JPH015A - Stabilized bensultap formulation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to stabilized S,S'-[2-(dimethylamino)trimethylene]bis-benzenethiosulfonate solid formulations. The preparation of the present invention is used as an agricultural and horticultural insecticide.

[Prior Art] S, S'-[2-(dimethylamino)trimethylene]bis-benzenethiosulfonate [-Product name: Bensultap, trade name: Lupan, hereinafter sometimes referred to as Bensultap. ] is an agricultural insecticide with excellent pest control effect shown by the following structural formula (e.g., Japanese Patent Publication No. 46-13755, No. 45-1884).
7), and has low toxicity to humans and animals, low toxicity to fish, and low toxicity to natural enemies of pests. Therefore, bensultap is mixed with a carrier/filling agent such as mineral powder and used in the field of Jl horticulture as a regular solid preparation such as 9-grain powder or Eiwa-Ko.

[Problems to be Solved by the Invention] However, bensultap is relatively unstable in a solid preparation obtained by mixing it with a carrier/filling agent (e.g. mineral powder), ) If stored for a long period of time, bensultap will gradually decompose, change color, or deteriorate, resulting in a decrease in the content of bensultap, the active ingredient.

In addition, in the bensultap mixed solid preparation obtained by mixing bensultap with II or two or more types of pesticide active substances in order to achieve a wide range of excellent medicinal efficacy and labor-saving simultaneous control, bensultap single solid preparation Decomposition and deterioration of pesticide active ingredients such as bensultap may be more pronounced than in the formulation.

[Means for Solving the Problems] The present invention provides S,S'-[2-(dimethylamino)trimethylene]bis-benzene thiosulfonate and hydrochloric acid, hydrobromic acid, phosphoric acid, @ acid, allenesulfonic acid.

The present invention relates to a stabilized solid preparation containing at least one of dichloroacetic acid and oxalic acid.

That is, the present invention relates to a stabilized solid preparation of bensultap, and the solid preparation of the present invention may contain other pesticidal active substances in addition to bensultap as an agrochemical active ingredient.

The present inventors have found that the stabilizing effect of the pesticide active ingredient (particularly bensultap) in this bensultap solid preparation is among various acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, allenesulfonic acid, dichloroacetic acid, and oxalic acid. It was found that it can be specifically obtained by Other commonly used acids, such as trichloroacetic acid and monochloroacetic acid, do not provide such a stabilizing effect at all.

The stabilizers of the present invention such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, 1-alenesulfonic acid, dichloroacetic acid, and oxalic acid are 1
It can be used as a species or as a mixture of two or more species.

Among these, dichloroacetic acid, hydrochloric acid, and a combination of hydrochloric acid and phosphoric acid are preferred. Particularly preferred is a combination of hydrochloric acid and phosphoric acid. A stabilizer made of a combination of hydrochloric acid and phosphoric acid is safe and harmless to humans and animals, does not cause problems such as soil acidification, and is suitable for industrial production. The stabilized solid preparation of the present invention has virtually no phytotoxicity to plants, and can be safely used without causing any harm to literary figures or animals either during or after application.

The solid preparation of the present invention is a mixture of bensultap and at least one of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, allenesulfonic acid, dichloroacetic acid, and oxalic acid as a stabilizer with a suitable solid carrier/filling agent. Or blended or solid carrier
Manufactured by adsorption on bulking agents. The solid preparation of the present invention is used as a powder, a powder DL, a permanently hydrated granule, a fine granule F, etc., preferably a granule, a fine granule F, and the like.

The formulation of the present invention may contain other agrochemical active ingredients and auxiliary ingredients such as dispersants, spreading agents, penetrants, wetting agents, thickeners, anti-caking agents, flocculants, binders, and antioxidants, as necessary. It's okay.

