{^{0.91g / cm 3, V E =}} 0.730cm 3 / g and a calcium carbonate powder T-3: a specific surface area of 5000 cm ² / g, average particle size 4.4
μm, moisture 0.2%, ρ = 2.71 g / cm ³ , ρa = 0.
_{^{70g / cm 3, V E =}} 1.06cm 3 / g calcium carbonate is a powder N-1: Octanol / water partition coefficient of 1.55 × 10 ⁴
Having a water solubility of 9.1 × 10 ⁻² p at 20 ° C.
pm cycloprothrin N-2: octanol / water partition coefficient 4.79 × 10 ⁴
Having a water solubility of 0.3 ppm at 20 ° C., and having a partition coefficient of octanol / water of 1.02 × 10 ^4.
Having a water solubility at 20 ° C. of 1.8 × 10 ⁻¹ p
pm, 6-methyl-3 [1-methyl-1- (3,5
-Dichlorophenyl) ethyl] -5-phenyl-2,3
-Dihydro-4H-1,3-oxazin-4-one a-1: Tripolyphosphate sodium salt g-1: Gum arabic r-1: Dioctyl sulfosuccinate sodium salt r-2: α-Sulfolaurate methyl sodium salt r-3: Naphthalenesulfonic acid sodium salt formalin condensate

Test Category 2 (Evaluation) 1) Evaluation of Productivity In Test Category 1, the following criteria were used to evaluate the motor current of the extruder during extrusion molding and the occurrence of squeak noise. The results are summarized in Table 3. ：: The motor current is stable at an average of 1.6 to 1.7 amperes, and there is no squeaking noise during extrusion. ：: The motor current is stable at an average of 1.7 to 2.0 amps. However, the squeak noise at the time of extrusion is slight. △: The current of the motor is as high as 2.0 to 2.4 amps on average, and the squeak noise at the time of extrusion is considerably large. Overload operation exceeding ampere and granulation cannot be performed continuously

2) Evaluation of Shape Retention In Test Category 1, the appearance of an extruded product extruded into a noodle shape from an extruder was evaluated according to the following criteria. Table 3 shows the results
Are shown together. ：: Uniform columnar shape, smooth surface, good shape retention △: Cylindrical overall, non-uniform cylinder, rough surface, poor shape retention ×: not cylindrical, Poor shape retention

3) Evaluation of strength of granulated wet product In test category 1, the dry weight of dust generated during drying was measured, and the dried product was converted into the target pesticide granules and the crushed product using a rotap sieving machine (C). 156 taps / min., 290 r.p. p. m and sieved for 5 minutes, and the dried weight of each sieved product was measured. From these measured values, the crushing rate was calculated by the following equation 3.

[0055]

[Equation 3] Crushing rate (%) = ｛(D + Tr) / (D + Tr +
Tp)｝ × 100

In the formula 3, D: dry weight of dust Tp: dry weight of target pesticide granule Tr: dry weight of crushed material

The following criteria were used to evaluate the calculated crushing rate.
The results are summarized in Table 3. ：: Crush rate is less than 5% ○: Crush rate is 5% or more and less than 10% △: Crush rate is 10% or more and less than 15% ×: Crush rate is 15% or more

4) Evaluation of dissolution of pesticide active ingredient A glass petri dish (14.5 cm in diameter, 10 cm in height)
After drying, Tone soil (sandy loam) 1
Then, 500 g of water was gently poured. Here, 16 mg of the pesticide granules obtained in Test Category 1 were applied to the surface.
Twelve hours later, 1 g of an aqueous solution was collected from a portion at a depth of 1 cm from the surface layer in the center of the petri dish, and this was used as a sample, subjected to high performance liquid chromatography under the following conditions, and the content of the pesticide active ingredient in the sample was analyzed. . Then, the dissolution ratio of the pesticidal active ingredient was calculated from the analytical value by the following formula 4.

Conditions for high-performance liquid chromatography Column: TOSOH TSK-GEL 80TM (manufactured by Tosoh Corporation) Column diameter: 4.6 mm, column length: 150 mm Column temperature: 35 ° C. Eluent: acetonitrile / water = 65/35 (0.07 %
Phosphoric acid addition) Eluent flow rate: 1 ml / min Detector: UV (230 nm)

[0060]

Formula 3: Elution ratio (%) = (E × 1000 / F) × 100

In the formula 4, E: the content of the pesticidal active ingredient contained in the collected sample (mg /
1 g water) F: Water solubility (ppm) of the pesticidal active ingredient at 20 ° C.

