JP3276186B2 - Stabilized herbicide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a herbicidal composition comprising a thiadiazabicyclononane compound and a water-soluble polymer compound, which has a high herbicidal effect and is stabilized.

[0002]

BACKGROUND OF THE INVENTION As a thiadiazabicyclononane derivative, 9-phenylimino-8-thia-1,6-
The diazabicyclo (4.3.0) nonan-7-one derivative has a herbicidal activity against weeds generated in upland fields and paddy fields at a low dose, and is highly selected for crops such as soybeans and corn. It is known that it has a property (JP-A-63-264489, EP-A-457714). When this thiadiazabicyclononane derivative is used in a field or the like as a herbicide, it is formulated into a suitable dosage form such as an emulsion, a wettable powder, a flowable and the like, diluted with water and sprayed.

In general, it is desirable that pesticides exhibit high activity at low doses, and various methods for increasing the activity of pesticide compounds have been studied. For example, a composition containing a co-pulverized pesticide compound and a water-soluble polymer compound (JP-A-1-308202), dissolving the pesticide compound and the water-soluble polymer compound in an organic solvent, and distilling off the solvent. And a composition containing the residue obtained by the above method (Japanese Patent Application Laid-Open No. 1-211504).

[0004]

When spraying a herbicide,
Spraying an excessive amount of drug is often required to obtain a sufficient effect, but it is not preferable to spray a large amount of drug because of the economic burden on farmers, the safety of humans and livestock, and the risk of environmental pollution. . There is a need for a pesticidal composition that does not cause harm to agricultural crops and that exhibits sufficient effects with a smaller amount of drug used. When the water-soluble polymer compound described above is added for the purpose of improving the herbicidal effect of the thiadiazabicyclononane derivative, the thiadiazabicyclononane derivative is decomposed during the storage thereof, and the original herbicidal effect of the compound is obtained. In addition, it may cause phytotoxicity to crops.

The present inventors have conducted intensive studies with the aim of improving the herbicidal effect of thiadiazabicyclononane derivatives. As a result, the thiadiazabicyclononane derivatives have an average molecular weight of 40,000.
If the above polyvinylpyrrolidone is contained and urea is added to these, or if necessary, by adding urea to the water-soluble polymer compound excluding polyvinylpyrrolidone having an average molecular weight of 40,000 or more in the thiadiazabicyclononane derivative, the herbicidal effect is improved. High, and long-term storage, agricultural
The present inventors have found a safe herbicidal composition and have completed the present invention.

The herbicidal composition of the present invention comprises a thiadiazabicyclononane derivative containing polyvinylpyrrolidone having an average molecular weight of 40,000 or more, if necessary, urea added thereto, or an average molecular weight of 40,000 or less. The water-soluble polymer compound excluding polyvinylpyrrolidone contains urea. The thiadiazabicyclononane derivative which is an active ingredient of the herbicidal composition of the present invention has a general formula

[0007]

Embedded image [Wherein X ¹ and X ² represent a hydrogen atom or a halogen atom, and Y represents a group

[0008]

Embedded image (Where R ¹ represents a hydrogen atom or an alkyl group;
² represents an alkyl group, a cycloalkyl group or an alkoxyalkyl group. ). Or the group

[0009]

Embedded image (Where X ³ represents an oxygen atom or a sulfur atom, and A is
Represents a linear or branched alkylene group, R ³ is a phenyl group, a halogen-substituted phenyl group, a cycloalkoxycarbonyl group, an alkylthio group, an alkoxycarbonyl group,
It represents an alkoxyalkoxycarbonyl group, an alkoxycarbonylalkylthio group, or an alkylthioalkoxycarbonyl group. 9) -Phenylimino-8 represented by
A thia-1,6-diazabicyclo (4,3,0) nonan-7-one derivative, which is a solid or liquid compound. Tables 1 to 9 show examples of thiadiazabicyclononane derivatives.

[0010]

[Table 1]

[0011]

[Table 2]

[0012]

[Table 3]

[0013]

[Table 4]

[0014]

[Table 5]

[0015]

[Table 6]

[0016]

[Table 7]

[0017]

[Table 8]

[0018]

[Table 9]

In the composition of the present invention, the mixing ratio of the thiadiazabicyclononane derivative varies depending on the mixing ratio of the water-soluble polymer compound and urea described later, but is usually 1% by weight.
60% by weight. The water-soluble polymer compound used in the present invention is a substance which is solid at normal temperature, and includes, for example, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyethylene glycol (average molecular weight of 950 or more), polyoxyethylene polyoxypropylene glycol (average molecular weight). Molecular weight of 5900 or more), polyvinylpyrrolidone, β-cyclodextrin, polyvinyl alcohol and the like.

