JP2931603B2 - Method for producing non-medical granules - Google Patents

Description

The present invention relates to a method for producing non-medical granules. More specifically, a solid active ingredient that is hardly soluble in water is wet-pulverized in water to form a slurry, which is mixed with a mineral fine powder carrier and extruded for granulation. The present invention relates to a method for producing a non-medical granule having improved economy and productivity by blending a compound represented by the formula (1) as a dispersant at the time of pulverization and a granulating property improving agent.

In the above formula, R ₁ represents a C _{2 to} C ₆ alkyl group, R ₂ and
R ₃ represents a hydrogen atom or an alkyl group of C ₁ ~C _6, X is an alkali metal or an ammonium group.

The object of the present invention is to improve the pulverizability and granulation properties by adding a small amount of a surfactant which simultaneously has a pulverizing efficiency improving action and a granulating property improving action at the time of wet pulverization of an object to be pulverized. To improve.

Solid active ingredients that are hardly soluble in water, especially compounds having biological activity such as pesticides, epidemiological agents, and fertilizers, generally require many pulverizations, and some of them are in the form of granules when used. Many are used.

In such a case, the method of pulverizing these hardly soluble solid compounds becomes an important problem. The pulverization of these compounds may be performed by dry pulverization or wet pulverization.In general, the desired particle size cannot be obtained by dry pulverization,
Even if the desired product is obtained in terms of particle size, there is a drawback that it is not economical, and a wet pulverization method of pulverizing an object to be pulverized as an aqueous suspension is often employed.

In wet milling, it is necessary that the compound be wetted with water and completely dispersed in water. If the water wet is bad, it will not be suspended, and if the dispersion is not complete, the suspension will aggregate,
The required particle size cannot be obtained. For this reason, an appropriate surfactant is often used as a dispersant in wet milling, but depending on the type of surfactant, the suspension foams during the milling process. May float and aggregate. Therefore, it is desirable that the surfactant used as the dispersant has a low foaming property, and even if foamed, the generated foam is easily erased.

On the other hand, granules are generally prepared by pulverizing and mixing an active ingredient with a powdery carrier and granulating the granulated product using a suitable granulator, or a granular carrier having an oil-absorbing ability (a powdered carrier is formed by a suitable method). After granulation, there are two types, one having a desired particle size and the other having a desired particle size after crushing a porous substance having an oil absorbing ability. It is produced by a method of absorbing components, a method of coating a granular carrier having no oil absorbing ability with a powdered or powdered active ingredient using a suitable binder, and the like. Among these methods, a machine for granulating the powdered active ingredient together with another powdery carrier or granulating the powdered carrier to produce a granular carrier containing no active ingredient is known. Although various methods are conceivable, in Japan, extrusion granulators are traditionally used in many cases. The carrier used for extrusion granulation is conventionally
It is mainly made of bentonite, which has plasticity by kneading and has a wide range of water suitable for granulation, and talc, which has good slippage and small granulation resistance, and has other carriers and other auxiliary components in an appropriate ratio. In many cases. However, bentonite and talc show alkalinity, and in particular, in the case of bentonite, the amount of water used is often limited because of its large water retention ability, which may cause hydrolysis depending on the active ingredient. . Therefore, recently, calcium carbonate and kaolinite-based or pyrophyllite-based clays have been often used as carriers that can be used for active ingredients that are relatively unstable. However, these carriers have a small amount of water suitable for granulation and a small plasticity, so that when the extruded particle size is small or when the carrier particle size is coarse, granulation is difficult, and in the case of clay, However, since the hardness is high, the wear of the equipment is large, and the wall and screen of the granulator are damaged quickly. Adding a large amount of kneading water to improve granulation may improve the granulation slightly, but this time, the load on the kneading machine will increase, or the granulated material will be aggregated in the dryer. As a result, there are disadvantages such as an increase in load on the dryer and a reduction in yield due to powdering during sizing.

Therefore, when a solid active ingredient that is hardly soluble in water is wet-pulverized and granules are obtained by extrusion granulation, a small amount of addition is required to improve the dispersant during wet pulverization and the granulation property during extrusion granulation. It is convenient if there is one that simultaneously has an action as an agent.