Among the above-mentioned stabilizers, phosphoric acid is an acid formed by hydration of diline pentoxide, such as orthophosphoric acid (preferably about 1% by weight or more), metaphosphoric acid, and pyrophosphoric acid.

As the allene sulfonic acid such as tripolyphosphoric acid or tetrapolyphosphoric acid, Cs-18 allene sulfonic acid such as benzenesulfonic acid and p-toluenesulfonic acid is used. Hydrochloric acid is preferably concentrated hydrochloric acid (approximately 35% by weight hydrochloric acid)
~2.2% by weight hydrochloric acid, hydrobromic acid preferably about 47%
~0.1% by weight hydrobromic acid and sulfuric acid are preferably concentrated sulfuric acid ~0.1% by weight sulfuric acid.

Hydrochloric acid (as HCl2), hydrobromic acid (as HCl2),
(as HBr), phosphoric acid (as FtaPO4), sulfuric acid (otso), allenesulfonic acid, dichloroacetic acid, or oxalic acid (if two or more types are used, the total amount) is based on the total weight of the final preparation. Approximately 0.05-10% by weight
The amount is desirably about 0.1 to 5% by weight.

Hydrochloric acid, hydrobromic acid, phosphoric acid used as stabilizers.

The sulfuric acid may be diluted with a diluent such as water, an organic solvent (e.g., alcohols such as methyl alcohol and ethyl alcohol, acetone, dichloromethane, etc.), a mixture of water and the above-mentioned organic solvent, if necessary. The stabilizer (if two or more types are used, the total amount) may be diluted to about 2 to 20 times the weight and added, and allenesulfonic acid, dichloroacetic acid, and oxalic acid may be powdered and mixed as necessary. Alternatively, it may be added after being dissolved or suspended in the above-mentioned organic solvent or a mixture of water and an organic solvent.

The content of bensultap in the preparation of the present invention may be about 0.1 to 90% by weight based on the entire final preparation.
Appropriate amounts are 10 to 10% by weight for granules and fine granules F, and approximately 10 to 90% by weight for wettable powders.

Preferably, the solid carrier/filling agent is, for example, clays (eg, kaolin, bentonite, acid clay, finely powdered clay, etc.), talcs (eg, talc powder).

Mineral powders such as silica (e.g., diatomaceous earth, mica powder, white carbon, etc.); plant-based powders such as soybean powder, tobacco powder, wheat flour, and wood flour; as well as calcium carbonate, sulfur powder, Activated carbon or the like may be used alone or in combination of two or more.

Examples of surfactants used as dispersants, spreading agents, penetrating agents, etc. include soaps, polyoxyethylene alkylaryl ethers (e.g., Neugea, E, Ni-1),
42 (E-A-142) ■, manufactured by Daini Kogyo Seiyaku Co., Ltd.),
Polyoxyethylene alkylaryl esters (e.g.
Nonal [F], manufactured by Toho Chemical Co., Ltd.), alkyl sulfates (e.g., Emarl Oo.

Kao v-fiy 40o, Kao Sekike:/manufactured by Co., Ltd.), Ayaki 2.7゜■ Sulfonate w4 (e.g., Neogen, Neogen To, Daiichi Kogyo Seiyaku Co., Ltd. 8 Neobere Sis 0. Kao soap ( (manufactured by Kochu Kasei Co., Ltd.), polyethylene glycol ethers (e.g., 7 Yubo/1z85./Yubo zt=ioo'', Niball I60, manufactured by Kochu Kasei Co., Ltd.), polyhydric alcohol esters (e.g., Tween 200. ) Vienna 80
Nonionic and anionic surfactants such as O, manufactured by Kao Soap Co., Ltd.) are used as necessary.

An example of an anti-caking agent is white carbon.

Talc, diatomaceous, magnesium stearate, etc., flocculants such as liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, etc., binding agents such as carboxymethyl cellulose sodium salt, dextrin, pregelatinized starch, polyvinyl alcohol, antioxidants For example, dibutylhydroxytoluene.

