JPH0699245B2 - Granular wettable pesticide composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a granular wettable pesticide composition, and more particularly to a granular wettable pesticide composition having improved physical properties.

[Conventional technology]

Agricultural chemicals are usually processed into powders, granules, wettable powders, sols, emulsions, etc., and used in a dosage form suitable for the purpose for rational application. Dust and granules are in their original form,
The wettable powder, sol and emulsion are diluted with water before use. Since the sol and emulsion are liquid, there is no powdering when diluted with water and the weighing is easy, while the wettable powder is safe in that it is not contained in combustible substances such as organic solvents, while water is The rising of finely divided particles at the time of dilution is unavoidable, which poses a safety and health problem for workers. Nowadays, when pesticides are required to be safe and rational, granular wettable powders are advantageous in handling and safety, and granulation of wettable powders is being promoted.

Conventionally, as a technique for producing a granular wettable powder, a method of blending starch and a hydratable inorganic salt (Japanese Patent Publication No. 53-12577),
A method of blending a saccharide, a naphthalenesulfonic acid type surfactant and an alkali metal phosphate (JP-A-57-163303),
Method for blending anionic and nonionic surfactants represented by the general formula R ₁ O (A ₁ O) _n SO ₁ M ₁ or R ₂ O (A ₂ O) _m COCH ₂ SO ₃ M _2. (JP-A-59-193803) and the like have already been proposed.

[Problems to be solved by the invention]

However, the conventional granular wettable powder as described above does not have sufficient physical properties required for granular wettable pesticides such as disintegration in water, dispersibility in water, and suspending properties, and does not quickly become a stable suspension. Or the dispersibility in water is deteriorated over time due to climatic effects such as moisture absorption during storage of the product, and the dispersibility in water is easily affected by the hardness of water, which is not always practical. there were.

The present invention solves the above-mentioned problems, and is not affected by the hardness of water when diluted with water, rapidly disintegrates and disperses into a stable suspension in water, and is not affected by moisture absorption and the like,
It is an object to provide a granular wettable pesticide composition that does not deteriorate with time.

[Means for solving problems]

The present invention is a pesticide active ingredient, and a copolymer of acrylic acid and itaconic acid having a molecular weight of 5000 to 20000, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid and styrene, a maleic acid and diisobutylene. A granular hydratable pesticidal composition comprising a copolymer and one or more polycarboxylic acid type surfactants selected from salts thereof with alkali metals, ammonia or amines.