In the present invention, the mixing ratio of the thiadiazabicyclononane derivative and the water-soluble polymer compound is 10: 1 to 1:25, preferably 5 to 1, by weight. : 1 to 1: 5, most preferably 1: 1 to 1: 3. The content of the thiadiazabicyclononane derivative and the water-soluble polymer compound in the composition is 1 to 99% by weight. Although the degree of decomposition of the thiadiazabicyclononane derivative varies depending on the type of the water-soluble polymer compound used, the higher the blending ratio of the water-soluble polymer compound, the higher the water solubility of the thiadiazabicyclononane derivative and the herbicidal effect Is stable, but the thiadiazabicyclononane derivative tends to be easily decomposed.

Next, a method for producing the herbicidal composition of the present invention will be described. A substance obtained by co-milling a thiadiazabicyclononane derivative and a water-soluble polymer compound (hereinafter referred to as a co-milled product) is used to simultaneously grind a solid thiadiazabicyclononane derivative and a water-soluble polymer compound. A mixture of solids. This mixture is pulverized for several minutes to several hours, for example, by pulverizing for several minutes to several hours with a dry pulverizer such as a ball mill or a roll mill, or by mixing with water and using a wet pulverizer using glass beads as a pulverizing medium. Can be manufactured.
When a powder X-ray diffraction measurement of the co-ground product or the evaporation residue is performed, a solid compound of the thiadiazabicyclononane derivative has a reduced or eliminated diffraction peak, and a decrease in crystallinity is observed.

A substance obtained by dissolving a solid or liquid thiadiazabicyclononane derivative and a water-soluble polymer compound in an organic solvent and then distilling off the organic solvent (hereinafter referred to as evaporation residue) is a thiadiaz. After the bicyclononane derivative and the water-soluble polymer compound are simultaneously dissolved in an organic solvent, the organic solvent can be distilled off under conditions such as heating under normal pressure or heating under reduced pressure. The organic solvent used is not particularly limited, but is preferably a solvent having a boiling point of 100 ° C. or lower, for example, methanol, ethanol, acetone, dichloromethane,
Chloroform and the like can be mentioned.

In the composition containing the co-ground product or the evaporation residue of the thiadiazabicyclononane derivative and the water-soluble polymer compound obtained as described above, in order to suppress the decomposition of the thiadiazabicyclononane derivative, Add urea. The method of blending urea is not particularly limited as long as urea is uniformly dispersed, and urea may be blended after obtaining a co-ground product or an evaporation residue, or may be blended with urea mixed. Although a pulverized product may be obtained, it is particularly preferable that the co-pulverized product of the thiadiazabicyclononane derivative and the water-soluble polymer compound or the evaporation residue and urea are previously pulverized and mixed by a dry pulverizer. The mixing ratio of thiadiazabicyclononane derivative: urea is 10: 1 to 1: 200, preferably 2: 1 to 1:20, and most preferably 1: 1 to 1: 5 by weight.
It is. When polyvinylpyrrolidone having an average molecular weight of 40,000 or more is used, it can withstand long-term storage without blending urea.

The herbicidal composition of the present invention can be formulated in the form of a solid such as a wettable powder or a wettable powder or a liquid form dispersed in water (flowable). In this case, a surfactant, a bulking agent, a binder, other auxiliaries, and the like usually used in agricultural chemical formulations can be used.

In the case of a solid form such as a wettable powder or a wettable powder for granules, a nonionic surfactant such as polyoxyalkylene alkylaryl ether or polyoxyethylene alkylphenyl ether, alkylbenzene sulfone is used as a surfactant. Surfactants such as acid salts, naphthalenesulfonates and ligninsulfonates; natural minerals such as clay, talc and diatomaceous earth as extenders; inorganic salts such as ammonium sulfate and calcium carbonate; lactose and sucrose , White carbon and the like are used as appropriate. In addition, a saccharide such as a carboxymethyl cellulose salt is appropriately used as a binder, and a higher fatty acid metal salt or the like is appropriately used as a physical property improver.

A surfactant, a bulking agent, and a physical property improver are blended with a co-ground product of a thiadiazabicyclononane derivative and a water-soluble polymer compound or a mixture of an evaporation residue and urea, mixed, pulverized, and mixed with water. A sump can be obtained. Similarly, a surfactant, an extender, a physical property improver, and a binder are blended, mixed, and pulverized, and then granulated by a method such as press granulation or stirring granulation, fluidized bed granulation, and dried. To obtain a wettable powder.

For flowability, nonionic surfactants such as polyoxyalkylene alkylaryl ether, polyalkylene glycol, polyoxyethylene alkylphenyl ether, alkylbenzene sulfonate, and polyoxyethylene alkylaryl ether sulfate are used as surfactants. Anionic surfactants such as salts, soybean oil, higher fatty acid metal salts, white carbon, heteropolysaccharides and the like as physical property improvers, ethylene glycol and propylene glycol as antifreezing agents, and water as a bulking agent are used. A urea, a surfactant, a physical property improver, an antifreezing agent, and water are mixed with a co-milled product of a thiadiazabicyclononane derivative and a water-soluble polymer compound or an evaporation residue, and then mixed and milled to obtain a flowable product. be able to.

