JPH014A - Stabilized bensultap solid 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. Used as an agricultural insecticide.

[Conventional technology]

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 (for example, Japanese Patent Publication No. 46-1
3755. 45-18847), 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/filler such as mineral powder and used as a regular solid preparation such as a single powder or a wettable powder.

[Problem to be solved by the invention]

However, bensultap is relatively unstable in the solid preparation obtained by mixing it with a carrier/filler (e.g. mineral powder), and if stored at room temperature (approximately 30°C) for a long period of time, Bensultap gradually decomposes, changes color, or deteriorates, resulting in a decrease in the content of Bensultap, the active ingredient.

In addition to bensultap, a mixed solid preparation of bensultap obtained by mixing one or more agricultural active substances with the aim of achieving a wider range of excellent medicinal efficacy and labor-saving simultaneous control is more effective than a single solid preparation of bensultap. In some cases, the decomposition and deterioration of pesticide active ingredients such as Bensultap may be significant.

[Means to solve the problem]

The present invention relates to S,S'-(1-(dimethylamino)trimedylene)bis-benzenethiosulfonate and titanium dioxide, calcium oxide, zinc oxide, magnesium oxide,
The present invention relates to a stabilized solid preparation containing at least one type of boron oxide.

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 the pesticide active ingredient.

The present inventors have discovered that the stabilizing effect of the agrochemical active ingredient (particularly bensultap) in this bensultap solid preparation is due to titanium dioxide (Tie) among various metal oxides.

Calcium oxide (Cab), zinc oxide (Z no ),
Magnesium oxide (MgO), boron oxide (B, Os
) was found to be specifically obtained by For example, aluminum oxide and silicon dioxide, which are used in the field of agricultural chemicals, do not have such a stabilizing effect at all.

These stabilizers such as titanium dioxide, calcium oxide, zinc oxide, magnesium oxide, and boron oxide may be used alone or in combination of two or more. Among these, plants (e.g.
Zinc oxide is preferred from the viewpoint of phytotoxicity to rice (rice) and safety to humans and animals during or after application. The stabilized solid preparation of the present invention has virtually no phytotoxicity to plants, and is harmless to humans and animals either during or after application and can be safely used.

The solid preparation of the present invention contains bensultap and titanium dioxide, calcium oxide, and zinc oxide as stabilizers.

It is produced by mixing or blending at least one of magnesium oxide and boron oxide with a suitable solid carrier/extending agent, or by adsorbing it onto a solid carrier/extending agent. The solid preparation of the present invention is a powder.

It is used in preparations such as powder DL, elongating agent, alimentary agent, and fine granule F.

These preparations may contain other agrochemical active ingredients, dispersants, spreading agents, penetrants, wetting agents, thickeners, anti-caking agents,
Auxiliary ingredients such as flocculants, binders, antioxidants, etc. may be added.

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% by weight, approximately 1 to 10% by weight in the case of granules and fine granules F, and approximately 10 to 90% by weight in the case of wettable powders.

Titanium dioxide as a stabilizer in the formulation of the present invention.

Calcium oxide, zinc oxide, magnesium oxide, or boron oxide may be used in l'N or in a mixture of two or more of them in an appropriate ratio, and the amount of the stabilizer added (2f1
When the above is used, the total amount 1i) is about 0.1 to 100 parts by weight, preferably about 0.5 to 50 parts by weight, per 1 part by weight of bensultap.

Titanium dioxide, calcium oxide, zinc oxide, magnenium oxide, and boron oxide are usually in powder form, preferably
Those having a particle size of about 100 μm or less are used.

Preferably, solid carriers/fillers include clays (e.g., kaolin, bentonite, acid clay, finely powdered clay, white carbon, etc.), talcs (e.g., talc powder, waxite powder, etc.), and silicas. (e.g., diatomaceous earth, mica powder, etc.), vegetable powders such as bean powder, tobacco powder, wheat flour, wood flour, etc., as well as one or two types of calcium carbonate, sulfur powder, activated carbon, etc. A mixture of the above is used.