4.4-Thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole, roseoctylphenol, mono(or di- or tri)(α-methylbenzyl)phenol, 2,6-tert-butyl-4- Methylphenol, pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. are used.

In addition to bensultap, the formulation of the present invention includes organic sulfur-based,
Ill or two or more types of pesticide active substances such as organophosphorus, organoarsenic, and organochlorine disinfectants, organophosphorus, organochlorine, carbamate, and pyrethroid insecticides, and various antibiotics. May be added.

Preferred examples of the above pesticide active substances are listed below. (
The name in parentheses after the word compound indicates a general customer or abbreviation, and this general customer or abbreviation may be used below.) Organic sulfur-based fungicide...Zinc ethylenebis(dithiocarbamate) (Zineb): Ethylenebis( Organophosphorus fungicides such as manganese dithiocarbamate (maneb); S-benzyldiisoprobyl phosphorothiolate (IBP); Organic arsenic fungicides such as 0-ethyldiphenylphosphorodithiolate (EDDP)... Iron methanarsonate (MAF)
), ammonium iron methanarsonate (MAFA
) and other organic base fungicides... pentachlorophenol (PC
P); Tetrachloroisophthalonitrile (TPN
): Other fungicides such as 4,5,6.7-titrachlorophthalide (futhalide)...5-methyl-1,2,4-triazolo[3,4-b]benzothiazole (tridiclazole) = Organophosphorus insecticides such as 3-allyloxy-1,2-benzisothiazole 1,1-dioxide (probenazole)...dimethyl 4-nitrotolyl phosphorothionate (MEP); S-1,
2-bis(ethoxycarbonyl)ethyl di.

Methyl phosphorothiorothionate (Marathon);
p-cyanophenyl dimethyl phosphorothionate
(CYAP) and other chlorine-based insecticides...6, 7, 8, 9, 10.10-
Carbamate insecticides such as hexachloroa-1,5,5a,6,9.9a-hexahydro-6,9-methano-2,4,3-benzodioxatiebine 3-oxyto (penzoevin)...l- Naphthyl N-methylcarbamate (NAC); m-tolyl N-methylcarbamate (MTMC); o-5ee-butylphenyl
N-methyl carbamate (BPMC); o-thumenyl N-methyl carbamate (MIPC); 3,
4-Xylyl N-methylcarbamate (MPMO)
; 3,5-xylyl N-methylcarbamate (
Pyrethroid insecticides such as XMC)...pyrethrins,
Allethrin, resmethrin, (RS)α-cyano-3-
Other insecticides such as phenoxybennol (S)-2-'(4-difluoromethoxyphenyl)-3-methylbutylade (flucitrinate)...S, S'-[2-(dimethylamino)trimethylene] Bisthiocarbamate (Cartap); 2-(4-ethquinphenyl)-2-methylpropyl 3-phenoxybenol ether (Ethofenbrox), and the like.

Antibiotics: plasticidin S, kasugamycin, polyoxin, oxotetracycline, validamycin A, etc. Among the above, preferred are validamycin A, prohenazole, l13P, l-lycyclazole, etofenbrox, flucitrinate, NAC, MPMC, MTM
C, BPMC, MI PC.

Particularly preferred are tridiclazole, etofenbrox, BPMC, MIPC, and propenazole.

The amount of pesticide active substances other than bensultap in the bensultap mixed solid preparation is 1% to the entire final preparation.
In the case of seeds, it is approximately 0. Ol to 20% by weight, preferably about 0.05 to 10% by weight, and in the case of two or more types, the total amount of the two or more pesticide active substances is about 0.01 to 2% by weight.
0% by weight, preferably a total of about 0.05 to 15% by weight.

Pesticide active ingredients that are liquid at room temperature or have a melting point around room temperature (such as etofenebrox) are dissolved or dispersed in a solvent, such as a high boiling point solvent such as phenylxylylethane, di-2-ethylhexyl adipate, or 2-ethylhexyldiphenyl phosphate. and may be used.