Based on the above findings, the present inventors have intensively studied for a substance having both the dispersing action at the time of wet pulverization and the action of improving the granulability at the time of extrusion granulation. The present invention was found to be effective, and the present invention was completed.

The compound used in the present invention is a compound represented by the above general formula (1), and is a salt of mono-, di- or trialkylnaphthalenesulfonic acid. Where R ₁ is C ₂ ~
A linear or branched alkyl group of C ₆ , R ₂ and R ₃ are a hydrogen atom or a linear or branched alkyl group of C _{1 to} C ₆ , and X is an alkali metal or ammonium The groups are respectively shown.

 Table 1 shows typical examples of such compounds.

The compound of the present invention is not limited thereto, but among the compounds represented by the general formula (1), R ₁ and R ₂ are both an alkyl group of C _{3 to} C ₄ , and R ₃ is a hydrogen atom , X is particularly preferably Na.

In the present invention, the water-insoluble solid compound is suspended in water using the compound represented by the general formula (1),
Grind using a suitable wet grinder. At the time of pulverization, a small amount of a pH adjuster, a stabilizer against light or oxidation, a pigment, an antifreezing agent, a thickener, an antisettling agent, and the like, which can be usually added to wet pulverization, can be added.

The solid compound hardly soluble in water in the present invention has a solubility in water at 25 ° C. of 100 ppm or less, preferably 10 pp.
It is a compound that is solid at room temperature of less than m. In the pesticide active ingredient, for example, the herbicide 4- (2,4-dichlorobenzoyl)
1,3-dimethyl-5-pyrazolyl p-toluenesulfonate
(Pyrazolate), 2- [4- (2,4-dichlorobenzoy)
l) -1,3-dimethylpyrazol-5-yloxy) acetophenone
(Pyrazoxifene), 2- [4- (2,4-Dichloro-
3-methylbenzoyl) -1,3-dimethylpyrazol-5-ylo
xy] -4'-methylaceto phenone (benzophenap), 3-Chloro-4-methyl-6- (N-2-chloro
-2-propenyl-N-phenyl-amino) piridazine (MT
-128), S, S-dimethyl- (difluoromethyl) -4-
(2-methylpropyl) -6- (trifluoromethyl) -3,5
-Pyridine dicarbothioate (MON72), O-3-tert-
butylphenyl-N-methyl-N- (6-methoxy-2-py
ridyl) thiocarbamate (N- [2 '
-(3'-methoxy) -thienylmethyl] -N-chloroac
eto-2,6-dimethylanilide (NSK-850), 1- (2-C
hlorobenzyl) -3- (α, α-dimethylbenzyl) urea
(JC-940), 2- (1,3-Benzothiazol-2-yloxy)
-N-methyl-acetanilide (mefenacet), (R
S) -2-bromo-N- (α, α-dimethylbenzyl) -3,
3-dimethylbutylamide (bromobutide), Methyl α-
(4,6-methoxypyrimidin-2-yl-carbamoylsulfamoy
l) -O-toluate (bensulfuron-methyl), 2-Meth
ylthio-4-ethylamino-6- (1,2-dimethylpropyla
mino) -s-triazine (dimetamethrin), α- (2-
naphthyloxy) propionanilide,
2,4,6-Trichlorophenyl 4'-nitrophenyl ether (chloronitrophen), 2,4-Dichlorophenyl 4'-nitro
phenyl ether (nitrophen), 2.4-dichlorophenyl
3'-methoxy-4'-nitrophenylether (chloromethoxynil), 3-[(Methoxycarbonyl) -amino] phenyl
(3-methylphenyl) carbamate, 4-Methylsulphonyl-2,6-dinitro-N, N-dipr
opylaniline (nitralin), 1- (α, α-dimethylb)
enzyl) -3- (p-tolyl) urea (Dimron), 3-
(3,4-Dichlorophenyl) -1-methoxy-1-methylur
ea (linuron), 3- (3,4-dichlorophenyl) -1,1
-Dimethylurea (diuron), 1- (2-Methylcycloh
exyl) -N'-phenylurea (sidulon), 3- (3-
Chloro-4-methoxyphenyl) -1,1-dimethylurea (methoxyuron), 1- (4-Chlorophenyl) -3- (2,
6-difluorobenzoyl) urea (diflubenzuron), 2,
4-Bis (iso-propylamino) -6-methylthio-1,3,5
-Triazine (promethrin), 2-Chloro-4,6-bis
(Ethylamino) -1,3,5-tri-azine (simazine), 2
-Chloro-4-ethylamino-6-iso-propylamino-1,
