JPH0747522B2 - Herbicide composition of flooded sewage paddy - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous suspension formulation composition for post-planting herbicidal herbicidal control of flooded sewage paddy fields and a spraying method thereof.

[Prior Art] Conventionally, as a formulation form of herbicides used in flooded sewage paddy fields, generally two types of granules, which have the advantage of being easily sprayed, and emulsions for spraying undiluted rice in the rice paddy occupy the majority, Emulsions and wettable powders, which are partially diluted with a large amount of water and sprayed, are used.

Granules are most often used because they are relatively easy to apply. This granule can be formulated by mixing the herbicidally active compound with a fine powder carrier such as bentonite, talc, and crepe, and then pulverizing the mixture, or by granulating the fine powder carrier to obtain a granular carrier. There are various methods such as uniformly mixing and adsorbing the herbicidally active compound.
Since these are subjected to granulation and drying steps or by adsorption, the herbicidally active compound is strongly adsorbed on the carrier, resulting in a decrease in effective utilization of the herbicidally active compound. For this reason, when applying the granules, the emulsion or wettable powder is diluted with a large amount of water, and in order to obtain the same herbicidal effect as compared with the case of applying, the herbicidally active compound in the granules is required. It is necessary to mix it in a large amount and spray it, which leads to high cost of the drug or is not preferable from the viewpoint of environmental pollution.

In addition, a certain amount of granules is required to be evenly distributed in the paddy field, and currently 3 to 4 kg per 10 are.
kg of product is sprayed. This product is a little heavy,
Furthermore, since it is considerably bulky, it has many disadvantages in terms of transportation, storage, etc. as compared with wettable powders or emulsions.

On the other hand, the emulsion for spraying undiluted rice before rice transplantation can be easily sprayed without the use of a device as in the case of spraying granules, and the amount of active ingredient sprayed per area is the same as when spraying granules. The same effect can be obtained with a little effort. However, spraying the undiluted solution of this emulsion after transplanting rice, that is, after transplanting seedlings with rice, has a drawback in that it causes serious phytotoxicity to paddy rice mainly due to an organic solvent contained in a large amount in the formulation. Therefore, the current undiluted spraying of emulsion can be applied only before rice transplanting. However, spraying a herbicide by spraying an undiluted emulsion prior to rice planting is not preferable from the standpoint of environmental pollution because the chemicals run off into the river due to the falling water during rice planting. In addition, the problem of toxicity and irritation to humans and small animals due to organic solvents in the formulation, and odor,
In addition, there are many problems such as the need to be careful during transportation and storage from the aspect of flammability.

Further, emulsions and wettable powders that have been used for dilution and spraying in a large amount of water conventionally require a great deal of labor at the time of spraying because the drug is diluted to about 50 to 100 water per 10 ares. For this reason, it is much less likely to be applied than granules or emulsions for spreading undiluted rice before planting. Further, in the case of emulsion, there is a problem caused by the above-mentioned organic solvent, and in the case of wettable powder, there is a problem in handling and working environment that fine powder is scattered during preparation of the spray liquid. is there.

In recent years, an aqueous suspension formulation has been developed in addition to an emulsion or powdery wettable powder as one of the agricultural chemical formulation forms to be used after diluting with a large amount of water. In general, when the pesticidal drug substance is a solid, this aqueous suspension preparation is pulverized into a fine powder with an average particle size of about 0.5 μ to 10 μ, and water is used as a dispersion medium to form a surfactant and, if necessary, a water-soluble formulation. It is a formulation in which a hydrophilic polymer and the like are blended and stabilized in a suspension state.

When used, this aqueous suspension preparation is diluted with a large amount of water of 50 to 100 per 10 are and sprayed in the same manner as a wettable powder in the form of emulsion or powder. In this case, it is possible to expect a medicinal effect equivalent to that obtained by diluting an emulsion or powdery wettable powder in a large amount of water and spraying it. Further, since the dispersion medium is water, there are no problems such as toxicity, irritation or bad odor to humans and small animals due to organic solvents, as compared with emulsions. However, since it is diluted with a large amount of water and then sprayed, a great deal of labor is required at the time of spraying, and it is not applied as a spraying method for paddy field herbicides.