Examples of surfactants used as dispersants, spreading agents, penetrants, etc. include soaps, polyoxine ethylene alkylaryl ethers (e.g., Neuge: /%l'-, x
--142 (E, A-142)'', manufactured by Dai-Kogyo Seiyaku), polyoxyethylene alkylaryl esters (e.g., Nonal 0. manufactured by Toho Chemical Co., Ltd.), alkyl sulfates (e.g., Emar 100. manufactured by Toho Chemical Co., Ltd.) =〇1ru40, manufactured by Kao Sekiken Co., Ltd.), alkyl sulfonates (e.g., Neogen ■, Neogen To, manufactured by Dai-Kogyo Seiyaku Co., Ltd., Neoperex 0. manufactured by Kao Soap Co., Ltd.),
Polyethylene glycol ethers (e.g. Nonibor/L
=85o, /Ebo/, 100o, Tsuyuball 160o
, manufactured by Sanyo Chemical Co., Ltd.), polyhydric alcohol extract + 71
/ type (e.g. Towie, 20 colors, Lie, 8P.

Nonionic and anionic surfactants such as those manufactured by Kao Soap Co., Ltd. are used as necessary.

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

Talc, diatomaceous earth, magnesium stearate, etc., flocculants such as liquid paraffin, ethylene glycol, ) ethylene glycol, triethylene glycol, etc., binding agents such as carboxymethylcellulose sodium salt, dextrin, pregelatinized starch, polyvinyl alcohol, oxidation As inhibitors, dibutylhydroxytoluene, 4゜4-thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole, paraoctylphenol, mono (or di or tri) (α-methylbenzyl)phenol, 2.6 -jert-butyl-4-methylphenol, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroquinphenyl)cobropionate, etc. are used.

In addition to bensultap, the formulation of the present invention includes organic sulfur-based,
IFI 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 abbreviation is shown in parentheses after the compound name, and this common name or abbreviation may be used in the following description) Organic sulfur fungicide...Zinc ethylenebis(dithiocarbamate) (Zineb) Organophosphorus fungicides such as ethylene bis(dithiocarbamic acid) manganese (maneb); S-benzyl diisopropyl phosphorothiolate (IBP); Organic arsenic fungicides such as 0-ethyl diphenylphosphorodithiolate (EDDP); ...Methanarsonate iron (MAF)
: Ammonium iron methanarsonate (M AF
Organic base fungicides such as A)...pentachlorophenol (PC
P); Tetrachloroisophthalonitrile (TPN)
Other fungicides such as 4,5,6,7-titrachlor[1phthalide (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-nitro-m-tolyl phosphorothionate (MEP); S-1,
2-Bis(ethoxycarbonyl)ethyl dimethyl phosphorothiorothionate (Marathon): p-anophenyl dimethyl phosphorothionate (CYAP)
) and other organochlorine insecticides...6,7,8,9,10.10-
Carbamate insecticides such as hexachlor 1.5,5a, 6,9.9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine 3-oxide (penzoevin)...l -naphthyl methyl carbamate (NAC); m-)lyl N-methyl carbamate (MTMC); o -5ec-butylphenyl N-methyl carbamate (BPMC): 0-cumenyl N-methyl carbamate (MIPC);
3,4-xylyl N-methylcarbamate (MPM
C); 3,5-xylyl N-methylcarbamate (XMC) Pyrethroid insecticide...pyrethrin, allethrin,
Antibiotics such as resmethrin...Other insecticides such as plasticidin S, kasugamycin, polyoxin, oxytetracycline, validamycin A...S, S'-(2-(dimethylamino)-trimethylene)bisutiocarbame. -t(cartap); 2-(4-ethoxyphenyl)-2-
Methylpropyl 3-phenoxybenzyl ether (
etofenbrox); (Rs)α-cyano-3
- phenoxybenzyl (S)-2-(4-difluoromethoxyphenyl)-3-methylbutyralate (flucitrinate) and the like.

Among the above, preferred are validamycin A, probenazole, IBP, tridiclazole, etofenbrox, flucitrinate, and NAC.

MPMC, MTMC, BPMC, MI PC.

Particularly preferably validamycin A, tridiclazole,
Etofuenbrox and fusaride.

Specific examples of the mixed preparation of the present invention include bensultap-ethofenbrox or pensultap-ethofenbrox-tricyclazole (or fusaride, or validamycin A).