In the present invention, the thiadiazabicyclononane derivative is co-ground with the water-soluble polymer or the urea is contained in the evaporation residue to stabilize the thiadiazabicyclononane derivative and increase water solubility, High herbicidal effect can be obtained with low dosage. The mixing ratio of urea is by weight, and the thiadiazabicyclononane derivative: urea is 2: 1.
To 1:20, preferably 1: 3 or more. The method of compounding urea may be a method in which urea is uniformly dispersed, and a crushed product of a thiadiazabicyclononane derivative and a water-soluble polymer compound or an evaporation residue and urea are previously crushed and mixed by a dry crusher. It is preferable to keep it. When a co-ground product is obtained in the presence of water, urea may be added together with other components used in the composition. A co-ground product of thiadiazabicyclononane derivative and polyvinylpyrrolidone having an average molecular weight of 40,000 or more, or a mixture of evaporation residue and urea,
According to the method described above, a formulation such as wettable powder, wettable powder, flowable and the like can be obtained.

[0029]

Next, the present invention will be described in detail with reference to examples and test examples, but the present invention is not limited to these examples. In addition, in each example, parts represent parts by weight.

Example A1 24 parts of compound 23, 72 parts of polyvinylpyrrolidone (average molecular weight: 40,000), polyoxyethylene alkylaryl ether sulfonate (trade name: Dicksol WK) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Part, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol W)
66) 2 parts are uniformly mixed and pulverized to obtain a wettable powder.

Example A2 10.7 parts of compound 23 and polyvinylpyrrolidone (average molecular weight 40,000)
0 parts, 53.3 parts of urea, 2 parts of polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku, trade name: Dixol WK), polyoxyethylene alkyl aryl ether sulfonate (Daiichi Kogyo Seiyaku) (Trade name: Dixsol W66) 2 parts are uniformly mixed and pulverized to obtain a wettable powder.

Example A3 50 parts of Compound 23 and 50 parts of polyvinylpyrrolidone (average molecular weight: 40,000) are mixed and pulverized for 45 minutes in a ball mill to obtain a co-pulverized product. 31.5 parts of the obtained co-crushed product, 2 parts of polyoxyethylene alkylaryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixol WK), 2 parts, manufactured by Kogyo Seiyaku, trade name: Dixsol W66), 1 part of calcium dodecylbenzenesulfonate, 2 parts of white carbon (manufactured by Shionogi & Co., trade name: Carplex 80),
61.5 parts of clay are uniformly mixed and pulverized to obtain a wettable powder.

Example A4 33.3 parts of compound 23 and polyvinylpyrrolidone (average molecular weight: 40,000)
3 parts are mixed and pulverized by a ball mill for 45 minutes to obtain a co-pulverized product. Further, 33.4 parts of urea is added and mixed and pulverized by a ball mill for 20 minutes. The resulting mixture of co-ground and urea 3
1.5 parts, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku, trade name: Dixsol WK) 2 parts, polyoxyethylene alkyl aryl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku, trade name) : Dixsol W66), 2 parts of calcium dodecylbenzenesulfonate, 2 parts of white carbon (trade name: Carplex 80, manufactured by Shionogi & Co., Ltd.) and 61.5 parts of clay are uniformly mixed and pulverized to obtain a wettable powder. obtain.

Example A5 A wettable powder is obtained by replacing polyvinylpyrrolidone (average molecular weight: 40,000) of Example A1 with polyvinylpyrrolidone (average molecular weight: 360,000).

Example A6 A wettable powder is obtained by replacing polyvinylpyrrolidone (average molecular weight: 40,000) of Example A2 with polyvinylpyrrolidone (average molecular weight: 360,000).

Example A7 25 parts of compound 23 and 75 parts of polyvinylpyrrolidone (average molecular weight: 40,000) were dissolved in a mixed solvent of 200 parts of acetone and 200 parts of ethanol, and heated at 40 ° C. under reduced pressure to remove acetone and ethanol. Distillation gives an evaporation residue. 96 parts of the obtained evaporation residue, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol WK) 2
Part, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol W)
66) 2 parts are uniformly mixed and pulverized to obtain a wettable powder.

Example A8 50 parts of Compound 23 and 50 parts of polyvinylpyrrolidone (average molecular weight: 40,000) are dissolved in 200 parts of acetone, and the mixture is heated at 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. Obtained evaporation residue 50
Parts, naphthalene sulfonate (manufactured by Kao, trade name: Demol N) 4 parts, calcium dodecylbenzenesulfonate 2
Parts, 24 parts of ammonium sulfate and 20 parts of clay are uniformly mixed and pulverized, 10 parts of water is added and kneaded, and the mixture is extruded and granulated from a screen having a diameter of 0.6 mm, and then dried to obtain a wettable powder.