Also, the aqueous suspension formulation is suitable for high-concentration small-quantity spraying in the air by an aircraft, but since it is sprayed in a fine mist, the drift of the drug to the residential area, urban area, etc. outside the spraying area becomes a problem. Has become. Airborne application of pesticides by aircraft in the field of paddy rice is applied only to insecticides and fungicides, not as a method of applying herbicides. This is because the rice planting date and time is different for each paddy field,
Since the growth condition of various weeds occurring after rice planting is different in each paddy field, it is necessary to spray the herbicide to each paddy field according to the growth condition of the weeds. This is because it is practically impossible to apply the method over a wide area such as airborne application.

JP-A-60-214701 and JP-A-60-215602 describe a suspension composition. As described in the specification, this is a soil mixing treatment or a treatment in a muddy water state on the assumption that it is applied as a pre-rice-plant treatment agent, and there is no description as a post-rice-plant treatment agent.

[Problems to be Solved by the Invention] As described above, all the herbicide formulation forms conventionally used in flooded sewage fields have various problems.

The inventors of the present invention can easily spray granules in the submerged paddy field as well as the emulsion for spraying the undiluted solution before rice transplanting, and weed the wettable powder or emulsion by diluting it in a large amount of water and spraying it. The present invention has been completed as a result of intensive studies to develop a herbicide formulation form that can fully exert the herbicidal effect of the active compound and that is less toxic to seedling rice such as immediately after rice planting. did.

[Means and Actions for Solving Problems] The present invention provides a herbicidally active compound having an average particle size of 0.5 to 5 μm and a solubility in water of 100 ppm or less (25 ° C.) of 1 to 60.
%, 30-95% water, the main component of the residue is a surfactant, and the surface tension is 36-65 dyne / cm (25 ℃). Provided is an aqueous suspension preparation composition for use (hereinafter referred to as the composition of the present invention) and a method for spraying a herbicide, which comprises spraying the aqueous suspension preparation composition directly onto a flooded sewage paddy field after planting. It is a thing.

The composition of the present invention is easy to spray, can exert sufficient herbicidal effect even when the amount of the active ingredient to be sprayed is smaller than that in the case of granules, and it shows phytotoxicity to seedling rice such as immediately after rice planting. It has excellent features such as less.

As the method for producing the composition of the present invention, for example, a method of previously finely pulverizing the herbicidal active compound with an air mill or a hammer mill and then dispersing the herbicidal active compound in water together with the surfactant, or mixing the herbicidally active compound in water to which the surfactant is added. Then
A method of dispersing while finely pulverizing with a wet pulverizer such as a ball mill, a vibration mill, a tower mill, a sand mill, or after pulverizing the herbicidally active compound to some extent in advance and dispersing it in water together with a surfactant, Examples include a method of atomizing with a crusher.

The surfactant that can be used is not particularly limited, and those conventionally used in the field of agricultural chemical formulations are used. Examples include lignin sulfonate, alkylallyl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl allyl. Anionic surfactants such as phosphate, polyoxyethylene alkylallyl ether sulfate, alkylnaphthalene sulfonate, polyoxyethylene styryl phenyl ether sulfate, polyoxyethylene alkyl allyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl Ether, polyoxyethylene sorbitan alkylate, polyoxyethylene glycol, polyoxyethylene alkyl ester, polyoxyalkylene glycol, etc. It can be mentioned non-ionic surfactants. These surfactants may be used alone or in combination of two or more, and the mixing ratio in the case of mixing may be arbitrarily selected.

Regarding the stabilization of the herbicidally active compound in the aqueous suspension preparation, a water-soluble polymer compound can be used as a protective colloid agent together with a surfactant having a dispersing effect. Examples of water-soluble polymers that can be used include gum arabic, sodium alginate, tragacanth gum, xanthan gum (xanthan gum), dextrin, gelatin, casein, glue, methyl cellulose, hydroxyethyl cellulose,
Examples thereof include hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, soluble starch, sodium polyacrylate and the like.

Similarly, for stabilizing the herbicidally active compound in the aqueous suspension preparation, an inorganic substance such as white carbon or bentonite, or a petroleum resin can be added.

Examples of the antifreezing agent of the aqueous suspension preparation in the cold season include ethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropanol,
Urea, alkali halide salts, etc. can be added.

Further, other components such as a silicone type defoaming agent or a fungicide may be blended.