3,5-triazine (atrazine), 2 ', 4'-Difluoro-
2- (α, α, α-trifluoro-m-tolyloxy) nicotin
anilide (Diflufenican) etc., 1-Nap of insecticide
hthyl N-methylcarbamate (carbaryl), 2-Chloro
-1- (2,4,5-trichlorophenyl) vinyl dimethylphos
phate (tetrachlorovinphos), 2-Tert-butylim
ino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydr
o-2H-1,3,5-thiadiazin-4-one (buprofezin), 2- (4-ethoxyphenyl) -2-methylpropyl-
3-phenoxybenzylether (Ethofenprox),
(S) -α-cyano-3-phenoxybenzyl (1R, 3S) -2,
2-dimethyl-3- (1,2,2,2-tetrabromoethyl) cyclo
propane carboxylate (tralomethrin), (RS) -α
-Cyano-3-phenoxy-benzyl = N- (2-chloro-
α, α, α-trifluoro-p-tryl) -D-vali-nate
(Fluvalinate), (RS) -α-cyano-3-phenoxy
benzyl (S) -2- (4-difluoromethoxyphenyl)-
3-methylbutylate (flucitrinate), 1,1-Bis
(P-chlorophenyl) 2,2,2-trichloroethanol (Dicofor), Trans-5- (4-chlorophenyl) -Nc
yclo-hexyl-4-methyl-2-oxo-thiazo-lidine-
3-carboxamide (Hesisathiazox), 3-Methyl-
1,5-bis- (2,4-xylyl) -1,3,5-triaza-penta-1,
4-diene (amitraz), 1- (4-Chlorophenyl)-
3- (2,6-difluorobenzoyl) urea (diflubenzuron), 1- [3,5-Dichloro-4- (3-chloro-5-t
rifluoromethyl-2-pyridyloxy) phenyl] -3- (2,
6-difluorobenzoyl) urea (chlorofluazuron),
(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetr
amethyl cyclo-propane carboxylate (fenpropatrin), 5-Chloro-N- ｛2- [2,3-dimethyl-4
-(2-ethoxyethyl) phenoxy] ethyl｝ -6-ethyl-
4-pyrimdinamine (Compound A), (1R, 4S, 5'S, 6R, 6 '
R, 8R, 13R, 20R, 21R, 24R)-(10E, 14E, 16E, 22Z) -21,24
-Dihydroxy-11,13,22, -trimethyl-2-oxo-3,7,19
-Trioxa tetracyclo [15,6,1,1, ^{4, 8,} 0 ^{20, 24]} pentacos
a-10,14,16,22-tetraene-6-spiro-2 '-(6'
-Methyl-5'-methyl tetra hydropyran) ( milbemycin _{A 3), (1R, 4S} , 5'S, 6R, 6R ', 8R, 13R, 20R, 21R,
24S)-(10E, 14E, 16E, 22Z) -21,24-dihydroxy-11,1
3,22-trimethyl-2-oxo-3,7,19-trioxatetracyclo
[15,6,1,1 ^{4, 8, 20, 24,} 0] pentacosa-10,14,16,22-tetr
aene-6-spiro-2 '-(6'-ethyl-5'-methyl
tetrahydropyran) (milbemycin A ₄ ) or the like with the fungicide Methyl 1- (butylcarbamoyl) -benzimidazol-4-
yl) benzimidazole (Siabenzazole), Dimethyl
4,4 '-(o-phenylene) bis (3-thioallophanate)
(Thiophanate methyl), 1,4-dichloro-2,5-dime
thoxybenzene (chloroneb), N, N '-[piperazine-
1,4-diylbis [(trichloromethyl) methylene]] difo
rmamide (Triphon), Zinc ethylenebis (dithiocar)
bamate) (polymeric) (Zineb), Manganese ethylen
ebis (dithiocarbamate) (polymeric) (Maneb), Ma
nganese ethylenebis (dithiocarbamate) (polymeri
c) complex with zinc salt (mancozeb), Tetrameth
ylthiuram disulphide (thiram), 5,10-Dihydro-5,1
0-dioxonaphtho [2,3-b] -1,4-dicarbonitrile
(ヂ Cyanone), N- (trichloromethylthio) cyclohe
x-4-ene-1,2-dicarboximide (captan), N-
(1,1,2,2-tetrachloroethyl-thio) cyclohex-4-e
ne-1,2-dicarboximide (captahole), Tetrachlor
oisophthalonitrile (chlorothalonil), N- (3,5-d
ichlorophenyl) -1,2-dimethylcyclo-propene-1,2
-Dicarboximide (procymidone), α, α, α-trifl
uoro-3'-iso-propoxy-o-toluanilide (flutranil), 1- (4-Chlorobenzyl) -1-cyclopenty
l-3-phenylurea (pencicuron), 6- (3,5-Di
(chloro-4-methyl-phenyl) -3 (2H) -pyridazino
ne (dicromedin), Diisopopyl-1,3-dithiolane-
2-ylidene malonaet (isoprothiolane), 3-ally
loxy-1,2-benzisothiazole 1,1-dioxide (provenazole), 4,5,6,7-Tetrachlorophthalide (fusaride), 3,4,5,6-Tetrachloro-N- (2,3-dichlorophe
nyl) phthalamic acid (Teclophthalam), Pentachlor
onitrobenzene (Kintzen), O-2,6-Dichloro-p
-Tolyl O, O-dimethyl-phosphorothioate (Turkish phosphomethyl), Bis (quinolin-8-olato) copper (oxin copper), Sulfur (sulfur) and the like. In addition to pesticides, it can be applied to poorly soluble epidemic control drugs, animal drugs, fertilizers, and the like.