Example A9 17.6 parts of compound 23 and polyvinylpyrrolidone (average molecular weight: 360,000)
7.6 parts and 64.8 parts of water are mixed and pulverized with a sand grinder (Igarashi Kikai) for 30 minutes to obtain a co-pulverized product. 70 parts of the obtained co-crushed product, 3 parts of polyalkylene glycol (manufactured by Kao, trade name: Agrisol S710), 0.1 part of heteropolysaccharide (manufactured by Sansei, trade name: Kerzan),
8 parts of ethylene glycol and 18.9 parts of water are mixed and stirred to obtain a flowable.

Example A10 15 parts of compound 23 and 15 parts of polyvinylpyrrolidone (average molecular weight 3600000)
And 70 parts of water are mixed and pulverized for 30 minutes with a sand grinder (manufactured by Igarashi Kikai) to obtain a co-pulverized product. This co-ground product 7
0 parts and 10 parts of urea, 3 parts of polyalkylene glycol (manufactured by Kao, trade name: Agrisol S710), 0.1 part of heteropolysaccharide (manufactured by Sanshin, trade name: Kerzan),
8 parts of ethylene glycol and 8.9 parts of water are mixed and stirred to obtain a flowable.

Example B1 11.1 parts of compound 23 and polyethylene glycol (average molecular weight: 20,000) 3
After dissolving 3.3 parts in 200 parts of acetone, the mixture is heated to 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. Further, 55.6 parts of urea was added thereto and mixed and pulverized by a ball mill for 20 minutes to obtain a mixture. 96 parts of the obtained mixture, polyoxyethylene alkyl aryl ether sulfonate (trade name: Dixsol WK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2
And 2 parts of polyoxyethylene alkylaryl ether sulfonate (trade name: Dixsol W66, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are uniformly mixed and pulverized to obtain a wettable powder.

Example B2 11.1 parts of compound 23 and polyvinylpyrrolidone (average molecular weight 10,000)
3 parts are mixed and pulverized by a ball mill for 45 minutes to obtain a co-pulverized product. Further, 55.6 parts of urea was added thereto, and the mixture was
Mix and grind for 0 minutes to obtain a mixture. The resulting mixture 96
Part, polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol WK) 2 parts,
2 parts of polyoxyethylene alkyl aryl ether sulfonate (trade name: Dixsol W66) are uniformly mixed and pulverized to obtain a wettable powder.

Example B3 33.3 parts of compound 65 and polyvinylpyrrolidone (average molecular weight 10,000)
3 parts are mixed and pulverized by a ball mill for 45 minutes to obtain a co-pulverized product. Further, 33.4 parts of urea is added and mixed and pulverized by a ball mill for 20 minutes. The resulting mixture of co-ground and urea 3
1.5 parts, polyoxyethylene alkyl aryl ether sulfonate (trade name: Dicksol WK)
2 parts, polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol W66) 2
Parts, 1 part of calcium dodecylbenzenesulfonate, 2 parts of white carbon (trade name: Carplex 80, manufactured by Shionogi & Co., Ltd.) and 61.5 parts of clay are uniformly mixed and pulverized to obtain a wettable powder.

Example B4 A wettable powder is obtained by replacing polyvinylpyrrolidone (average molecular weight 10,000) of Example B2 with β-cyclodextrin.

Example B5 33.3 parts of Compound 29 and 33.3 parts of hydroxypropylcellulose are mixed and ground by a ball mill for 45 minutes to obtain a co-ground product. Urea 3
Add 3.4 parts and mix and crush with a ball mill for 20 minutes.
31.5 parts of a mixture of the obtained co-milled product and urea, 2 parts of a polyoxyethylene alkylaryl ether sulfonate (trade name: Dixsol WK), 2 parts of a polyoxyethylene alkylaryl ether sulfonate (previously Out,
Trade name: 2 parts of Dixzol W66), 1 part of calcium dodecylbenzenesulfonate, 2 parts of white carbon (trade name: Carplex 80), clay 61.
5 parts are uniformly mixed and pulverized to obtain a wettable powder.

Example B6 11.1 parts of Compound 7 and polyvinylpyrrolidone (average molecular weight 10,000) 33.3
Was dissolved in a mixed solvent of 200 parts of acetone and 200 parts of ethanol, and then heated to 40 ° C. under reduced pressure to distill off acetone and ethanol to obtain an evaporation residue. Further, 55.6 parts of urea were mixed and ground with a ball mill for 20 minutes. To obtain a mixture. 96 parts of the obtained mixture, 2 parts of polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol WK), polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol) W6
6) Mix and pulverize 2 parts uniformly to obtain a wettable powder.

Example B7 20 parts of Compound 1 and 20 parts of polyethylene glycol (average molecular weight: 20,000) are dissolved in 200 parts of acetone, and the mixture is heated at 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. Further, 60 parts of urea is added thereto and mixed and pulverized by a ball mill for 20 minutes to obtain a mixture. 50 parts of the obtained mixture, 4 parts of naphthalene sulfonate (trade name: Demol N, manufactured by Kao Corporation), 2 parts of calcium dodecylbenzenesulfonate, 24 parts of ammonium sulfate, and 20 parts of clay are uniformly mixed and pulverized. The resulting mixture is kneaded, extruded and granulated from a screen having a diameter of 0.6 mm, and then dried to obtain a wettable powder.