Furthermore, the formulation of the present invention includes step mites, nematicides, herbicides,
Plant hormones, plant growth regulators, military agents.

Attractants, repellents, pigments, fertilizers, etc. can be mixed and used together.

Among the formulations of the present invention, the wettable powder is preferably diluted with water or the like, for example, by about 30 to 4000 times, or increased by about 300 to 3000 times, and then sprayed. The hydrating agent of the formulation of the present invention usually has a bensultap concentration of 50 to 1O.
It is preferable to use it after diluting it to about QOppm.

When the preparation of the present invention is used as an agricultural insecticide, the amount of bensultap used in the composition is approximately 3 per 10 are.
0g to about 500g is suitable.

The preparation of the present invention is applied directly to the foliage or applied to the base of the plant. That is, it can be processed by a method known per se. The formulation of the present invention is suitable for use against various pests of rice, vegetables (e.g., cabbage, Chinese cabbage, radish, cucumber, potato, etc.), fruit trees (e.g., mandarin oranges, pears, etc.), tea, tobacco, etc., such as the lepidoptera, such as the Japanese snail moth, the stag beetle moth, and the rice caterpillar.

Fall armyworm, fall armyworm.

White cabbage moth, diamondback moth, fall armyworm moth 1 tamamanaginuwaba, white spotted moth, nano borer moth, and tobacco moth.

To exterminate pests by spraying or treating the tea leafhopper, rice leafhopper of Moptera, green leafhopper of Hemiptera, teal thrips of Thrips, rice leafminer of Diptera, etc. when they occur. In addition, by spraying or treating in advance, the outbreak of various pests can be prevented for a long period of time.

The formulation of the present invention can be produced by methods known per se, as shown above and more specifically in the Examples below.

[Effects of the Invention] According to the present invention, decomposition of bensultap in the formulation is suppressed even after long-term storage, and therefore, a bensultap-containing agricultural chemical formulation that is stable, has virtually no phytotoxicity to plants, and is extremely useful for plant protection can be obtained. . In addition, other agrochemically active substances that could not be mixed with bensultap in the past can also be blended. The solid preparation of the present invention has an excellent utilization rate of organic components after spraying with agricultural chemicals, and can be manufactured industrially very easily.

Hereinafter, the present invention will be explained in further detail by describing Reference Examples, Examples, and Test Examples. Note that all percentages and parts used herein refer to percentages and parts by weight unless otherwise specified.

Reference example! Powder DL 93.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and ethofenebrox were added to phenylxylylethane (hereinafter referred to as high-boiling solvent) at a concentration of 50 parts. 1.2 parts of dissolved solution, 2.2 parts of white carbon, liquid paraffin (Torriless CO
Add 0.3 part of (hereinafter abbreviated as De-Res C) and mix thoroughly with a crusher. Then, it is crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Reference example 2 Granules bensultap 4 parts, dextrin 6 parts, surfactant (
2 parts of Noniball 85o (manufactured by Sanyo Kasei Co., Ltd., hereinafter abbreviated as surfactant) and 100 parts of clay were weighed out and mixed well. 12 parts of water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen 1.0 am diameter) to obtain a wet molded product. Then, after drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Reference Example 3 Granules Bensultap 4 parts, Ethofenbrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of surfactant, and a total of 100 parts of clay, and mix the total amounts thoroughly. Add 12 parts of water to the mixture, knead it, and pass the kneaded product through an extrusion granulator (
Granulate with a screen (1.0 m diameter) to obtain a wet molded product.

Then, after drying, the granules are sized to obtain 32 mesh granules from the 1O mesh.