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, the amount is about 0.01 to 20% by weight, preferably about 0.05 to 10% by weight, and in the case of two or more types, the total amount is about 0.01 to 20% by weight. 1% to 20% by weight, preferably a total of about 0.805 to 15% by weight.

Pesticide active ingredients that are liquid at room temperature or have a melting point near room temperature (e.g. etofenbrox) may be mixed with a high boiling point solvent such as phenylxylylethane, di-2-ethylhexyl adipate or 2-ethylhexylphenyl phosphate. It may be used after being dissolved or dispersed.

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

It is also possible to mix and use attractants, repellents, pigments, fertilizers, etc.

Among the formulations of the present invention, the hydrating powder is preferably dispersed with water, for example, in an amount of about 30 to 4000 times, preferably about 300 to 3000 times. The hydrating agent of the formulation of the present invention is preferably used after being diluted to a bensultap concentration of about 50 to 11,000 pp.

When the preparation of the present invention is used as an agricultural insecticide, the amount of bensultap used is approximately 3 per 10 ares in the composition.
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 preparation of the present invention can be applied to rice, vegetables (e.g., cabbage, Chinese cabbage, radish, cucumber, potato, etc.), fruit trees (e.g., mandarin oranges, pears, etc.), tea, tobacco, etc. ,
Fall armyworm, fall armyworm.

C, V % Jtsu, diamondback moth, armyworm moth, tamanagi moth, white thorn moth, nano worm moth, tobacco moth.

Green leafhopper, W1-order rice beetle, cucumber beetle, Hemiptera: black-and-white leafhopper, green leafhopper,
Spray or treat thrips in the order Thripsidae and rice leafminer fly in the Diptera order when they occur 2:
By doing so, pests can be exterminated, and 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.

〔Effect 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 substantially no phytotoxicity to plants, and is extremely useful for plant protection can be obtained. In addition, other good medicinal active substances that could not be blended with bensultap in the past can also be blended, and the solid preparation of the present invention not only has an excellent utilization rate of active ingredients after spraying pesticides, but also has an extremely high industrial value. Easily manufactured.

Hereinafter, reference examples, examples, and test examples will be described to provide a detailed explanation of the present invention. Note that all parts used herein indicate parts by weight.

Reference example! Powder DL: 96.5 parts of fine powder clay, 2.2 parts of Bensultap, 1.0 part of white carbon, liquid paraffin ■ (Use Toryless C, hereinafter abbreviated as Toryless C) 0.
Add 3 parts and mix thoroughly using a crusher. Then, it is crushed with a flash mixer to obtain Bensultap powder DL. (
Bensultap = 13.1% decomposition after storage at 60°C/1 week) Reference Example 2 Powder DL 94.1 parts of fine powder clay, 262 parts of Bensultap, 50 parts of etofenbrox in phenylxylylethane (hereinafter abbreviated as solvent) 1.2 parts of solution dissolved to give a concentration of % by weight, 2.2 parts of white carbon, Toriless C
Add 23 parts of O and mix thoroughly using a crusher. Then, it is crushed with a flash mixer to obtain a bensultap/ethofenbrox mixed powder DL.

Reference Example 3 Powder DL 95.4 parts of fine powder clay, 2.2 parts of Bensultap,
Add 1.1 parts of tridiclazole, 1.0 part of white carbon, and 13 parts of Toriless C0, and mix thoroughly with a crusher. Then, it is crushed with a flash mixer to obtain a bensultap/tridiclazole mixed powder DL. (Bensultap: 24.6% decomposition after storage at 60°C/1 week) Reference Example 4 Powder DL 93.0 parts of fine powder clay, 2.2 parts of Bensultap,
1. A solution prepared by dissolving 1.1 parts of tridiclazole and etofenbrox in a solvent to a concentration of 50% by weight.
Add 2 parts of white carbon, 2.2 parts of white carbon, and 3 parts of Toriless C00, and mix thoroughly using a crusher. Then, it is crushed with a flash mixer to obtain a mixed powder of Bensultap, tridiclazole, and etofenbrox DL.