From the calculated elution ratio, evaluation was made according to the following criteria.
The results are summarized in Table 3. ◎: Elution ratio is 90% or more ：: Elution ratio is 60% or more and less than 90% Δ: Elution ratio is 30% or more and less than 60% ×: Elution ratio is less than 30%

[0063]

[Table 3]

In Table 3, * 1: Not evaluated because no extruded product was formed

[0065]

As is apparent from the above description, the present invention described above has an advantage of improving productivity by reducing extrusion resistance at the time of extrusion molding, and providing a granulated wet product obtained by extrusion molding with sufficient strength. This has the effect of simultaneously improving the yield by giving it, and improving the medicinal effect by making it easier for the pesticidal active ingredient to readily elute into water from the produced pesticide granules.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Takashi Kaji, Inventor, Takashi Kaji, Ami Research Center, 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture (72) Inventor Shunjo Maruyama, Inashiki-gun, Ibaraki Ami-cho, Ami-cho Chuo 8-3-1, Rh ヌ ne-Poulenc Agro Co., Ltd.

Claims (9)

[Claims] 1. A hydrated composition containing a carrier, a surfactant and water is prepared, and after the hydrated composition is extruded to form vacancies, the vacancies are impregnated with an agricultural chemical active ingredient. In the method for producing pesticide granules by using the following carrier A as a carrier and the following surfactant B as a surfactant, the surfactant B is used in an amount of 0.1 to 5 per 100 parts by weight of the carrier A. A method for producing a pesticide granule, comprising preparing a water-containing composition containing 3 to 14 parts by weight of water and 3 to 14 parts by weight of water. Carrier A: Specific surface area is 1,000 to 30,000 cm ² / g, average particle diameter is 0.7 to 20 μm, and water content is 0.
Calcium carbonate powder of 2% by weight or less Surfactant B: One or more selected from organic phosphates represented by the following formula 1 (In the formula 1, R: a hydrocarbon group having 1 to 18 carbon atoms Y: a residue obtained by removing a hydroxyl group from a polyoxyalkylene diol having 1 to 100 repeating oxyalkylene units M: H or a monovalent base m, n : 1 or 2 and an integer satisfying m + n = 3) 2. The carrier A has a specific surface area of 1500 to 800.
0cm a ² / g, and the average particle size of the calcium carbonate powder is 2.5~15μm claim 1 pesticidal granules method according. 3. The carrier A has a bulk density of 0.50 to 0.95.
The method for producing pesticide granules according to claim 1 or 2, which is g / ml calcium carbonate powder. 4. A surfactant B wherein R in the formula 1 has 8 carbon atoms.
An organic phosphoric ester in the case where Y is a residue obtained by removing a hydroxyl group from a polyoxyethylene diol having 2 to 10 repeating oxyethylene units, wherein Y is a straight-chain alkyl group of from 1 to 12; A method for producing the pesticide granule according to the above. 5. The surfactant B according to claim 1, wherein M in the formula 1 is an organic phosphate when M is an alkali metal.
5. The method for producing a pesticide granule according to 2, 3, or 4. 6. The surfactant B is a mixture of an organic phosphoric acid monoester when m in the formula 1 is 1 and an organic phosphoric diester when m in the formula 1 is 2. The method for producing a pesticide granule according to 1, 2, 3, 4, or 5. 7. A water-containing composition is one containing water in a proportion of 3 to 15% by volume based on the void specific volume V _E of the support A obtained by the equation 2 below (ml / g) claims 1, 2,
7. The method for producing a pesticide granule according to 3, 4, 5, or 6. (Equation 2) (In the formula 2, ρ: true density of the carrier A ρa: bulk density of the carrier A} where 0.5 ≦ ρa ≦ 0.95
(G / ml)｝ 8. The agrochemical active ingredient is an agrochemical active ingredient having an octanol / water partition coefficient of 10 ⁴ to 10 ⁸ or an agrochemical active ingredient having a water solubility at 20 ° C. of from 1 to 0.001 ppm. The method for producing a pesticide granule according to 3, 4, 5, 6, or 7. 9. A pesticide granule obtained by the method for producing a pesticide granule according to claim 1, 2, 3, 4, 5, 6, 7, or 8.