JPH09315902A - Granular agrochemical - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a granular agrochemical capable of preventing the agrochemical from sticking itself while storing a long period, easily using the one because powder thereof hardly going up and useful as an excellent insecticide, bactericide, herbicide, etc., by blending a specified anhydrous silica with an active ingredient of an agrochemical. SOLUTION: This granular agrochemical is obtained by combining an active ingredient of the agrochemical with an anhydrous silica having about 5-20nm average diameter. The granular agrochemical is preferably used as a water-soluble granular agrochemical. A water-soluble active ingredient of the agrochemical having >=0.1g/ml solubility in water at 20 deg.C is preferably used as the active ingredient of the agrochemical. Acephate, nitenpyram, cartap hydrogen chloride salt, etc., are especially used and the acephate is most preferable. A content of the active ingredient of the agrochemical based on the total granular agrochemical is about 10-95wt.% and the content of the anhydrous silica is about 0.1-3wt.%. The granular agrochemical hardly causes a chemical injury and is easily used because of being water-soluble.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to pesticide granules which prevent caking and have less dusting. The pesticidal granules of the present invention can be used as excellent pesticide granules for insecticidal, sterilizing, weeding, etc., which are easy to handle because they prevent caking property during long-term storage and have little dusting during use.

[0002]

2. Description of the Related Art Conventionally, high boiling point solvents such as calcium carbonate, lactone and phenylxylylethane have been used as anti-caking agents in the field of agricultural chemical formulations (JP-A-53-53).
15425, JP-A-59-216801, JP-A-63-
107903). JP-A-6-128102 describes a granular wettable powder containing an agrochemical active ingredient and diatomaceous earth. Further, JP-A-7-2612 describes a solid agricultural chemical preparation containing acephate and a calcined product of synthetic silicic acid. However, there is no description in any of the publications regarding pesticide granules containing anhydrous silica having an average particle size of 5 to 20 nm and use of anhydrous silica for preventing solidification of the pesticide granules.

[0003]

The conventional water solvent, which is in the form of powder, has a problem of dusting during measurement of a drug or preparation of a drug solution, and lack of fluidity makes it difficult to measure. There was a drawback. Further, in the granular form, there was a problem of solidification during long-term storage. The liquid formulation has a drawback that it cannot be applied to an agrochemical active ingredient that is easily decomposed in a state of being dissolved in water. Further, since it is a liquid, it has to be put in a solid container such as a glass bottle or a plastic bottle, which causes problems such as breakage of the container and a large storage space. In addition, the current situation is that it is not environmentally friendly, such as the problem of disposal of used containers. From the viewpoint of worker protection, it is difficult to solve these problems with conventional powdery water solvents in order to make powder-free preparations that are easy to weigh. It's a problem. Therefore, there has been a demand for the development of pesticide granules which have less dusting, are easy to measure and handle, and are convenient to store and store. In particular, pesticide granules containing a water-soluble pesticide active ingredient may solidify due to pressurization, humidification or the like when stored for a long period of time, and measures to prevent solidification are required.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has predicted that by blending anhydrous silica having an average particle size of 5 to 20 nm with an agrochemical active ingredient. It was also found that pesticide granules that prevent caking even outside can be obtained with less dusting. Furthermore, the present inventors have completed the present invention as a result of further research and examination based on these findings.

That is, the present invention provides (1) a granule containing an agrochemical active ingredient and anhydrous silica having an average particle size of about 5 to 20 nm, and (2) a granular aqueous solvent as described above (1).
The granules described in (1) above, wherein the agricultural chemical active ingredient (3) is a water-soluble agricultural chemical active ingredient having a solubility in water at 20 ° C. of about 0.1 g / ml or more, and (4) the agricultural chemical active ingredient is A granule according to the above (1), which is acephate, nitenpyram, cartap hydrochloride or validamycin A,
(5) The granule according to (1) above, wherein the agrochemical active ingredient is acephate, and (6) the granule according to (1) above, wherein the content of the agrochemical active ingredient is about 10 to 95% by weight based on the whole preparation. , (7) The content of anhydrous silica is about 0.1 to 3% by weight with respect to the whole preparation, and (8) anhydrous for preventing solidification of the pesticide granules. Regarding the use of silica. The TM used in the present specification
Means a registered trademark.