In the composition of the present invention, the herbicidal drug substance that can be used has a solubility in water of 100 ppm or less at 25 ° C. When the herbicidal drug substance having a solubility in water of 100 ppm or more is applied to the composition of the present invention, the active ingredient is washed away by water leakage of the paddy field, or the active ingredient is flushed to the river by being dissolved in the submerged water of the paddy field. The herbicidal effect of the herbicide drug substance may not be fully exerted. If the herbicidal drug substance has a solubility in water of 100 ppm or less at 25 ° C, a stable herbicidal effect can be obtained without such a problem.

The herbicidally active compound that can be used in the composition of the present invention is not particularly limited as long as it has a solubility in water of 100 ppm or less at 25 ° C, and specific examples thereof include the following compounds. It goes without saying that the compounds that can be used in the composition of the present invention are not limited to the compounds of this specific example. This compound No. is cited in the description below.

Compound No. Compound name 1 O-4-tert-butylphenyl N- (6-methoxy-2-pyridyl) -N-methylthiocarbamate 2 O-3-tert-butylphenyl N- (6-methoxy-2-pyridyl) -N-methylthiocarbamate 3 O-4-chloro-3-ethylphenyl N- (6-
Methoxy-2-pyridyl) -N-methylthiocarbamate 4 O-4-bromo-3-ethylphenyl N- (6-
Methoxy-2-pyridyl) -N-methylthiocarbamate 5 3-tert-butyl-4-chlorophenyl N- (6
-Methoxy-2-pyridyl) -N-methylcarbamate 6 O-4-trifluoromethylphenyl N- (6-
Methoxy-2-pyridyl) -N-methylthiocarbamate 7 1- (α, α-dimethylbenzyl) -3- (4-methylphenyl) urea [general name: Daimlon] 8 N- (α, α-dimethylbenzyl)- 2-bromo-
3,3-Dimethylbutyramide [generic name: bromobutide] 9 2- (2-naphthyloxy) propionanilide [generic name: naproanilide] 10 2- (2,4-dichloro-3-methylphenoxy) propionanilide [test name : MY-15] 11 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl p-toluenesulfonate [generic name: pyrazolate] 12 4- (2,4-dichlorobenzoyl) -1, 3-Dimethyl-5-phenacyloxypyrazole [generic name: pyrazoxifene] 13 4- (2,4-dichloro-3-methylbenzoyl)-
1,3-dimethyl-5- (4-methylphenacyloxy)
Pyrazole [Test name: NY-71] 14 5-Benzyloxy-4- (2,4-dichlorobenzoyl) -1-methylpyrazole [Test name: NC-310] 15 2,4,6-Trichlorophenyl 4-nitro Phenyl ether [generic name: chloronitrophene] 16 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether [generic name: clomethoxynil] 17 2,4-dichlorophenyl 3-methoxycarbonyl-
4-nitrophenyl ether [generic name: bisphenox] 18 2-chloro-4-trifluoromethylphenyl 4
-Nitro-3- (tetrahydropyran-3-yloxy) phenyl ether [Test name: MT-124] 19 N-methyl-2- (2-benzothiazolyloxy)
Acetanilide [Test name: NTN-801] 20 2 ', 3'-Dichloro-4-ethoxymethoxybenzanilide [Test name: HW-52] 21 5-tert-Butyl-3- (2,4-dichloro-5-) Isopropoxyphenyl) -1,3,4-oxadiazole-
2 (3H) -one [generic name: oxadiazon] 22 2-amino-3-chloro-1,4-naphthoquinone [generic name: ACN] 23 2-[(4,6-dimethoxypyrimidin-2-yl)
Aminocarbonylaminosulfonylmethyl benzoic acid methyl ester [Test name: DPX-84] 24 3,7-Dichloro-8-quinolinecarboxylic acid [Test name:
BAS-514] 25 5-[(4,6-dimethoxypyrimidin-2-yl)
Aminocarbonylaminosulfonyl] -1-methylpyrazole-4-carboxylic acid ethyl ester [Test name: NC-3
11] 26 3-chloro-2- [2-fluoro-4-chloro-5
-(1-Propinyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole [Test name: S-275] These herbicidally active compounds are selected according to the weed species to be weeded. One kind may be used alone, or two or more kinds may be mixed and mixed, and the mixing ratio in the case of mixing may be arbitrarily selected. These herbicidally active compounds, in an aqueous suspension formulation,
It is contained in the range of 1 to 60%. Further, the composition of the present invention,
It contains 30 to 95% water, and the main component of the balance is a surfactant.