Reference example 4 Granules Bensultap 4 parts, Dextrin 6 parts, Triku [10
Weigh out 2.3 parts of acetic acid, 2 parts of surfactant, and clay so that the total amount is 100 parts, and mix the total amounts well. 12 parts of water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen 1, Oam diameter) to obtain a wet molded product. After drying this, granulate it to obtain 32 mesh granules from 1O mesh.

Reference Example 5 Weigh out 4 parts of Bensultap granules, 6 parts of dextrin, 1.5 parts of monochloroacetic acid, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well. 12 parts of water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet molded product. Then, after drying, the granules are sized to obtain 10 to 32 mesh granules.

Reference Example 6 Wettable powders 69.5 parts of clay for wettable powders were added with Bensultap 1O15.
11.0 parts of a solution prepared by dissolving etofenbrox in a high boiling point solvent to a concentration of 50 parts.

Add 5.0 parts of white carbon and 4.0 parts of surfactant, and mix thoroughly using a crusher. Then, it is pulverized with a fine pulverizer to obtain a mixed permanent agent of bensultap and etofenbrox.

Reference Example 7 Weigh out 4 parts of Bensultap granules, 4 parts of BPMC, 6 parts of dextrin, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well.

12 parts of water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen 1, Oam diameter) to obtain a wet molded product. Then, after drying, the granules are sized to obtain 10 to 32 mesh granules.

Reference Example 8 Weigh out 4 parts of Bensultap granules, 4 parts of MIPC, 6 parts of dextrin, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well.

Add 12 parts of water to the mixture, knead it, and granulate the kneaded product using an extrusion granulator (screen 1.0 mm + diameter) to obtain a wet molded product. Next, after drying this, it is sized and sized from 10 metsuyu to 3
Obtain 2 meshes of granules.

Reference Example 9 4 parts of bensultap granules, 4 parts of tridiclazole, 6 parts of dextrin, 2 parts of surfactant, and clay were added to the total amount of 100 parts, and the total amount was thoroughly mixed. 1 part water to the mixture
2 parts were added and kneaded, and the kneaded product was granulated using an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet molded product. Then, after drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Reference Example 10 Weigh out 4 parts of bensultap granules, 8 parts of probenazole, 6 parts of dextrin, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well. 1 part water to the mixture
2 parts were added and kneaded, and the kneaded product was granulated using an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet molded product. Then, after drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Examples Examples! Powder DL A solution prepared by dissolving 0.7 parts of concentrated hydrochloric acid (approximately 35%) in 1.4 parts of methanol is added to 2.2 parts of Bensultap and kneaded using a grinder. Thoroughly dry the mixture in a vacuum dryer (pulverize if the dried material forms lumps), and add 92.3 parts of finely powdered clay, 1.1 parts of tridiclazole, and high-boiling point ethofenbrox to this. Add 1.2 parts of a solution dissolved in a solvent to a concentration of 50 parts, 2.2 parts of white carbon, and 13 parts of Trireth C0, and mix thoroughly with a grinder. The mixture is then crushed using a flash crusher to obtain a mixed powder of bensultap/tridiclazole/ethofenebrox DL.

Example 2 Powder DL Add 2.2 parts of benzenesulfonic acid to 2.2 parts of benzultap and mix well with a grinder. To this, fine powder clay 9
0.8 parts, 1.1 parts of tridiclazole, 1.2 parts of a solution prepared by dissolving ethofenbrox in a high boiling point solvent to a concentration of 50 parts, 2.2 parts of white carbon, Toriless C
003 parts were added, thoroughly mixed with a grinder, and then crushed with a flash grinder to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 3 Powder DL Add 3.0 parts of oxalic acid to 2.2 parts of Bensultap and mix well with a crusher. To this, 90.0 parts of finely powdered clay, 1.1 parts of tridiclazole, and 1.2 parts of a solution prepared by dissolving ethofenbrox in a high boiling point solvent to a concentration of 50 parts,
Add 2.2 parts of white carbon and 0.3 parts of Trireth CO, and mix thoroughly with a grinder.