The concentration of these poorly water-soluble compounds in the suspension is
Higher is more economically advantageous. In general, the limit is about 70% for organic compounds, but in some cases, it can be as high as 75% or more for inorganic compounds. When the flow rate of the compound to be pulverized is coarse, it is often advantageous to carry out coarse pulverization in advance using a dry or wet type applicable pulverizer and then to pulverize by the following steps.

Other auxiliaries which may be added to the suspension include pH adjusters such as organic or inorganic acids and alkalis, antioxidants such as BHT and propyl gallate, and hydroxy-4-n-octoxybenzophenone. Such ultraviolet absorbers, various dyes used for the purpose of stabilizing or identifying the base agent, ethylene glycol, propylene glycol, antifreezing agents such as salt bitol, dextrin and starch derivatives thereof etherified or esterified, Polyvinyl alcohol (PVA) and its modified products, carboxymethylcellulose (CMC), methylcellulose, cellulose derivatives such as hydroxypropylcellulose, gum arabic,
Natural gums such as xanthan gum and lanthanum, salts of natural high molecular organic acids such as alginic acid and humic acid, thickeners such as high molecular weight polyethylene glycol or polyethylene oxide, bentonite, acid clay, smectite, laponite, white carbon However, in general, if the viscosity of the suspension is high, it is difficult to economically obtain extremely fine particle size, so it is advantageous not to increase the viscosity of the suspension more than necessary. It is. For this reason, a method is often employed in which these auxiliaries are not added, but pulverized at a low viscosity and a high content, and these auxiliaries are added to the suspension after the pulverization.

The amount of the compound represented by the general formula (1) used for wetting and dispersing these compounds in water may be any as long as the above object can be achieved, and is usually 5% or less in the suspension. is there.

The wet pulverizer suitable for pulverizing the suspension wet-dispersed in water in this way is a medium stirring type pulverizer represented by an attritor or a sand mill, and a high-speed rotary impact shear pulverizer represented by a wet hammer mill. And a wet high-speed rotary crusher represented by a colloid mill. The particle size of the resulting pulverized material is usually the concentration and viscosity of the suspension, the pulverization time and / or number, the type and size of the ball, the hammer or stirring blade, the rotation of the grinding wheel, the distance between the hammer and the liner, or between the grinding wheels. The size is adjusted by the spacing of the screen, the opening diameter of the screen, etc., but when the desired particle size is fine, it is also possible to install two or more of these pulverizers in series and perform continuous pulverization.