The composition of the present invention is particularly suitable as a formulation form for spraying a herbicide after rice planting, that is, after transplanting seedling rice.

The composition of the present invention can be applied easily and easily without using a special device, as in the case of the granules or the emulsion for pre-rice transplanting. Further, even if the amount of the active ingredient of the herbicide to be sprayed is smaller than that in the method of spraying the granule, a sufficient herbicidal effect equal to or higher than that of the method can be obtained.
Further, unlike the emulsion for spraying undiluted solution before rice planting, a major feature is that even if sprayed after rice planting, there is little chemical damage to the seedling transplanted rice.

The composition of the present invention has a solubility in water at 25 ° C of 100 p
The average particle size of the herbicidal active compound of pm or less is 0.5 to 5 μm.
It is an aqueous suspension pharmaceutical composition containing a compound within the range. Therefore, when the composition of the present invention is directly applied to the flooded sewage paddy after rice planting without further diluting it with water, the water surface and the water are rapidly spread and settled, with respect to the weeds on the entire surface of the paddy field. A sufficient herbicidal effect can be expressed.

When spraying an undiluted solution before rice padding onto paddy fields, you are taught to shake the bottles one by one to the left and right every 5 to 6 steps (about 3 m) while walking straight. When spraying the composition of the present invention on a paddy field, the fact that the herbicidal effect can be expressed even in a wide area which is not inferior to that in the case of spraying this emulsion for pre-rice planting solution is truly surprising. is there.

On the other hand, in the case of an aqueous suspension preparation composition containing an herbicidally active compound having an average particle size of 5 μm or more, the spread on the water surface and in water is insufficient even if it is sprayed directly without further diluting with water. Therefore, the herbicidal effect is exhibited only in a very small area where the liquid medicine drops. Therefore, in order to exert the herbicidal effect on the entire surface of the paddy field, it is necessary to spray it evenly and uniformly over the entire surface of the paddy field, which is not practical.

Incidentally, in order to make the average particle diameter of the herbicidal active compound 0.5 μm or less, enormous energy is required for pulverization, which causes a practically inconvenient problem.

The composition of the present invention is an aqueous suspension preparation composition having physical properties of surface tension of 36 to 65 dyne / cm (25 ° C). Therefore, when directly spraying the composition of the present invention to the submerged sewage paddy after planting without further diluting it with water, even if the chemical solution contacts the seedling rice leaf blade, the chemical solution itself Due to its physical properties, it is almost not attached to the medicinal part, and it is repelled and drops as drops to the surface of the rice field, avoiding the chemical damage caused by the adhesion of the medicinal solution to the leaf part of the seedling paddy rice to the extent that there is no practical problem. You can The chemical liquid dropped on the surface of the paddy field spreads and settles on the surface and in the water, and exerts a sufficient herbicidal effect on the weeds on the entire surface of the paddy field.

On the other hand, when an aqueous suspension formulation with a surface tension of less than 36 dyne / cm (25 ° C) was sprayed directly onto the paddy fields after rice planting, the leaf sap that contacted the seedlings of the rice seedlings became moist without being repelled. Adheres and causes serious phytotoxicity due to herbicidally active compounds, surfactants and other auxiliaries. For this reason,
It cannot be applied directly to the paddy field after rice planting.

It becomes a more serious problem when the emulsion for spraying the undiluted solution before rice transplanting is sprayed after rice transplanting. That is, in the case of an emulsion, the affinity between the drug solution and the rice leaf blade part is very high due to the large amount of organic solvent contained in the formulation. It can be observed that the leaf fluid that has come into contact with the leaf part is largely repelled into the leaf blade without being repelled. Paddy rice contacted with this emulsion causes irreversible and serious phytotoxicity.

When the surface tension of the aqueous suspension preparation is higher than 65 dyne / cm (25 ° C), practically inconvenient problems such as poor dispersibility of the herbicidally active compound in the preparation occur.

As described above, the composition of the present invention, even if the chemical solution comes into direct contact with the paddy field of the paddy rice after being sprayed directly onto the paddy field after planting without further diluting it with water, drops onto the surface of the paddy field without sticking. The composition of the present invention, which causes almost no phytotoxicity and further falls on the surface of the paddy field, spreads and sinks on the surface of the water and the water using the water of the paddy field under flooding, and is sufficient for weeds on the entire surface of the paddy field. It has an epoch-making performance of expressing a herbicidal effect.