Example B8 15 parts of compound 23, 15 parts of polyvinylpyrrolidone (average molecular weight 10,000) and 70 parts of water were mixed with a sand grinder (Igarashi Kikai Co., Ltd.).
For 30 minutes to obtain a co-ground product. 70 parts of this co-ground product, 10 parts of urea, 3 parts of polyalkylene glycol (supra, trade name: Agrisol S710), heteropolysaccharide (trade name: Kerzan, manufactured by Sanseki Co., Ltd.)
0.1 parts, 8 parts of ethylene glycol and 8.9 parts of water are mixed and stirred to obtain a flowable.

Example B9 33.3 parts of compound 21 and polyethylene glycol (average molecular weight: 20,000) 6
6.7 parts are mixed and ground in a ball mill for 45 minutes to obtain a co-ground product. 31.5 parts of the obtained co-ground product, 10 parts of urea, 5 parts of polyoxyethylene alkylaryl ether (trade name: Newcol 564, manufactured by Nippon Emulsifier Co., Ltd.), and 0 heteropolysaccharides (trade name: Kelzan) 0 .
15 parts, 8 parts of ethylene glycol and 45.35 parts of water are mixed and stirred to obtain a flowable.

Example B10 25 parts of Compound 1 and 75 parts of polyvinylpyrrolidone (average molecular weight: 40,000) were dissolved in a mixed solvent of 200 parts of acetone and 200% of ethanol, and heated at 40 ° C. under reduced pressure to remove acetone and ethanol. Distillation gives an evaporation residue. 76.8 parts of the obtained evaporation residue, 19.2 parts of urea, polyoxyethylene alkyl aryl ether sulfonate (trade name: Dicksol W)
K) 2 parts of polyoxyethylene alkyl aryl ether sulfonate (trade name: Dicksol W6)
6) Mix and pulverize 2 parts uniformly to obtain a wettable powder.

Example B11 50 parts of compound 8 and 50 parts of polyvinylpyrrolidone (average molecular weight: 40,000) were dissolved in a mixed solvent of 200 parts of acetone and 200 parts of ethanol, and heated at 40 ° C. under reduced pressure to form acetone. Ethanol is distilled off to obtain an evaporation residue. The obtained evaporation residue (33.3 parts), urea (16.7 parts), naphthalenesulfonic acid salt (described above, trade name: Demol N) (4 parts), calcium dodecylbenzenesulfonate (2 parts), ammonium sulfate (24 parts), and clay (20 parts) were uniformly mixed. The mixture is kneaded by adding 10 parts of water, kneaded, extruded through a screen having a diameter of 0.6 mm and granulated, and then dried to obtain a wettable powder.

Example B12 17.6 of Compound 12
Parts and polyvinylpyrrolidone (average molecular weight 360,000)
17.6 parts and 64.8 parts of water are mixed and pulverized with a sand grinder (described above) for 30 minutes to obtain a co-pulverized product. 28 parts of the obtained co-ground product, 42 parts of urea, 3 parts of polyalkylene glycol (supra, trade name: Agrisol S710), 0.1 part of heteropolysaccharide (supra, trade name: Kelzan) 0.1
Parts, 8 parts of ethylene glycol and 18.9 parts of water are mixed and stirred to obtain a flowable.

Example B13 15 parts of Compound 18 and 15 parts of polyvinylpyrrolidone (average molecular weight 3600000)
And 70 parts of water are mixed and pulverized with a sand grinder (described above) for 30 minutes to obtain a co-pulverized product. 28 parts of this co-ground product, 42 parts of urea, polyalkylene glycol (see above, trade name:
Agrisol S710) 3 parts, heteropolysaccharide (described above, trade name: Kelzan) 0.1 part, ethylene glycol 8 parts, water 8.9 parts are mixed and stirred to obtain a flowable.

(Comparative Example A1) 24 parts of compound 23, 72 parts of polyvinylpyrrolidone (average molecular weight 10,000), polyoxyethylene alkylaryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol WK) 2
Part, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol W)
66) 2 parts are uniformly mixed and pulverized to obtain a wettable powder.

Comparative Example A2 50 parts of Compound 23 and 50 parts of polyvinylpyrrolidone (average molecular weight 10,000) were mixed and pulverized for 45 minutes in a ball mill to obtain a co-pulverized product. 31.5 parts of the obtained co-crushed product, 2 parts of polyoxyethylene alkylaryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixol WK), 2 parts, manufactured by Kogyo Seiyaku, trade name: Dixsol W66), 1 part of calcium dodecylbenzenesulfonate, 2 parts of white carbon (manufactured by Shionogi & Co., trade name: Carplex 80),
61.5 parts of clay are uniformly mixed and pulverized to obtain a wettable powder.