In the agrochemical granules of the present invention, the agrochemical active ingredient may be any agrochemical active ingredient such as insecticide, fungicide and herbicide, as long as it is solid at room temperature, and one or more kinds thereof may be used. The pesticidal active ingredient can be used. Examples of the pesticide active ingredient corresponding to this are as follows. [Insecticide] pyridafenthion, dimethoate, PM
P, CVMP, dimethylvinphos, acephate, salicion, DEP, NAC, MTMC, MIPC, PH
C, MPMC, XMC, bendiocarb, pirimicarb, mesomel, oxamyl, thiodicarb, cypermethrin, cartap hydrochloride, thiocyclam, bensultap, diflubenzuron, teflubenzuron, chlorfluazuron, buprofezin, hexthiazox, fenbutazin oxide, pyridaben, clofentezin , Nitenpyram and the like. [Fungicide] Diram, thiuram, captan, TPN, fusaride, tolclofos-methyl, fosetyl, thiophanate-methyl, benomyl, carbendazole, thiabendazole, dietofencarb, iprodione, vinclozolin, procymidone, fluorimido, oxycarboxyne, mepronil, flutolanil, pencyclon, metalaxyl, Oxadixyl, triadimefon, hexaconazole, triphorine, blasticidin S, kasugamycin, polyoxine, validamycin A, mildiomycin, PCNB, hydroxyisoxazole, dazomet, dimethyrimol, diclomedine, triazine, ferrimzone, probenazole, isoprothiolane, tricyclazole, pyroquilon. , Oxolinic acid, etc.

[Herbicides] MCP, MCPB, triclopyr, naproanilide, CNP, clomethoxynil, bifenox, MCC, pyributycarb, DCPA, bromobutide, mefenacet, naprobamide, diphenamide, propyzamide, ashram, DCMU, linuron, dimuron, methyldaimuron, tebuchuron,
Bensulfuron-methyl, simazine, atrazine, cimetrin, ametrine, promethrin, dimetamethrin, metribuzin, bentazone, oxadiazone, pyrazolate, benzophenap, prodiamine, glyphosate,
Bialaphos, aloxidim, imazosulfuron, azimsulfuron, pyrazosulfuron-ethyl, shinosulfuron, etc. In addition, the pesticidal active ingredient which is solid at room temperature is not limited to these. Among the above pesticide active ingredients, the solubility in water at 20 ° C is 0.1 g / ml.
The above water-soluble agrochemical active ingredients are preferable, for example, acephate, nitenpyram, cartap hydrochloride, validamycin A and the like are preferable, and acephate is particularly preferable.

In the pesticide granules of the present invention, as anhydrous silica, high temperature (100%) in oxyhydrogen flame of silicon tetrachloride is used.
SiO ₂ obtained by hydrolysis is used. Specifically, Aerosil 130, Aerosil 200,
One type or two or more types selected from Aerosil 200V, Aerosil 300CF, Aerosil R972 (trade name, manufactured by Nippon Aerosil) and the like are used. Among these anhydrous silicas, for example, Aerosil 200, Aerosil 200V and the like are preferable, and Aerosil 200 and the like are particularly preferable. Further, as these anhydrous silica,
For example, those having an average particle size of usually about 5 to 20 nm, preferably about 7 to 15 nm, more preferably about 10 to 12 nm are preferable.

In addition to the pesticide granules of the present invention, other additives commonly used in pesticide granules can be used.
For example, surfactants, binders, stabilizers, colorants, preservatives, extenders and the like can be freely used, and these may be selected according to the kind of the agrochemical active ingredient used.
As the surfactant, any surfactant such as a normal nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used, and one or more of these surfactants can be used. You may use. As the nonionic surfactant, for example, polyoxyethylene alkyl ether,
Polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene ether, polyoxyethylene alkyl ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, block copolymer of ethylene oxide and propylene oxide, higher fatty acid alkanol amide, etc. are used. To be As the cationic surfactant, for example, an alkylamine salt,
A quaternary ammonium salt or the like is used.