Pesticide active ingredient used in the present invention, insecticide, fungicide,
It is a component having an activity as a pesticide such as an acaricide and a herbicide, and examples thereof include the following. That is, as an insecticide, 2-methoxy-4H-1,3,2-
Benzodioxaphosphorin-2-sulfide (salithione), dimethyl (3-methyl-4-nitrophenyl) thiophosphate (MEP), 2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethylphosphate ( CVM
P), 2-chloro-1- (2,4-dichlorophenyl) vinyldimethylphosphate (dimethylvinphos), dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (DEP), dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate (dimethoate), 2
-Chloro-1- (2,4-dichlorophenyl) vinyldiethylphosphate (CVP), 0,0-dimethyl-S-phthalimidomethyldithiophosphate (PMP), 0,0-dimethyl-S [5-methoxy-1 , 3,4-thiadiazol-2 (3
H) -Onyl (3) -methyl] dithiophosphate (DMT
P), 0,0-diethyl-3,5,6-trichloro-2-pyridylphosphorothioate (chlorpyrifos), 0, S-dimethyl-N-acetylphosphoroamidothioate (acephate), 0,0-diethyl-0. -(3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate) pyridaphenthione), 1-naphthyl-N-methylcarbamate (NAC), metatryl-N-methylcarbamate (MTMC), 3,4-xylyl -N-methyl carbamate (MPMC), 3,5-xylyl-N-methyl carbamate (XMC), 2-secondary butylphenyl-N-methyl carbamate (BPMC), S-methyl-NN [(methylcarbamoyl) oxy] thio Acetoimidate (Mesomel), 2-isopropoxyphenyl-N-methylcarbamate (PHC), 1,3-bis (carbamoylti) E) -2-
(N, N-dimethylamino) propane hydrochloride (cartap), 6-methyl-2,3-quinoxaline dithiocarbamate (quinoxaline), ethyl 4,4'-dichlorobenzylate (chlorobenzilate), ethyl-0- Benzoyl-3-chloro-2,6-dimethoxybenzohydrochimate (benzoate), isopropyl 4,4'-dibromobenzylate (phenisobromolate), tricyclohexyltin hydro-oxide (Plectran); 5-methyl-1,2,4-triazolo [3,4
-B] -benzothiazole (tricyclazole), 3 '
-Isopropoxy-2-methylbenzanilide (Mepronil), zinc ethylene bisdithiocarbamate (Zineb), Manganese ethylene bisdithiocarbamate (Manneb), methyl-1- (butylcarbamoyl)-
2-benzimidazole carbamate (Benomyl), N
-Trichloromethylthiotetrahydrophthalimide (captan), tetrachloroisophthalonitrile (TP
N), 2,3-dicyano-1,4-dithiaanthraquinone (dithianon), 1,2-bis (3-methoxycarbonyl-2)
-Thioureido) benzene (thiophanatemethyl) sulfur, 4,5,6,7-tetrachlorophthalide (phthalide),
Cupric hydroxide, polyoxin complex, blasticidin-S-benzylaminobenzene sulfonate (blasticidin S), streptomycin hydrochloride (streptomycin), N- (parafluorophenyl) -dichloromaleimide (fluorimide) ); As a herbicide, 3-isopropyl-2,1,3-benzo-
Thiadiadinone- (4) -2,2-dioxide (Bentazone), 1- (α, α-Dimethylbenzyl) -3- (paratolyl) urea (Daimuron), 2-Methylthio-4,6-
Bis-ethylamino-s-triazine (cimetrin),
3,4-Dichloropropionanilide (DCPA), S- (4
-Chlorobenzyl) -N, N-diethylthiocarbamate (benchocarb), 3- (3,4-dichlorophenyl)
-1-Methoxy-1-methylurea (linuron), 2-
Chlor-2 ', 6'-diethyl-N- (methoxymethyl)
-Acetanilide (arachlor), α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-para-toluidine (trifluralin), 2-chloro-4,6-bis (ethylamino) -s- Examples include triazine (CAT) and gibberellin. These pesticidal active ingredients can be used alone or in combination of two or more.

Polycarboxylic acid type surfactant is a polymer having a molecular weight of 5000 to 20000 having a carboxylic acid as a structural unit, a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, and maleic acid. One or more selected from styrene copolymers, maleic acid and diisobutylene copolymers, and salts thereof with alkali metals, ammonia or amines.

The granular wettable pesticidal composition of the present invention may contain an anionic surfactant in addition to the pesticidal active ingredient and the polycarboxylic acid surfactant. Examples of the anionic surfactant include sodium alkylbenzene sulfonate, sodium lignin sulfonate, ethylene oxide alkyl sulfate ester salt and the like, and sodium dodecylbenzene sulfonate and sodium lignin sulfonate are particularly preferable.

The mixing ratio of each of the above components is 20 to 90% by weight of the agricultural chemical active ingredient,
0.3 to 10% by weight of polycarboxylic acid type surfactant and 0 to 5% by weight of anionic type surfactant are desirable.

The granular wettable pesticidal composition of the present invention, in addition to these components, diatomaceous earth, talc, clay, bentonite, inorganic mineral powders such as calcium carbonate, and water-soluble powders such as lactose, fructose, glucose, etc. as carriers. As a binder, starch, CMC, sodium alginate, etc. can be added, and as a grinding aid, silica sand, amorphous hydrous sodium silicate (white carbon), etc. can be added. If necessary, a decomposition inhibitor, a coloring agent, a defoaming agent, etc. can be added.

The granular wettable pesticidal composition of the present invention is a mixture of these components and formed into a granular form. The production method is to add the necessary amount of a grinding aid, a carrier, a binder, a decomposition inhibitor, a colorant, an antifoaming agent, etc. to the agrochemical active ingredient, polycarboxylic acid type surfactant and anionic type surfactant in the above mixing ratio. , Mix evenly and then pulverize. For crushing, impact type crusher, ball mill,
It can be carried out by a crusher such as a jet atomizer. Then, an appropriate amount of water is added to the obtained fine powder, and the mixture is kneaded and kneaded, then granulated using a granulator and dried to obtain the target product. Granulation can be carried out by a granulator such as an extrusion granulator, a pressure granulator, a fluidized bed granulator and a spray dryer, and a crush granulation method may be adopted. The particle size of the obtained wettable powder is usually preferably 0.1 to 2 mm.