(Comparative Example A3) 25 parts of Compound 23 and 75 parts of polyvinylpyrrolidone (average molecular weight 10,000) were dissolved in a mixed solvent of 200 parts of acetone and 200 parts of ethanol, and heated at 40 ° C. under reduced pressure to remove acetone and ethanol. Distillation gives an evaporation residue. 96 parts of the obtained evaporation residue, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol WK) 2
Part, polyoxyethylene alkyl aryl ether sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Dixsol W)
66) 2 parts are uniformly mixed and pulverized to obtain a wettable powder.

(Comparative Example A4) 50 parts of Compound 23 and 50 parts of polyvinylpyrrolidone (average molecular weight 10,000) are dissolved in 200 parts of acetone, and the mixture is heated at 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. Obtained evaporation residue 50
Parts, naphthalene sulfonate (manufactured by Kao, trade name: Demol N) 4 parts, calcium dodecylbenzenesulfonate 2
Parts, 24 parts of ammonium sulfate and 20 parts of clay are uniformly mixed and pulverized, 10 parts of water is added and kneaded, and the mixture is extruded and granulated from a screen having a diameter of 0.6 mm, and then dried to obtain a wettable powder.

(Comparative Example A5) 17.6 parts of compound 23 and polyvinylpyrrolidone (average molecular weight 10,000)
6 parts of water and 64.8 parts of water are mixed and pulverized for 30 minutes with a sand grinder (manufactured by Igarashi Kikai) to obtain a co-pulverized product. 70 parts of the obtained co-ground product and polyalkylene glycol (manufactured by Kao Corporation,
3 parts of trade name: Agrisol S710), 0.1 part of heteropolysaccharide (manufactured by Sanshin, trade name: Kelzan), 8 parts of ethylene glycol, and 18.9 parts of water are mixed and stirred to obtain a flowable.

(Comparative Example A6) A wettable powder is obtained by replacing polyvinyl pyrrolidone (average molecular weight 10,000) of Comparative Example A1 with polyethylene glycol (average molecular weight 20,000).

(Comparative Example A7) A wettable powder is obtained by replacing polyvinyl pyrrolidone (average molecular weight 10,000) of Comparative Example A1 with hydroxypropyl cellulose.

(Comparative Example A8) 25 parts of compound 23 and 75 parts of urea were mixed and pulverized in a ball mill for 45 minutes to obtain a co-pulverized product. 40 parts of the obtained co-ground product, 4 parts of naphthalene sulfonate (trade name: Demol N, manufactured by Kao), 2 parts of calcium dodecylbenzenesulfonate, and 54 parts of clay are uniformly mixed and ground to obtain a wettable powder.

(Comparative Example A9) Compound 23 (10 parts), naphthalenesulfonic acid salt (manufactured by Kao, trade name: Demol N) 4
Parts, 2 parts of calcium dodecylbenzenesulfonate, 24 parts of diatomaceous earth, and 60 parts of clay are uniformly mixed, and then pulverized with a jet oimizer to obtain a wettable powder.

(Comparative Example A10) 10 parts of Compound 23, 5 parts of polyoxyethylene alkylaryl ether (manufactured by Nippon Emulsifier, trade name: Newcol 564), 0.2 part of heteropolysaccharide (manufactured by Sanseki, trade name: Kerzan) 0.2 Department,
After uniformly mixing 8 parts of ethylene glycol and 76.8 parts of water, the mixture is pulverized for 30 minutes with a sand grinder (manufactured by Igarashi Kikai) to obtain a flowable product.

(Comparative Example B1) 25 parts of Compound 23 and 75 parts of polyethylene glycol (average molecular weight: 20,000) are dissolved in 200 parts of acetone, and the mixture is heated at 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. Obtained evaporation residue 9
6 parts, polyoxyethylene alkyl aryl ether sulfonate (trade name: Dicksol WK) 2
And 2 parts of polyoxyethylene alkylaryl ether sulfonate (trade name: Dixsol W66) are uniformly mixed and pulverized to obtain a wettable powder.

(Comparative Example B2) 25 parts of Compound 23 and 75 parts of polyvinylpyrrolidone (average molecular weight 10,000) were mixed and pulverized by a ball mill for 45 minutes to obtain a co-pulverized product. 96 parts of the obtained co-ground product, 2 parts of polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol WK), polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixzo) -W66) is uniformly mixed and pulverized to obtain 2 parts.

(Comparative Example B3) A wettable powder is obtained by replacing the polyvinylpyrrolidone (average molecular weight 10,000) of Comparative Example B2 with β-cyclodextrin.

(Comparative Example B4) 50 parts of Compound 29 and 50 parts of hydroxypropylcellulose were mixed and pulverized for 45 minutes with a ball mill to obtain a co-pulverized product. The obtained co-crushed product 21
Part, polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol WK) 2 parts,
Polyoxyethylene alkyl aryl ether sulfonate (supra, trade name: Dixsol W66) 2 parts, calcium dodecylbenzenesulfonate 1 part, white carbon (supra, trade name: carplex 80) 2 parts, clay 72 The mixture is uniformly mixed and pulverized to obtain a wettable powder.