As the anionic surfactant, for example,
Naphthalenesulfonic acid polycondensate Metal salt, alkenyl sulfonate, formalin condensate of naphthalene sulfonate, alkyl naphthalene sulfonate, lignin sulfonate, alkylallyl sulfonate, alkyl allyl sulfonate sulfate, etc. Compounds, sodium polystyrene sulfonate, sodium polycarboxylic acid, ammonium polyoxyethylene distyryl phenyl ether sulfate, higher alcohol sulfonates, higher alcohol ether sulfonates, dialkyl sulfosuccinates, higher fatty acid alkali metal salts, etc. To be Among the above, the surfactant used in the present invention is preferably an anionic surfactant or a nonionic surfactant. In particular, as the nonionic surfactant, those having an HLB value in the range of 9 to 13 are preferable from the viewpoint of solubility in water and moistening action. As the anionic surfactant, a surfactant containing sodium dioctylsulfosuccinate or ammonium polyoxyethylene distyryl phenyl ether sulfate as a main component is preferable. More specifically, examples of the anionic surface active agent, (manufactured by Takemoto Oil & Fat Co.) Newkalgen EP-70G ^TM mainly composed of sodium dioctyl sulfosuccinate, NEOCOL SW-C ^TM (Dai-ichi Kogyo Seiyaku ( Co., Ltd.), Sanmorin OT-70 ^™ (manufactured by Sanyo Kasei Co., Ltd.), polyoxyethylene distyryl phenyl ether sulphate ammonium as a main component DIXZOL WK, DIXZOL 60A (Idomo Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured) and the like are used. Examples of the nonionic surfactant having an HLB value of 9 to 12 include polyoxyethylene alkylphenyl ether (eg, polyoxyethylene nonylphenyl ether [NP-85 ^™ ], manufactured by Takemoto Yushi Co., Ltd.) and ethylene oxide. And a block copolymer of propylene oxide (eg, Newpol PE-64 ^™ , manufactured by Sanyo Kasei Co., Ltd.) and the like are used.

A water-soluble binder or the like is preferably used as the binder. Examples of such water-soluble binders include dextrin, polyvinyl alcohol, gum arabic, sodium alginate, polyvinylpyrrolidone,
Glucose, sucrose and the like are used, and dextrin and the like are particularly preferable. By containing these water-soluble binders, the pesticide granules of the present invention can further increase the granule strength without impairing the disintegration dispersibility in water. Examples of the stabilizer include phosphoric acid and PAP.
(Isopropyl acid phosphate) Auxiliary agents and the like are used. As the colorant, for example, cyanine green G, erio green B400, or the like is used. As the preservative, for example, butyl paraben, potassium sorbate, etc. are used. As the bulking agent, for example, lactose, heavy saw, ammonium sulfate, urea, sucrose and the like are used.

The content of the agrochemical active ingredient in the agrochemical granules of the present invention is usually about 5 to 95% by weight, preferably about 10 to 95% by weight, more preferably about 30 to 95% by weight, based on the whole preparation. And more preferably about 50 to 95% by weight. The anhydrous silica is generally used in the range of about 0.1 to 3% by weight, preferably about 0.3 to 3% by weight, more preferably about 0.5 to 2% by weight, based on the whole preparation.
The surfactant may be added in an amount of usually about 10% by weight or less, preferably about 5% by weight or less, based on the whole preparation.
The binder is usually about 20% by weight or less based on the whole preparation,
It may be added preferably in the range of about 10% by weight or less. The coloring agent is usually about 0.3% by weight or less based on the whole preparation,
It may be added preferably in the range of about 0.1% by weight or less.
In addition, additives such as stabilizers and preservatives may be added usually in an amount of about 10% by weight or less based on the whole preparation.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The pesticide granules of the present invention can be produced by a wet extrusion granulation method or a dry granulation method used for the production of ordinary pesticide granules. Of these, the wet granulation method can be usually produced by extrusion granulation using about 1 to 10 parts by weight of water with respect to 100 parts by weight of the formulation solid content. In the case of the dry granulation method, it can be produced only by consolidation without using water. Specifically, in the case of the wet granulation method, the agricultural chemical active ingredient, anhydrous silica, and if necessary, a surfactant, a binder and the like are uniformly mixed with a kneader or the like. For example, of the components to be blended, a solid component is appropriately mixed, a liquid component is dropped therein, and further mixing is continued. In this case, when the solid component is a lump, it is preferable to pulverize the powder into an appropriate powder by coarse pulverization or the like to facilitate the mixing operation.
Suitable powder particles have a particle size of about 1 to 100 μm. Next, an appropriate amount of water is added to the mixture, and the mixture is further kneaded with a kneader. This kneading is carried out to such an extent that the kneaded material gives smooth stickiness and is suitable for extrusion granulation in the subsequent step. Then, the kneaded product is granulated by a usual wet extrusion granulator, dried and sieved to obtain granules.