The granular wettable pesticidal composition of the present invention is put into water and dispersed therein to prepare a spray solution for use. The amount of the granular wettable pesticide composition added to water is arbitrary, but is preferably about 0.3 to 20% by weight. The application method of the spray solution is applied to the fields and the like in a manner according to each pesticide active ingredient.

〔Example〕

Next, the present invention will be described with reference to examples. All parts are parts by weight.

Example 1 80 parts of tricyclazole, 3 parts of a sodium salt of a copolymer of maleic acid and styrene (molecular weight: 15000), 3 parts of diatomaceous earth
Parts, 3 parts of silica sand, and 11 parts of lactose are added and mixed, and then finely pulverized with a jet ohmizer, and an appropriate amount of water is added and kneaded. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a tricyclazole granular wettable powder.

Example 2 To 80 parts of tricyclazole, 3 parts of a sodium salt of a copolymer of maleic acid and styrene (molecular weight: 15000), 2 parts of sodium dodecylbenzenesulfonate, 3 parts of diatomaceous earth, 3 parts of silica sand, and 9 parts of lactose were added and mixed. After that, it is pulverized with a jet ohmizer and kneaded by adding an appropriate amount of water. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a tricyclazole granular wettable powder.

Example 3 To 80 parts of TPN, 3 parts of a sodium salt (molecular weight 12000) of a copolymer of maleic acid and diisobutylene, 3 parts of diatomaceous earth, 2 parts of starch, and 12 parts of glucose were added and mixed, and then finely powdered with a jet omizer. Then, add an appropriate amount of water and knead. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. After drying this granulated product, it is sized and TP
An N granular wettable powder was obtained.

Example 4 To 80 parts of TPN was added 3 parts of a sodium salt of a copolymer of maleic acid and diisobutylene (molecular weight 12000), 3 parts of sodium ligninsulfonate, 3 parts of diatomaceous earth, 2 parts of starch, and 9 parts of glucose, and after mixing. Finely pulverize with a jet omizer and add an appropriate amount of water and knead. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a TPN granular wettable powder.

Example 5 To 70 parts of dimethylvinphos part, 5 parts of sodium salt (molecular weight of 8000) of a copolymer of acrylic acid and itaconic acid, 10 parts of white carbon, 4 parts of starch, and 11 parts of clay were added and mixed, and then jet-oed. Pulverize with a mizer, granulate while spraying water in a fluidized bed granulator, dry and then sizing,
A granular wettable powder of dimethylvinphos was obtained.

Example 6 70 parts of dimethylvinphos, 5 parts of sodium salt of a copolymer of acrylic acid and itaconic acid (molecular weight: 8000), 3 parts of sodium dodecylbenzenesulfonate, 10 parts of white carbon
Parts, 4 parts starch, and 8 parts clay were added and mixed,
The mixture was pulverized with a jet atomizer, granulated while spraying water in a fluidized bed granulator, dried and then sized to obtain a dimethyl vinphos granular wettable powder.

Example 7 40 parts of MEP is adsorbed on 40 parts of white carbon, and an ammonium salt of a copolymer of maleic acid and styrene (molecular weight 5000)
After 3 parts and 17 parts of clay are added and mixed, the mixture is pulverized with an impact type pulverizer, and an appropriate amount of water is added and kneaded. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a MEP granular wettable powder.

Example 8 To 75 parts of CAT, 5 parts of an animium salt (molecular weight 10,000) of a copolymer of acrylic acid and itaconic acid, 3 parts of sodium ligninsulfonate, 3 parts of diatomaceous earth, 3 parts of starch, and 11 parts of fructose were added and mixed. , Pulverized with a jet omizer, granulated while spraying water in a fluidized bed granulator, dried and then granulated to obtain a CAT granular wettable powder.

Comparative Example 1 To 80 parts of tricyclazole, 2 parts of sodium alkylnaphthalenesulfonate, 2 parts of sodium hexametaphosphate, 3 parts of diatomaceous earth, 3 parts of silica sand, and 10 parts of lactose were added and mixed, and then finely pulverized with a jet ohmizer to obtain an appropriate amount. Add water and knead. This is put into an extrusion type granulator with a hole diameter of 0.8 mm.
Add a screen to granulate. The granulated product was dried and then sized to obtain a tricyclazole granular wettable powder.

Comparative Example 2 To 80 parts of tricyclazole, 3 parts of a sodium salt of formalin naphthalenesulfonate, formalin condensate, 2 parts of sodium tripolyphosphate, 3 parts of diatomaceous earth, 3 parts of silica sand, and 9 parts of lactose were added and mixed, and then pulverized with a jet ohmizer. , Add an appropriate amount of water and knead. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a tricyclazole granular wettable powder.