The suspension milled in this way, if necessary,
The above-mentioned stabilizer, thickener, soft coagulant and various auxiliary agents such as a suitable diluent are added to prepare a stable suspension, mixed with a carrier and extruded and granulated.

The suspension pulverized using the compound represented by the general formula (1) can be used as a granule containing bentonite or talc as a main carrier. Calcium, calcium carbonate, gypsum,
Particularly excellent effects are exhibited when an inorganic calcium salt such as calcium phosphate or a kaolinite-based or pyrophyllite-based clay is used as a main carrier. The term "main carrier" as used herein means that the substantial carrier is composed of these carriers, and the total amount of these carriers is 1/2 of the total amount of the granules.
This is the case when occupying the above.

In the granules, in addition to the main carrier, other types of carriers and binders, surfactants, stabilizers, dyes, attractants and other auxiliary ingredients that can be added to the usual granules may be blended. it can.

Such carriers include, in addition to the above-mentioned bentonite and talc, acid clay, zeolite, diatomaceous earth, feldspar powder, powders of natural minerals such as silica sand powder, synthetic silica and potassium silicate called so-called white carbon, In addition, titanium white, synthetic inorganic mineral powder such as alumina, ammonium sulfate, potassium chloride, sodium tripolyphosphate,
Inorganic salts such as sodium hexametaphosphate, sugar, starch, lactose, ground powder, cereal powder, rice cereal, coffee, coconut, coconut and other powders, and organic powders such as activated carbon and carbon black can be used.

Examples of the binder include sodium and calcium salts of lignin sulfonic acid, starch, dextrin obtained by cutting starch into an appropriate size with an enzyme, acid or alkali, starch derivatives obtained by etherifying or esterifying these, polyvinyl alcohol, and the like. Denatured products, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose; natural gums such as gum arabic and xanthan gum; salts of natural high molecular organic acids such as alginic acid and humic acid; high molecular weight polyethylene glycol or polyethylene oxide; Can be used. In the case of granules mainly used for paddy fields, those which disintegrate and disperse in water are generally used.As such a binder for such granules, those which can be dissolved in water to form a low-viscosity aqueous solution are desirable, Preferable examples thereof include sodium or calcium salts of ligninsulfonic acid, low molecular weight dextrin, polyvinyl alcohol (PVA), sodium salt of carboxymethyl cellulose (CMC-Na), and gum arabic.

The surfactant is added for the purpose of improving the wetting of the particles, disintegration and dispersion in water, and controlling the dissolution of the main agent. The surfactant may be appropriately selected from anionic, nonionic, cationic and amphoteric surfactants according to these purposes. A frequently used surfactant is a polycarboxylic acid type as a disintegrating and dispersing agent for granules in water, or a polysulfonic acid type, or a polysoap which is a copolymerization type thereof, and is blended for imparting water wettability. But not limited to dodecylbenzene sulfonate.

Stabilizers include carrier solid acid activity inhibitors such as ethylene glycol and polyethylene glycol, propylene glycol and polypropylene glycol, pH regulators such as organic acids and propyl acid phosphate, and BHT and propyl gallate. An antioxidant, an ultraviolet absorber such as hydroxy-4-n-octoxy-benzophenone, or the like can be used.

Dyes are sometimes used for the purpose of stabilizing or recognizing a base material. Depending on the purpose, a dye such as blue, red or yellow may be appropriately selected and used.

The attractant is compounded to attract pests and the like, and sugar, molasses, fragrance and the like are used.