Reference Example 5 Powder DL 93.8 parts of fine powder clay, 2.2 parts of Bensultap,
1.2 parts of a solution prepared by dissolving etofenbrox in a solvent to a concentration of 50% by weight, validamycin A 01
3 parts, white carbon 2.2 parts.

Add 83 parts of Torriless CO, thoroughly mix with a crusher, and then crush with a flash mixer to obtain a mixed powder of bensultap/ethofenbrox/validamycin A DL.

Reference example 6 Granules Bensultap 4 parts, Dextrin 6 parts, Noniball 8 parts
Weigh out 2 parts of 5o (manufactured by Kochu Kasei Co., Ltd.) (hereinafter abbreviated as surfactant) and 100 parts of clay, and mix well. Water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen diameter: 1.01) to obtain a wet molded product. After drying this, it is sized and put into 32 pieces from the IO mesh.
Obtain Metsuyu granules.

Reference Example 7 Wettable powders 69.5 parts of clay for wettable powders were added with Bensultap 1O85.
11.0 parts of a solution prepared by dissolving etofenbrox in a solvent to a concentration of 50% by weight.

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 8 Powder DL 78.0 parts of fine powder clay, 2.2 parts of Bensultap,
Solution 1.2 in which 1.1 parts of tridiclazole and etofenebrox were dissolved in a solvent to a concentration of 50% by weight.
part, white carbon 2.2 parts.

Toryless CO, 3 parts, and aluminum oxide powder 15
．． 0 parts were added, thoroughly mixed with a crusher, and then crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Reference Example 9 Powder DL 91.4 parts of finely powdered clay, 2.2 L of bensultap ethofene block and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4=hydroxyphenyl)] propionate 50% by weight of each in the solvent
Concentration and solution solution dissolved to have a concentration of 5% by weight 1.
Add 2 parts, 2.7 parts of Fusaride, 2.2 parts of white carbon, and 3 parts of Toliless C0, mix thoroughly with a crusher, then crush with a flash mixer,
Ethofenebrox/futhalide mixed powder DL is obtained.

Reference Example 1O Powder DL 78.0 parts of fine powder clay, 2.2 parts of Pensultap,
1.1 parts of tridiclazole, etofenebrox and pentaerythrityl-tetrakis [3-(3,5-di-
1.2 parts of a solution prepared by dissolving t-butyl-4-hydroxyphenyl) cobropionate in a solvent to a concentration of 50% by weight and 5% by weight, respectively, 2.2 parts of white carbon, 23 parts of Trireth CO, and silicon dioxide. Add 15.0 parts of powder, thoroughly mix with a grinder, and then crush with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenebrox DL.

Examples Example 1 Powder DL 1.2 parts of a solution prepared by dissolving 78.0 parts of finely powdered clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and ethofenbrox in a solvent to give a concentration of 50% by weight. ,
2.2 parts of white carbon, 33 parts of Trireth CO and magnesium oxide powder particle size: (45 μm or less) 15.0
and mix well with a grinder. Then, it is crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 2 Powder DL 1.2 parts of a solution prepared by dissolving 78.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of trifuclazole, and ethofenbrox in a solvent to give a concentration of 50% by weight, Add 2.2 parts of white carbon, 3 parts of Trireth C00, and 15.0 parts of boron oxide powder (particle size: 45 μm or less), and thoroughly mix with a grinder. Then, it is crushed with a flash mixer to obtain Hensultap/tridiclazole/ethofenbrox mixed powder DL.

Example 3 Powder DL 1.2 parts of a solution prepared by dissolving 78.0 parts of fine powder clay, 12.2 parts of bensultawa, 1.1 parts of tridiclazole, and ethofenbrox in a solvent to give a concentration of 50% by weight,
Add 2.2 parts of white carbon, 3 parts of Trireth C00, and 15.0 parts of zinc oxide powder (particle size: 45 μm or less) and thoroughly mix with a grinder.

Then, crush it with a flash mixer to make bensultap/tridiclazole/ethofenbrox mixed powder D.
Get L.