The mixture is then crushed using a flash grinder to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 4 Powder DL Add 0.7 parts of dichloroacetic acid to 2.2 parts of Bensultap and 2.2 parts of white carbon, and mix well with a grinder. To this, 92.3 parts of fine powder clay, 1.1 parts of tridiclazole
1.2 parts of a solution prepared by dissolving 50 parts of etofenebrox in a high boiling point solvent, and 0.3 parts of Trireth C were added, and the mixture was thoroughly mixed using a grinder. The mixture is then crushed using a flash wetter to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 5 Weigh out 4 parts of Bensultap granules, 6 parts of dextrin, 3 parts of oxalic acid, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well. Add 12 parts of water to the mixture, knead it, and extrude the kneaded product into a granulator (screen, 1.o+m
diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 10 to 32 mesh granules.

Example 6 Granules Bensultap 4 parts, etofenebrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of oxalic acid, 2 parts of surfactant, and a total of 100 parts of clay, and mix the total amounts well. Add 12 parts of water to the mixture, knead it, and extrude the kneaded product using a granulator (screen).

1,0 mm diameter) to obtain a wet molded product. After drying this, sort it! From 0 mesh to 32 mesh granules are obtained.

Example 7 Granules Bensultap 4 parts, Ethofenbrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of surfactant, and 86 parts of clay, and mix the entire amounts thoroughly. 6 parts of 10% hydrochloric acid and 6 parts of water are added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen, 1.0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 8 Granules Bensultap 4 parts, etofenebrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of surfactant, and 86 parts of clay, and mix the entire amounts thoroughly. 11.5 parts of 7% hydrobromic acid was added to the mixture and kneaded, and the kneaded product was extruded and granulated by 11 m (
The mixture is granulated using a screen (diameter: 1.0 mm) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the 1O mesh.

Example 9 Granules Bensultap 4 parts, etofenebrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of surfactant, and 85 parts of clay, and mix the entire amounts thoroughly. 4 parts of 10% hydrochloric acid and IO parts of 10% phosphoric acid were added to the mixture and kneaded, and the kneaded mixture was extruded into a granulator (screen).

1.0 mm diameter) to obtain a wet molded product. this,
After drying, the granules are sized to obtain 32-mesh granules from 0-mesh to 32-mesh.

Example IO Granules Weigh out 4 parts of Bensultap, 6 parts of dextrin, 2 parts of dichloroacetic acid, 2 parts of surfactant, and clay to make a total of 100 parts, and mix the total amounts well. 12 parts water to the mixture
The mixture is then extruded into a granulator (screen,
1.0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 10 to 32 mesh granules.

Example 11 Granules Bensultap 4 parts, Ethofenbrox 1.5 parts,
Weigh out 6 parts of dextrin, 2 parts of surfactant, and 85 parts of clay, and mix the entire amounts thoroughly. 4 parts of 10% hydrochloric acid and 10 parts of 10% sulfuric acid were added to the mixture and kneaded, and the kneaded product was extruded into a granulator (screen).

1.0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the 1O mesh.

Example 12 Concentrated hydrochloric acid (approximately 35%) in 1015 parts of wettable powder bensultap 3.0
A solution prepared by dissolving 1 part in 4.0 parts of methanol is added thereto, and the mixture is kneaded using a grinder. Dry the mixture thoroughly in a vacuum dryer (
If the dried material forms clumps, crush it). A solution containing 67.5 parts of wettable powder clay and ethofenbrox dissolved in a high boiling point solvent to a concentration of 50 parts! Add 1.0 parts, 5.0 parts of white carbon, and 4.0 s of surfactant,
Mix thoroughly using a crusher. Then, it is pulverized with a fine pulverizer to obtain a bensultap/ethofenbrox mixed hydrating powder.