On the other hand, in the case of the dry granulation method, the pesticide active ingredient,
The anhydrous silica is mixed uniformly by a mixer. The mixture is granulated with a dry granulator. The dry granulation method is inferior in water disintegration and dispersibility in water as compared with the wet granulation method, but does not require a surfactant or a binder,
Moreover, there is an advantage that there are no kneading and drying steps. If necessary, the granulated product is sized to obtain a desired agricultural chemical granule. The sizing is performed in a range where the mesh size does not pass through 300 μm but 1700 μm. The obtained granules preferably have a major axis in the range of about 0.5 to 5.0 mm. The bulk density of the pesticide granules of the present invention thus obtained is usually preferably in the range of about 0.1 to 1.2 g / ml,
A range of about 0.5 to 1.0 g / ml is particularly preferred. The use amount of the pesticide granules of the present invention varies depending on the kind and content of the pesticide active ingredient contained, but is usually about 100 to 5000 g per 10 ares, preferably about 200 to 400.
0 g. The pesticide granules of the present invention are usually used as a granular aqueous solvent. Since anhydrous silica does not usually dissolve in water, the term “water solvent” as used herein means 9
It means that 7% by weight or more is dissolved. As the method of using the pesticide granules of the present invention, a known method generally used for spraying pesticides can be used. For example, the pesticidal granules of the present invention are usually dissolved and diluted in water before use. For example, about 100 to 20,000 times (about 1 g / 100 ml
It is preferable to use it after diluting it to 1 g / 20000 ml). The pesticide granules of the present invention are preferably stored in a moisture-proof container or the like in order to avoid moisture. As such a container, for example, a plastic bottle, a polyethylene bottle, a polyethylene laminated aluminum foil packaging, a polyethylene bag, etc. are convenient.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to Reference Examples, Examples and Test Examples, but the scope of the present invention is not limited thereto. All% and parts used herein are% by weight and parts by weight, unless otherwise specified.

[Reference Example 1] Production of granules A containing 50% acephate 50 parts acephate, 0.5 part surfactant Newpol PE-64, 0.1 part cyanine green G, 49.
After thoroughly mixing 4 parts of lactose, 6 parts of water was added to 100 parts by weight of the formulation solid content, and a kneader (Kikusui Seisakusho, KM-1.
According to 5), kneading was carried out at room temperature until a smooth stickiness was produced. The kneaded product was granulated into cylindrical granules using an extrusion granulator (Kikusui Seisakusho, RG-5M) using a screen having a diameter of 0.8 mm. The obtained granules were dried at 60 ° C. for 1 hour to obtain granules A containing 50% acephate.

[0016]

[Reference Example 2] Production of granule B containing 50% acephate 50 parts acephate, 0.5 part surfactant NP-8
After thoroughly mixing 5, 3.0 parts of dextrin, 0.1 part of cyanine green G, 2.0 parts of titanium oxide and 44.4 parts of lactose, 7 parts of 100 parts by weight of formulation solids were added. Water was added, and the same procedure as in Reference Example 1 was performed to obtain Granule B containing 50% acephate.

[0017]

[Reference Example 3] Production of granule C containing 50% acephate 50 parts acephate, 0.2 parts surfactant DIXZOLE WK, 0.1 part cyanine green G, 2.0 parts white carbon (Carplex CS-5 (Shionogi Pharmaceutical Co., Ltd.), 47.7 parts of lactose were thoroughly mixed, and then 100
9 parts of water was added to parts by weight of formulation solids, and the following Reference Example 1 was used.
Granules C containing 50% acephate were obtained by the same procedure as described above.