Example 4 Powder DL 1.2 parts of a solution prepared by dissolving 78.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and ethofenbrox in a solvent to give a concentration of 50% by weight,
Add 2.2 parts of white carbon, 13 parts of Trireth C0, and 5.0 parts of calcium oxide powder (particle size: 45 μm or less) and thoroughly mix with a crusher. Then, crush with a flash mixer, - Obtain Etofenebrox mixed powder DL.

Example 5 Powder DL 1.2 parts of a solution prepared by dissolving 83.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and ethofenbrox in a solvent to a concentration of 50% by weight,
2.2 parts of white carbon, 3 parts of Trireth CO, and calcium oxide powder (particle size: 45 μm or less) I O,0
and mix well with a grinder. Then, it is crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 6 Powder DL 1.2 parts of a solution prepared by dissolving 88.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and ethofenbrox in a solvent to a concentration of 50% by weight,
2.2 parts of white carbon, 3 parts of Trireth GO, and calcium oxide powder (particle size: 4.5 μm or less)5.
Add 0 parts and mix thoroughly using a grinder. Then, it is crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 7 Powder DL 90.8 parts of fine powder clay, 2.2 parts of bensultap, 1.1 parts of tridiclazole, and 1.2 parts of a solution of ethofenbrox dissolved in a solvent to a concentration of 50% by weight,
2.2 parts of white carbon, 3 parts of Toryless G O, and 2.2 parts of calcium oxide powder (particle size: 45 μm or less)
and mix well with a grinder. Then, it is crushed with a flash mixer to obtain a mixed powder of bensultap/tridiclazole/ethofenbrox DL.

Example 8 Powder DL A solution prepared by dissolving 84.1 parts of finely powdered clay, 22 parts of Bensultap, and ethofenbrox in a solvent to a concentration of 50% by weight! , 2 parts, white carbon 2.2 parts, Toriless C013 parts and zinc oxide powder (particle size: 45
(μm or less) and mix thoroughly with a grinder.

Then crush it with a flash mixer and use Bensurutap.
Ethofenebrox mixed powder DL is obtained.

Example 9 Powder DL 83.8 parts of fine powder clay, 2.2 parts of bensultap, 1.2 parts of a solution prepared by dissolving ethofenbrox in a solvent to a concentration of 50% by weight, validamycin A 013
parts, 2.2 parts of white carbon, 33 parts of Trireth CO, and 10 parts of magnesium oxide powder (particle size: 45 μm or less)
．． Add 0 parts and mix thoroughly using a grinder. It is dried and crushed with a flash mixer to obtain a mixed powder of bensultap/ethofenbrox/validamycin A DL.

Example 1 O granules Bensultap 4 parts, dextrin 6 parts, surfactant 2
1 part, 25 parts of titanium dioxide powder (particle size: 45 μm or less) and clay to make a total of 100 parts, and thoroughly mix the whole mixture. 12 parts of water is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen 1, OL! 1 m 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, Dextrin 6 parts, Surfactant 2
1 part, 25 parts of zinc oxide powder (particle size: 45 μm or less) and 100 parts of clay, and mix well. Water 121 is added to the mixture and kneaded, and the kneaded product is granulated using an extrusion granulator (screen diameter: 1.0 m) to obtain a wet molded product. After drying, the granules are sized to obtain 32 mesh granules from the IO mesh.

Example I2 Wettable powder Add Bensultap 1005 to 54°5 parts of clay for wettable powders.
parts, 11.0 parts of a solution prepared by dissolving etofenbrox in a solvent to a concentration of 50% by weight, white carbon 5
．． 0 parts, surfactant 4.0 parts, zinc oxide powder (particle size: 4
Less than 5 μm 5. Add part θ and mix thoroughly using a grinder.

Then, it is ground in a fine grinder to obtain a mixed permanent agent of bensultap and etofenbrox.

Example 13 Powder DL 81.4 parts of fine powder clay, 2.2 parts of bensultap, 2.7 parts of fusaride, ethofenbrox and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4- 1.2 parts of a solution dissolved in a hydroxyphenyl cobquilobionate solvent to a concentration of 50% by weight and 5% by weight, respectively, 2.2 parts of white carbon, 93 parts of Trireth C0, and zinc oxide powder (particle size: Add 10.0 parts (45 μm or less) and thoroughly mix with a grinder. Then, it is crushed with a flash mixer to obtain a bensultap/ethofenebrox/futhalide mixed powder DL.