Example 13 Weigh out 4 parts of Bensultap granules, 4 parts of BPMC, 6 parts of dextrin, 2 parts of surfactant, and 82.6 parts of clay, and thoroughly mix the total amounts. 4 parts of 10% hydrochloric acid and IO parts of 10% phosphoric acid are added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen, 1.0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 14 Granules Bensultap 4 parts, MIPC4L dextrin 6 parts,
Weigh out 2 parts of surfactant and 82.6 parts of clay and mix the entire amount thoroughly. 4 parts of 10% hydrochloric acid and 10 parts of 10% phosphoric acid are added to the mixture and compacted, and the kneaded product is granulated using an extrusion granulator (screen, 1.0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 15 Bensultap/Tridiclazole Granules 4 parts of bensultap, 4 parts of tridiclazole, 6 parts of dextrin, 2w of surfactant, and 82.6 parts of clay are weighed out and the total amount is thoroughly mixed. 4 parts of 10% hydrochloric acid to the mixture;
Add IO parts of 10% phosphoric acid, knead, and extrude the kneaded product using a granulator (screen).

1, OIl+m diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 16 Weigh out 4 parts of Bensultap granules, 8 parts of probenazole, 6 parts of dextrin, 2 parts of surfactant, and 78.6 parts of clay, and thoroughly mix the total amounts. Add 4 parts of 10% hydrochloric acid to the mixture, 10
% 10 parts of phosphoric acid was added and kneaded, and the kneaded product was passed through an extrusion granulator (
The mixture is granulated using a screen (diameter of 1.0 m+a) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 17 Granules Bensultap 4 parts, Ethofenbrox 1.5 parts,
6 parts dextrin, 2 parts surfactant, antioxidant (pentaerythrityl-tetrakis [3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionate 30
, 2 parts and 85 parts of clay and mix the entire amount well. 3.4 parts of 10% hydrochloric acid and 10 parts of 10% phosphoric acid were added to the mixture and kneaded, and the kneaded product was passed through an extrusion granulator (screen, 1.
0 mm diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example 18 Granules Bensultap 4 parts, etofenebrox 1.5 parts,
6 parts dextrin, 2 parts surfactant, antioxidant (pentaerythrityl-tetrakis [3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionate 10
．． Weigh out 2 parts and 85.2 parts of clay and mix the whole amount well. Add 2.7 parts of 10% hydrochloric acid and 10% phosphoric acid lθ to the mixture.
The mixture is then extruded into a granulator (screen,
1. On+m diameter) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the 1O mesh.

Test Example 20 g of each of the mixed preparations obtained in Examples 1 to 18 and Reference Example 1-10 is placed in a sample bottle, sealed tightly and stored at a predetermined temperature for a predetermined period of time. Then, the sample is taken out, a certain amount (100 mg in terms of Bensultap) is accurately weighed, shaken with acetonitrile 25 for 20 minutes, and extracted. The content of bensultap in the extract was determined by high performance liquid chromatography (column: Nucleosil).
il) IO-C1m.

Measured using Gascro Kogyo Co., Ltd., elution solvent, acetonitrile:water (60-40 v/v). The decomposition rate (%) of Bensultap is calculated from the following formula.

Bensultap decomposition rate (%) == (Left below) Table 1 Stability of bensultap/tridiclazole/ethofenebrox mixed powder DL (Left below) Table 2 Bensultap/Etofenebrox Table 4 Bensultap - Ethofenebrox mixture Table 5 Stability of bensultap mixed granules Based on the above results, bensultap solid formulation contains hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and allenesulfonic acid.

It is clear that bensultap is significantly stabilized when dichloroacetic acid and oxalic acid are mixed.

Procedural amendment April 1, 1986

Claims (1)

[Claims] Contains S,S'-[2-(dimethylamino)trimethylene]bis-benzenethiosulfonate and at least one of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, allenesulfonic acid, dichloroacetic acid, and oxalic acid. Stabilized solid formulation