Comparative Example B5 25 parts of Compound 7 and 75 parts of polyvinylpyrrolidone (average molecular weight 10,000) were dissolved in a mixed solvent of 200 parts of acetone and 200 parts of ethanol, and heated at 40 ° C. under reduced pressure to remove acetone and ethanol. Evaporate to obtain an evaporation residue. 96 parts of the obtained evaporation residue, 2 parts of polyoxyethylene alkylaryl ether sulfonate (supra, trade name: Dixsol WK), polyoxyethylene alkylaryl ether sulfonate (supra, trade name: Dixzo-) 2 parts) are uniformly mixed and pulverized to obtain a wettable powder.

(Comparative Example B6) 50 parts of Compound 1 and 50 parts of polyethylene glycol (average molecular weight: 20,000) are dissolved in 300 parts of acetone, and the mixture is heated at 40 ° C. under reduced pressure to distill off acetone to obtain an evaporation residue. The obtained evaporation residue 20
Parts, naphthalene sulfonate (supra, trade name: Demol N) 4 parts, calcium dodecylbenzenesulfonate 2
Parts, 24 parts of ammonium sulfate and 50 parts of clay are uniformly mixed and pulverized, kneaded by adding 10 parts of water, extruded through a screen having a diameter of 0.6 mm, and dried to obtain a wettable powder.

Comparative Example B7 17.6 parts of Compound 23 and polyvinylpyrrolidone (average molecular weight 10,000)
6 parts, 64.8 parts of water with a sand grinder (described above) 3
The mixture is pulverized for 0 minutes to obtain a co-pulverized product. 70 parts of the obtained co-ground product, 3 parts of polyalkylene glycol (supra, trade name: Agrisol S710), 0.1 part of heteropolysaccharide (supra, trade name: Kelzan), 8 parts of ethylene glycol, and 18.9 water Mix and stir the parts to obtain a flowable.

(Comparative Example B8) Compound 3 (33.3 parts) and β-cyclodextrin (66.7 parts) were added to a ball mill with a ball mill.
Mix and grind for 5 minutes to obtain a co-milled product. 40 parts of the obtained co-ground product, 5 parts of polyoxyethylene alkyl aryl ether (supra, trade name: Newcol 564), 0.15 heteropolysaccharide (supra, trade name: Kerzan) 0.15
Parts, 8 parts of ethylene glycol and 46.85 parts of water are mixed and stirred to obtain a flowable.

Comparative Example B9 25 parts of Compound 23 and 75 parts of urea were mixed and pulverized for 45 minutes by a ball mill to obtain a co-pulverized product. 40 parts of the obtained co-ground product, 4 parts of naphthalene sulfonate (trade name: Demol N), 2 parts of calcium dodecylbenzenesulfonate, and 54 parts of clay are uniformly mixed and ground to obtain a wettable powder.

(Comparative Example B10) 10 parts of thiadiazabicyclononane derivative, 4 parts of naphthalene sulfonate (trade name: Demol N), 2 parts of calcium dodecylbenzenesulfonate, 24 parts of diatomaceous earth, clay After uniformly mixing 60 parts, the mixture is pulverized with a jet oimizer to obtain a wettable powder.

Next, description will be made with reference to test examples. Test Example 1 Herbicidal Effect Test A plastic pot (120 square centimeters in surface area) was filled with field soil, and soybeans, onamimomi, aobilyu,
Seeds of various seeds of Noasagao, after growing for 14 days in a greenhouse, dilute a predetermined amount of the preparation prepared according to each example with water,
Plants were sprayed with foliage at a rate of 250 liters per 10 ares using a small sprayer. Also, at 50 ° C. by the method shown in Test Example 2.
Each of the preparations stored for 14 days under the above temperature conditions was similarly subjected to foliar application to plants. After the treatment, the plants were grown in a greenhouse, and 21 days after the treatment, the herbicidal effect and the degree of chemical damage were investigated based on the following criteria. The results are shown as indices in Table 10, Table 11,
The results are shown in Tables 12, 13, and 14.

Index 5: Withering 4: 75% to less than 99% herbicidal effect (phytotoxicity) 3: 50% to less than 75% herbicidal effect (phytotoxicity) 2: 25% to less than 50% herbicidal effect (phytotoxicity) 1: 1% to less than 25% herbicidal effect (phytotoxicity) 0: No herbicidal effect (no phytotoxicity)

[0075]

[Table 10]

[0076]

[Table 11]

[0077]

[Table 12]

[0078]

[Table 13]

[0079]

[Table 14]

Test Example 2 Stability test of thiadiazabicyclononane derivative The preparation prepared according to each example was placed in a glass screw bottle and placed in a thermostat set at 50 ° C. for 14 days and at room temperature for 6 months. After storage for a while, analysis was performed by high performance liquid chromatography, and the residual ratio of the compound to the analysis value before storage at 50 ° C. was determined. The results are shown in Tables 15 and 16.