When these auxiliaries and active ingredients are solids, they are often mixed and granulated after pulverizing all or part of them with a suitable pulverizer. The pulverizer can be either dry or wet.However, if all of the raw materials to be granulated are pulverized with a wet pulverizer, the amount of kneading water becomes too large to be granulated by the extrusion granulation method. Then, only a part of the auxiliaries is wet-pulverized, and then uniformly mixed with the remaining auxiliaries and granulated. When a compound containing a liquid, a compound having a low melting point, or a compound which is unstable to water or heat is contained in the formulation, it is often difficult to commercialize it simply by mixing it with another powdery component. In such a case, the components may be used alone or as a mixture of two or more, and in some cases, may be heated and melted, or may be diluted with an appropriate solvent to be in a liquid form, and may be used as an oil-absorbing powdery auxiliary. After being absorbed, pulverized and treated in the same manner as the powder raw material, or obtained by granulating and drying other components that can be granulated by a usual method, these liquids are obtained by the method described above. In many cases, a method is employed in which the desired granules are obtained by uniformly absorbing the components.

In these steps, a hammer mill, a jet mill, a pin mill, a roller mill, a boring mill, a roll crusher or the like is used as a dry pulverizer, and a sand mill, an attritor, a colloid mill or the like is used as a wet pulverizer. As a mixer, a ribbon mixer, a V-type mixer, a rotary mixer, or the like is used. As a kneading machine, a continuous kneader is often used. A mold mixer or the like may be used.

Kneading is accomplished by adding a wet-pulverized suspension to a powdered auxiliary and mixing with these kneading machines, in which case it may be diluted with water if necessary, When there are auxiliary agents which are soluble in water, they are often dissolved in a suspension and kneaded.

Raw materials crushed, mixed and kneaded by these steps are:
In the next step, it is granulated by an extrusion granulator. Extrusion granulators include a horizontal extrusion type, a vertical type called a basket type, and a granulator that extrudes at high pressure using a roller.The present invention is effective for any of these models. Can be used for

The so-called somen-like granulated wet product obtained by these extrusion granulators is dried using a suitable dryer.
Fluid bed dryers are often used for drying,
A rotary kiln or a shelf-type ventilation dryer can also be used.
The resulting dried product is sized using a suitable sizing machine and then turned into a product.If the product is completely dried and then sieved using a crusher, powdering of the grains occurs and the yield is reduced. If the particle size is reduced to a level close to the target particle size due to inadequate impact at the stage until complete drying,
Grain size can be easily adjusted with relatively small energy, and not only the yield can be reduced, but also the load on the equipment in the final size-regulating stage can be significantly reduced.

If liquid or liquid components are to be absorbed by the obtained granules, in the subsequent step, pour the liquid raw material while mixing the granules with an appropriate mixer, and absorb uniformly to obtain the product. I do. If the mixer used for absorbing the liquid raw material is a type that mixes at high speed, the particles are likely to be crushed,
It is advantageous to use a mixer with less crushing of the grains, such as a conical mixer, a V-type mixer or a rotary mixer.

The non-medical granules thus obtained mean those used for purposes other than direct administration to the human body, such as pesticides, epidemics, veterinary drugs, fish pond drugs, fertilizers, soil
pH adjusters and the like are included. As long as the granules use the extrusion granulation method during the process, regardless of the particle size of the final product, granules (297 to 1680 μm) and powders and granules (44 to 297 μm) on the registration of agricultural chemicals
m) or a particle size distribution coarser than 1680 μm. Further, regardless of the method of use and the final product form, the obtained granule may be used as it is, or a suspension may be prepared by adding water at the time of use and used as a spraying agent. Further, the tablet may be further processed for tableting, or may be divided into small containers such as capsules for use.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited thereto.

(Example 1) In a solution of 1 part of Compound No. 51 in Table 1 in 36 parts of water, 63 parts of a pyrazolate raw material was added and mixed to form a slurry.
This slurry was pulverized for 1 hour with an Attritor 1S (Mitsui Miike Seisakusho). Separately, 65.62 parts of heavy calcium carbonate (Adachi Lime Industry Co., Ltd.) and Pentonite (Toyo Jun Kogyo Co., Ltd.)
20 parts of Hotaka), 2.0 parts of sodium tripolyphosphate, and 1.5 parts of AMICOL No. 1 (Nissen Chemical Industry Co., Ltd.) were charged and diluted with 8 parts of water added to 17 parts of the above suspension while mixing. After adding and kneading the liquid, the mixture is granulated with an extruder granulator EXK-1 (Fuji Paudal Co., Ltd.) with a screen diameter of 0.7 mm, dried and sieved with a sieve with an opening diameter of 1.000 mm and 0.500 mm. The resulting mixture was sized to obtain sunbird granules.