[0018]

[Reference Example 4] Production of granules D containing 95% acephate 95 parts acephate, 0.5 part surfactant Newpol PE-64, 1.0 part dextrin, 0.1 part cyanine green G, 3 After thoroughly mixing 4 parts lactose,
Granule D containing 95% of acephate was prepared by the same procedure as in Reference Example 1 except that 8 parts of water was added to 100 parts by weight of solid formulation.
I got

[0019]

Example 1 Preparation of Granules E Containing 10% Nitenpyram 10 parts Nitenpyram, 0.5 parts Surfactant Dixsol WK, 0.1 parts Cyanine Green G, 2.0 parts Aerosil 200, 87. After thoroughly mixing 4 parts of a heavy saw, 5 parts of water was added to 100 parts by weight of the solid content of the preparation to obtain granules E containing 10% of nitenpyram by the same procedure as in Reference Example 1.

[0020]

Example 2 Acephate 25%, Cartap Hydrochloride 2
Preparation of granules F containing 5% 25 parts acephate, 25 parts cartap hydrochloride,
0.5 parts of surfactant NP-85, 0.3 parts of phosphoric acid,
0.1 part cyanine green G, 2.0 part Aerosil 2
After thoroughly mixing 00, 47.1 parts of lactose, 5 parts of water was added to 100 parts by weight of the formulation solid content, and acephate 25% and cartap hydrochloride 25 were added in the same procedure as in Reference Example 1 below.
% Granules F were obtained.

[0021]

Example 3 Preparation of Granules G Containing 50% Acephate 50 parts acephate, 0.2 parts surfactant Dixsol WK, 0.1 part cyanine green G, 2.0 parts Aerosil 200, 47. After thoroughly mixing 7 parts of lactose, 6 parts of water was added to 100 parts by weight of the solid content of the preparation to obtain Granule G containing 50% of acephate by the same procedure as in Reference Example 1.

[0022]

Example 4 Preparation of Granule H Containing 75% Cartap Hydrochloride 75 parts Cartap Hydrochloride, 0.5 part Surfactant Neupol PE-64, 0.3 part phosphoric acid, 0.1 part Cyanine Green G, 1.0 part Aerosil 200, 23.1
After sufficiently mixing 1 part of lactose, 4 parts of water was added to 100 parts by weight of the solid content of the preparation to obtain granules H containing 75% cartap hydrochloride by the same procedure as in Reference Example 1 below.

[0023]

Example 5 Preparation of Granules I Containing 50% Cartap Hydrochloride, 5% Validamycin A 50 parts Cartap Hydrochloride, 5 parts Validamycin,
0.5 parts of surfactant NP-85, 0.3 parts of phosphoric acid,
0.1 part cyanine green G, 2.0 part Aerosil 2
After thoroughly mixing 00, 0.05 parts of butylparaben and 42.05 parts of lactose, 4 parts are added to 100 parts by weight of the solid formulation.
Granules I containing 50% cartap hydrochloride and 5% validamycin A were obtained by the same procedure as in Reference Example 1 by adding water.

[0024]

Example 6 Preparation of Granule J Containing 95% Acephate 95 parts acephate, 0.2 part surfactant Dixsol WK, 0.1 part cyanine green G, 0.5 part Aerosil 200, 4. After thoroughly mixing 2 parts of lactose,
Granules J containing 95% of acephate were prepared by the same procedure as in Reference Example 1 except that 4 parts of water was added to 100 parts by weight of solid formulation.
I got

[0025]

Example 7 Preparation of Granule K Containing 50% Acephate 50 parts acephate, 0.5 part surfactant Newpol PE-64, 0.1 part cyanine green G, 2.0
Parts of Aerosil 200 and 47.4 parts of lactose were thoroughly mixed, and then 6 parts of water was added to 100 parts by weight of the solid content of the preparation to obtain Granule K containing 50% acephate by the same procedure as in Reference Example 1. It was

[0026]

Example 8 Nitenpyram 10%, Validamycin A5
Of granules L containing 10% nitenpyram, 5 parts validamycin, 0.5
Parts of surfactant Newpol PE-64, 0.1 part of cyanine green G, 1.0 part of Aerosil 200, 0.0
After thoroughly mixing 5 parts of butylparaben and 83.35 parts of heavy saw, 3 parts of water was added to 100 parts by weight of the solid content of the formulation, and nitenpyram 10% was added in the same manner as in Reference Example 1 below.
Granules L containing 5% of validamycin A were obtained.