Comparative Example 3 To 80 parts of TPN, 3 parts of ethylene oxide nonyl phenyl ether sulfate ammonium salt, 3 parts of ethylene oxide nonyl phenyl ether, 3 parts of diatomaceous earth, 2 parts of starch, and 9 parts of glucose were added and mixed, and then mixed with a jet atomizer. Pulverize and add an appropriate amount of water and knead. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. This granulated product is dried and then sized, and TPN
A granular wettable powder was obtained.

Comparative Example 4 80 parts of TPN, 3 parts of naphthalenesulfonic acid sodium salt formalin condensate, 1 part of sodium dialkylsulfosuccinate
Parts, sodium tripolyphosphate 3 parts, diatomaceous earth 3 parts,
2 parts of starch and 8 parts of glucose are added and mixed, and then finely pulverized with a jet ohmizer, and an appropriate amount of water is added and kneaded. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. This granulated product is dried and then sized,
A TPN granular wettable powder was obtained.

Comparative Example 5 To 70 parts of dimethylvinphos was added 3 parts of ethylene oxide styrenated phenol ether ammonium sulfate, 3 parts of ethylene oxide styrenated phenol ether, 10 parts of white carbon, 4 parts of starch, and 10 parts of clay, and after mixing, a jet ohmizer. Was pulverized, granulated while spraying water in a fluidized bed granulator, dried and then sized to obtain dimethyl vinphos wettable powder.

Comparative Example 6 To 70 parts of dimethylvinphos, 3 parts of ethylene oxide nonylphenol ether sulfate sodium salt, 2 parts of ethylene oxide nonylphenol ether, 10 parts of white carbon, 4 parts of starch, and 11 parts of clay were added and mixed, and then mixed in a jet atomizer. It was then pulverized, granulated while spraying water in a fluidized bed granulator, dried and then sized to obtain a dimethyl vinphos granular wettable powder.

Comparative Example 7 40 parts of MEP is adsorbed on 40 parts of white carbon, 5 parts of ammonium sulfate, 5 parts of starch, and 10 parts of clay are added and mixed, then finely pulverized by an impact pulverizer, and an appropriate amount of water is added and kneaded. . This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator. The granulated product was dried and then sized to obtain a MEP granular wettable powder.

Comparative Example 8 To 75 parts of CAT, 4 parts of sodium chloride, 3 parts of sodium ligninsulfonate, 3 parts of diatomaceous earth, 3 parts of starch, and 12 parts of fructose were added and mixed, and then finely pulverized with a jet ohmizer, and an appropriate amount of water was added. And knead. This is granulated by attaching a screen with a hole diameter of 0.8 mm to an extrusion type granulator.
The granulated product was dried and then sized to obtain a CAT granular wettable powder.

The following tests were conducted on the granular wettable powders prepared in Examples 1 to 8 and Comparative Examples 1 to 8 described above.

Test example (1) Disintegration in water 9 cm in diameter containing 50 ml of 20 ° C. 3 degree hard water or 20 degree hard water
Into a petri dish, 5 particles of the granular wettable powder are put, and the time until the particles disintegrate and the prototype does not stay is measured, and the average value of 5 particles is calculated. The shorter the disintegration time, the better.

(2) Dispersibility in water 20 g of the granular wettable powder as a sample is placed in a 200 ml beaker containing 200 ml of 3 degree hard water or 20 degree hard water at 20 ° C, and 2 minutes later, 1 second per second along the inner circumference of the beaker using a glass rod. At the speed of
Stir 10 times to the right and 10 times to the left, stir, and immediately load the contents.
Place on a 42 mesh screen. If there is residue in the beaker, pour it on the sieve with a little water. After 30 seconds transfer the residue on the sieve to a 100 ml beaker with a small amount of water, 1
Dry at 05 ° C and weigh. Then, the dispersibility in water (%) is calculated by the following formula. The higher the dispersibility in water, the better.

a formula (3) Suspendability Accurately weigh 0.5 g of the sample wettable powder in a 100 ml beaker and mix well with 20 ° C 3 ° hard water or 20 ° hard water 50 ml little by little to disperse well, and 250 ml with stopper Transfer to a graduated cylinder, add the same 3 degree hard water or 20 degree hard water as above to 250 ml, and let stand for 15 minutes. 3 per minute
Stir vigorously upside down 0 times and let stand for 15 minutes. After allowing to stand, a test solution is collected from the center of the solution using a 25 ml whole pipette, and the pesticide active ingredient in the test solution is analyzed. The higher the susceptibility (%), which is the susceptibility obtained by calculating the percentage of the active ingredient for measurement with respect to the theoretical value when the test solution is suspended uniformly, the better.