[0081]

[Table 15]

[0082]

[Table 16] Test Example 3 Measurement of water solubility of thiadiazabicyclononane derivative To a preparation prepared according to each example in an amount equivalent to 500 mg as a thiadiazabicyclononane derivative, 1 liter of distilled water at 20 ° C. was added, and a dissolution tester manufactured by Toyama Sangyo Co., Ltd. (NTR-VS6
The paddle was rotated at a speed of 50 revolutions per minute using a mold.
One hour later, 1 ml was collected, filtered through a 0.2 micrometer-membrane filter, and analyzed by high performance liquid chromatography to determine the concentration in water. Table 1 shows the results
5 and Table 16.

EFFECTS OF THE INVENTION A herbicidal composition comprising the thiadiazabicyclononane derivative of the present invention and a polyvinylpyrrolidone having an average molecular weight of 40,000 or more, or an aqueous solution excluding the thiadiazabicyclononane derivative and a polyvinylpyrrolidone having an average molecular weight of 40,000 or more The herbicidal composition containing a water-soluble polymer and urea is safe for agricultural products even when stored for a long period of time because the thiadiazabicyclononane derivative does not change into a highly harmful substance during storage. Further, a herbicidal composition containing a substance obtained by co-milling a thiadiazabicyclononane derivative and a water-soluble polymer or a substance obtained by dissolving in an organic solvent and then distilling off the organic solvent is used as a herbicide composition. The water solubility of the Asian zabicyclononane derivative is increased, and a high herbicidal activity is obtained. Furthermore, the herbicidal composition containing urea can obtain a high herbicidal activity even at a lower concentration. Since the herbicidal composition of the present invention containing a substance obtained by distilling off the organic solvent does not contain an organic solvent, it is highly safe for humans and animals, and has no problems such as environmental pollution.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) A01N 43/90 103 A01N 25/10 A01N 25/22 A01N 43/36 A01N 47/28

Claims (7)

(57) [Claims] 1. A compound of the general formula [Wherein X ¹ and X ² represent a hydrogen atom or a halogen atom, and Y represents a group (Where R ¹ represents a hydrogen atom or an alkyl group;
² represents an alkyl group, a cycloalkyl group or an alkoxyalkyl group. ) Or a group (Where X ³ represents an oxygen atom or a sulfur atom, and A is
Represents a linear or branched alkylene group, R ³ is a phenyl group, a halogen-substituted phenyl group, a cycloalkoxycarbonyl group, an alkylthio group, an alkoxycarbonyl group,
It represents an alkoxyalkoxycarbonyl group, an alkoxycarbonylalkylthio group, or an alkylthioalkoxycarbonyl group. 9) -Phenylimino-8-thia-1,6-diazabicyclo (4.3.
0) Nonan-7-one derivative and average molecular weight of 40,000
A herbicidal composition containing the above polyvinylpyrrolidone. 2. The herbicidal composition according to claim 1, wherein urea is added to the herbicidal component. 3. A process according to claim 1 of the general formula 9-phenylimino-8-thia-1,6-diazabicyclo (4.3.
0) A herbicidal composition comprising a nonan-7-one derivative, a water-soluble polymer compound excluding polyvinylpyrrolidone having an average molecular weight of 40,000 or more, and urea. 4. A method according to claim 1, wherein 9-phenylimino-8-thia-1,6-diazabicyclo (4.3.
0) The ratio of the nonan-7-one derivative to polyvinylpyrrolidone or the water-soluble polymer is from 10: 1 to 1:25 by weight.
The herbicidal composition according to claim 1 or 3, wherein 5. The compound of claim 1 wherein 9-phenylimino-8-thia-1,6-diazabicyclo (4.3.
0) The ratio of nonan-7-one derivative to urea is 1 by weight.
The herbicidal composition according to claim 2 or 3, wherein the range is from 0: 1 to 1: 200. 6. The 9-phenylimino-8-thia-1,6-diazabicyclo represented by the general formula of claim 1 (4.
3.0) Nonan-7-one derivative and average molecular weight of 4000
The herbicidal composition according to claim 1 or 2, comprising a substance obtained by co-milling 0 or more polyvinylpyrrolidone or a substance obtained by dissolving in an organic solvent together with polyvinylpyrrolidone having an average molecular weight of 40,000 or more and then distilling off the organic solvent. 7. A 9-phenylimino-8-thia-1,6-diazabicyclo represented by the general formula of claim 1.
3.0) Nonan-7-one derivative and average molecular weight of 4000
Contains a substance obtained by co-grinding a water-soluble polymer excluding polyvinylpyrrolidone of 0 or more with urea or a water-soluble polymer excluding polyvinylpyrrolidone having an average molecular weight of 40,000 or more, and a substance obtained by dissolving the organic solvent in an organic solvent and then distilling off the organic solvent. The herbicidal composition according to claim 3.