(Example 2) While 1 part of Compound No. 41 in Table 1 was dissolved in 36 parts of water, 63 parts of a pyrazolate raw material was added and mixed to form a slurry.
This slurry was pulverized for 1 hour with an Attritor 1S (Mitsui Miike Seisakusho). Separately, 68.8 parts of heavy calcium carbonate (Adachi Lime Industry Co., Ltd.), 20 parts of bentonite (Toyo Jun Kogyo Co., Ltd., Hotaka-India), 20 parts of Nauta Mixer (Hosokawa Micron Co., Ltd.), and AMICOL No. 1 Co., Ltd.) 1.
To 5 parts of the mixture, while mixing, add 10 parts of the above suspension to 2.0 parts of Toxanone GR30 (Sanyo Kasei Kogyo Co., Ltd.) and 8.0 parts of water, add a diluted suspension, knead the mixture, and extrude. EXK−
Use a type 1 (Fuji Paudal Co., Ltd.)
The mixture was granulated with a diameter of 7 mm, dried and sieved with a sieve having an opening diameter of 1.000 mm and a 0.500 mm sieve to obtain a granule for Xsakarin granules.
97.5 parts of the base particles were charged into a Nauta mixer, and 2.5 parts of a marshette raw material were added and mixed to obtain Kusakarin granules 25.

(Example 3) Compound 3 in Table 1 was dissolved in 3 parts of water in 37 parts of water.
60 parts of Compound A bulk was added and mixed to form a slurry. This slurry was pulverized by a Dynomill KDL type (Shinmaru Enterprises Co., Ltd.) using glass beads having a diameter of 0.5 mm at a rotation speed of 4500 rpm and a supply speed of 3 L / hr. Siegrite in Nauta mixer (Siegrite Mining Co., Ltd.)
38.6 parts, 35 parts of bentonite, 1.0 part of cellogen 5A (Daiichi Kogyo Seiyaku Co., Ltd.) and 0.2 parts of neogen powder (Daiichi Kogyo Seiyaku Co., Ltd.) were added, and 40 parts of the above suspension was added with mixing. After kneading, basket-type extrusion granulator (Co., Ltd.)
It was extruded and granulated from a screen opening diameter of 0.6 mm using Kikusui Seisakusho. After drying, the granules were sieved in a range of 0.840 mm to 0.149 mm to obtain a granular wettable powder containing 25% of compound A.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Akiyoshi Kawagishi 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Co., Ltd. Satoshi Nakajima 1041 Yasu, Yasu-cho, Yasu-gun, Shiga Prefecture Within Sankyo Co., Ltd. (56) References JP-A-60-19774 (JP, A) JP-A-62-171552 (JP, A) JP-A-60-100565 (JP) JP-A-53-9315 (JP, A) JP-A-64-79154 (JP, A) JP-B-38-10550 (JP, B1) JP-A-1-503690 (JP, A) (58) Surveyed field (Int.Cl. ⁶ , DB name) B01J 2/20 A01N 25/12 C05G 3/00

Claims (4)

(57) [Claims] 1. A solid active ingredient which is hardly soluble in water is wet-pulverized in water to form a slurry, which is mixed with a mineral fine powder carrier and extruded for granulation. A method for producing a non-medical granule, which comprises blending a compound represented by the general formula (1) as a property improving agent. [Wherein, R ₁ represents a C ₂ -C ₆ alkyl group, R ₂ and R ₃ represent a hydrogen atom or a C ₁ -C ₆ alkyl group, and X represents an alkali metal or ammonium group. ] 2. The method for producing non-medical granules according to claim 1, wherein the main carrier is an inorganic calcium salt or pyrophyllite or kaolinite clay. Wherein R ₁ of the compound represented by the general formula (1) and
R ₂ is alkyl group of C ₃ -C _4; method of manufacturing a non-medical granules according to claim (1) or (2) wherein R _3, characterized in that a hydrogen atom. 4. The method according to claim 1, wherein the solid active ingredient is a biocide for agricultural use or a biocide for epidemic prevention.
Or the method for producing a non-medical granule according to (2).