Table 1 shows the results of the test conducted immediately after the production of the granular wettable powder and after storage in a paper bag for 1 year.

Example 9 70 parts of tricyclazole to 5 parts of a sodium salt of a copolymer of maleic acid and styrene (molecular weight 15000), 3 parts of sodium dodecylbenzenesulfonate, 10 parts of white carbon
Parts, 4 parts of starch and 8 parts of clay were added and mixed, then pulverized with a jet omizer and granulated while spraying water in a fluidized bed granulator. After drying, the granules were sized to obtain a tricyclazole wettable powder.

Example 10 70 parts of TPN, 5 parts of sodium salt of a copolymer of maleic acid and diisobutylene (molecular weight 12000), 10 parts of white carbon
Parts, 4 parts of starch and 11 parts of clay were added and mixed, then pulverized with a jet ohmizer and granulated while spraying water in a fluidized bed granulator. After drying, the particles were sized to obtain a TPN granular wettable powder.

Example 11 To 70 parts of dimethylvinphos was added 10 parts of a sodium salt (molecular weight 8000) of a copolymer of acrylic acid and itaconic acid, 10 parts of white carbon, 4 parts of starch and 6 parts of clay, and the mixture was mixed with a jet atomizer. It was then pulverized and granulated while spraying water in a fluid bed granulator. After drying, the particles were sized to obtain a dimethyl vinphos granular wettable powder.

Comparative Example 9 To 70 parts of tricyclazole was added 5 parts of sodium polyacrylate (manufactured by Toagosei Chemical Industry Co., Ltd.), 3 parts of sodium dodecylbenzenesulfonate, 10 parts of white carbon, 4 parts of starch and 8 parts of clay, and after mixing, It was pulverized with a jet omizer and granulated while spraying water in a fluidized bed granulator. After drying, the granules were sized to obtain a tricyclazole wettable powder.

Comparative Example 10 70 parts of TPN, 5 parts of sodium polyacrylate (manufactured by Toagosei Co., Ltd.), 10 parts of white carbon, and 4 starches
Parts and 11 parts of clay were added and mixed, then finely pulverized by a jet ohmizer and granulated while spraying water in a fluidized bed granulator. After drying, the particles were sized to obtain a TPN granular wettable powder.

Comparative Example 11 70 parts of dimethylvinphos, 10 parts of sodium polyacrylate (manufactured by Toagosei Chemical Industry Co., Ltd.), 10 parts of white carbon
Parts, 4 parts of starch and 6 parts of clay were added and mixed, then pulverized with a jet omizer and granulated while spraying water in a fluid bed granulator. After drying, the particles were sized to obtain a dimethyl vinphos granular wettable powder.

Immediately after the production of the granular wettable powders prepared in Examples 9 to 11 and Comparative Examples 9 to 11, the results of the tests shown in the above Test Examples are shown in Table 2.

[Effects of the Invention] As is clear from the above description, the granular hydratable agrochemical composition of the present invention has good water disintegrability, water dispersibility and suspension without being affected by the hardness of the dilution water used. Granular hydratable pesticidal composition, which has various physical properties required, and deterioration of various physical properties is not a practical problem even when the product is stored for a long period of time. A compatible pesticide composition is obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area A01N 57/14 C 9159-4H

Claims (4)

[Claims] 1. A pesticide active ingredient, a copolymer of acrylic acid and itaconic acid having a molecular weight of 5000 to 20000, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid and styrene, maleic acid and diisobutylene. And a polycarboxylic acid type surfactant selected from salts of these alkali metals, ammonia or amines. 2. The granular wettable pesticidal composition according to claim 1, wherein the agrochemical active ingredient is one or more selected from insecticides, fungicides, acaricides and herbicides. 3. The granular wettable pesticidal composition according to claim 1 or 2, further comprising an anionic surfactant. 4. An anionic surfactant is one or more selected from sodium alkylbenzene sulfonate, sodium lignin sulfonate, and ethylene oxide alkyl sulfate ester salt.
The granular wettable pesticidal composition according to the item.