[0027]

Example 9 Preparation of Granules M Containing 75% Acephate 75 parts acephate, 0.5 part surfactant NEWPOL PE-64, 1.0 part dextrin, 0.1 part cyanine green G, 2 0.0 copies of Aerosil 200, 21.
After thoroughly mixing 4 parts of lactose, 6 parts of water was added to 100 parts by weight of the solid content of the preparation to give Granules M containing 75% of acephate by the same procedure as in Reference Example 1.

[0028]

[Test Example 1] Disintegration in water 500 ml of water is put in a 500 ml cylinder, and a sample is added to this so that the concentration of the active ingredient is 500 ppm. The disintegration property was evaluated in the following three stages. A: One-half or more of the preparation collapsed before reaching the bottom B: One-half or more of the preparation not collapsed before reaching the bottom

[0029]

[Test Example 2] Dispersibility in water 500 ml of water is put in a 500 ml cylinder, and a sample is added to this so that the active ingredient concentration is 500 ppm. The presence or absence of dispersion of the sample was confirmed every time the cylinder was inverted once (180 ° × 2), and the number of inversions required to form primary particles was measured.

[0030]

[Test Example 3] Caking Cylindrical pot made of hard PVC (internal diameter 8 cm, height 12 cm)
Put test grains so that the height is 6 cm, and smooth the surface so that it becomes flat. 1-2m above the inner diameter of the pot
m A small hard PVC disc and weight are placed on it, and the load is 25
g / cm ² . Put the pot in a plastic bag (thickness 0.03 mm), stop the mouth with a rubber band so that it will not be in a pressurized state, leave it at 40 ° C for 3 days and at 0 ° C for 2 days, remove the load, and tilt the pot. Determine the status of consolidation. {Evaluation method} -The pot is inclined and no solidification is observed. + The pot tilts and solidifies, but easily collapses with a light impact. Or there is a lump of 5 mm or less. ++ The pot is tilted and there is solidification, and about half the amount does not collapse with a light impact. Or there is a lump of 5 mm or more. ++ It almost doesn't collapse even if the pot is tilted and a strong shock is given. The results of Test Examples 1 to 3 are shown in Table 1.

[0031]

[Table 1] From Table 1, it was found that the granular aqueous solvent of the present invention was excellent in water disintegration property, water dispersibility and caking property.

[0032]

EFFECTS OF THE INVENTION The pesticide granules of the present invention suppress the occurrence of dusting during the weighing of medicines and the preparation of drug solutions, are not only easy to weigh and handle, but also prevent the solidification during long-term storage. It has the characteristics of prevention and less chemical damage. In addition, it is a formulation that disintegrates and dissolves easily in water and can be used in place of conventional powdery water solvents and liquids.

Claims (8)

[Claims] 1. A pesticide active ingredient and an average particle size of about 5 to 2
Granules containing anhydrous silica of 0 nm. 2. The granule according to claim 1, which is a granular aqueous solvent. 3. The granule according to claim 1, wherein the agricultural chemical active ingredient is a water-soluble agricultural chemical active ingredient having a solubility in water at 20 ° C. of about 0.1 g / ml or more. 4. The granule according to claim 1, wherein the pesticidal active ingredient is acephate, nitenpyram, cartap hydrochloride or validamycin A. 5. The granule according to claim 1, wherein the agrochemical active ingredient is acephate. 6. The granule according to claim 1, wherein the content of the agrochemical active ingredient is about 10 to 95% by weight based on the whole preparation. 7. The granule according to claim 1, wherein the content of anhydrous silica is about 0.1 to 3% by weight based on the whole preparation. 8. Use of anhydrous silica to prevent the solidification of pesticide granules.