Example 14 Powder DL 83.8 parts of fine powder clay, 2.2 parts of bensultap, ethofenbrox and pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)cobropionate] as a solvent 1.2 parts of a solution dissolved in 50% by weight and 5% by weight, respectively, 0.3 parts of validamycin A, and 2.2 parts of white carbon.
part, 13 parts of Trireth C0 and zinc oxide powder (particle size: 4
Add 10.0 parts (5 μm or less) and mix thoroughly with a grinder. Then, crush it with a flash mixer and add bensultap ψ etofenbrox/validamycin A mixed powder D.
Get L.

Example 15 Powder DL 84.1 part of fine powder clay, 2.2 parts of Bensultap,
Ethofenbrox and pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate were dissolved in a solvent to a concentration of 50% by weight and 5% by weight, respectively. Solution 1
．． 2 parts, white carbon 2.2 parts, Toriless C013
and zinc oxide powder (particle size: 45 μm or less) I O,
Add 0 parts and mix thoroughly using a grinder. Then, it is crushed with a flash mixer to obtain a bensultap/ethofenbrox mixed powder DL.

Example 16 Powder DL 83.0 parts of fine powder clay, 2.2 parts of bensultap, 1.1 L of tridiclazole, ethofenebrox and pentaerythrityl-tetrakis [3-(3,5-di-t-
butyl-4-hydroxyphenyl) cobropionate in a solvent at a concentration of 50% by weight, 1.2 parts of a solution, and 2.2 parts of white carbon.

Toriless 0063 parts and zinc oxide powder (particle size: 45μ
m or less) and mix thoroughly with a crusher. Next, crush it with a flash mixer and mix it with a Henstle tap.
Tridiclazole/Etofenbrox mixed powder DL
get.

Test Example Example 1~! 20 g of each of the mixed preparations obtained in Example 6 and Reference Example 1-10 was placed in a sample bottle, sealed tightly, and stored at a predetermined temperature for a predetermined period of time. Next, take out the sample, accurately weigh a certain amount (100 mg in terms of Bensultap), shake with 25 d of acetonitrile for 20 minutes, and extract. Nil-containing Henstletap in the extract was analyzed using high-performance liquid chromatography (column: Nucleosil).
osil) I O-C+s.

Manufactured by Gascro Industries, elution solvent, acetonitrile; water (60
:40 v/v)). The decomposition rate (%) of Bensultap is calculated from the following formula.

Bensultap decomposition rate (%) − The test results are shown in Tables 1 to 6.

Table 1 Stability of bensultap/ethofenbrox powder mixture DL Table 2 Stability of bensultap/ethofenbrox/validamycin A powder mixture DL Table 3 Bensultap/tridiclazole/ET Table 5 Bensultap/ethofenbrox Table 6 Bensultap/Etofenbrox Based on the above results, Bensultap solid preparation contains titanium dioxide, calcium oxide, zinc oxide,
It is clear that bensultap is significantly stabilized when mixed with magnesium oxide or boron oxide.

Procedural amendment dated June 2, 1988 1, Indication of the case, Patent Application No. 31473 of 1988 2, Name of the invention Stabilized bensultap solid preparation 3, Relationship with each case to be amended Patent applicant Address: 2-27 Doshomachi, Higashi-ku, Osaka Name (29)
3) Takeda Pharmaceutical Co., Ltd. Representative: Junsei Umemoto 4゜Agent address: 2-17-85-5, Jusanhonmachi, Yodoyo-ku, Osaka City, Detailed description of the invention column 6 of the specification to be amended, Amendment Contents (1) Page 8, line 5, page 18, line 11, page 19, line 4, and page 25, lines 13 to 14 of the present specification.

In line 5 of page 26, line 18 of the same page, and line 11 of page 27, ")]propionate" is corrected to "[)propionate]."

that's all

Claims (1)

[Scope of Claims] A stable product containing S,S'-[2-(dimethylamino)trimethylene]bis-benzenethiosulfonate and at least one of titanium dioxide, calcium oxide, zinc oxide, magnesium oxide, and boron oxide. solid formulation.