When spraying the composition of the present invention, the composition of the present invention is used without further dilution in water. For spraying, a stock solution of the composition of the present invention is dropped onto the entire surface of a paddy field under flooding, or a drop operation is performed for work at the time of rice planting, and water is input after rice planting. It is also possible to spread the chemicals over the entire surface of the paddy field by performing a dripping process directly with the inflow water at the intake of.

The amount of the aqueous suspension formulation used in the present invention is not particularly limited,
From the viewpoint of spraying labor and formulation, the range is preferably 0.1 to 4 per 10 ares, and more preferably 0.3 to 2 per 10 ares.

Without diluting the composition of the present invention with further water, the composition is sprayed directly by drops, so that the volume of the stock solution sprayed to 10 ares is 0.
It can be prepared in the range of 1 to 4, and in comparison with the application amount of 3 kg to 4 kg per 10 are when applying granules, the volume weight of the product can be greatly reduced, and therefore the product can be transported.・ It is very advantageous in terms of storage.

[Examples] Next, examples of formulations of the composition of the present invention and comparative examples of aqueous suspension formulations, wettable powders, emulsions and granule formulations used for comparison will be described.

In the examples and comparative examples, “part” means part by weight.

Example 1 30 parts of compound No.2, 5 parts of ethylene glycol, 0.15% xanthan gum (xanthan gum) + 0.15% guar gum aqueous solution, 60.5 parts, which had been dry pulverized with a pin mill 160Z type (manufactured by Fuji Sangyo Co., Ltd.) in advance, Solpol 9838P [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 2nd section, Solpol 9047K
[Product name, manufactured by Toho Chemical Industry Co., Ltd.] Part 2, Pronal EX
-150 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 0.5 parts of hard glass beads with a diameter of 1 to 1.5 mm for grinding, and a four-cylinder sand grinder [manufactured by Igarashi Machinery Co., Ltd.]
Pulverization for 2 hours at 00 rpm gave a uniform aqueous suspension formulation.

About the thus obtained aqueous suspension preparation, ESB-IV full automatic flat surface tension meter [Kyowa Scientific Co., Ltd.]
As a result of measuring the surface tension using
℃).

The average particle size was measured using SK Laser Micron Sizer [manufactured by Seishin Enterprise Co., Ltd.], and the result was 1.5 μm.

In Examples 2-14 and Comparative Examples 1-8, the same operation as in Example 1 was performed to obtain aqueous suspension preparations. The surface tension (25 ° C.) and average particle size of each component and the obtained aqueous suspension preparation are described below.

Example 2 Compound No. 2 6 parts Ethylene glycol 3 parts Solpol 9047K 2 parts Solpol 9838P 2 parts Xanthan gum 0.15% + guar gum 0.15% Aqueous solution 86.5 parts Pronal EX-150 0.5 parts Surface tension 39.5 dyne / cm Average particle size 1.6μ Example 3 Compound No. 1 6 parts Ethylene glycol 3 parts Solpol 9047K 3 parts Xanthan gum 0.075% + guar gum 0.075% Aqueous solution 87.5 parts Pronal EX-150 0.5 parts Surface tension 51.7dyne / cm Average particle size 1.5μ Example 4 Compound No. 2 6 Part Ethylene glycol 3 parts Sorpol 9047K 2 parts Xanthan gum 0.075% + guar gum 0.075% Aqueous solution 88.5 parts Pronal EX-150 0.5 parts Surface tension 56.0 dyne / cm Average particle size 1.7μ Example 5 Compound No. 2 6 parts Ethylene glycol 3 parts Solpol 9047K 3 parts Solpol 7465 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 1 part Xanthan gum 0.15% + guar gum 0.15% aqueous solution 85.5 parts Pronal EX-150 0.5 parts Nipseal NS-K [Product name: manufactured by Nihon Silica Industry Co., Ltd.] 1 part Surface tension 56.4 dyne / cm Average particle size 1.6μ Example 6 Compound No. 2 30 parts Ethylene glycol 5 parts Solpol 7465 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 1 part Solpol 9047K 2 parts Solpol 9838P 2 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 58.5 parts Pronal EX-150 0.5 parts Nipseal NS-K [trade name, Nippon Silica Industrial Co., Ltd.] 1 part Surface tension 37.3 dyne / cm Average particle size 1.5μ Example 7 Compound No. 19 6 parts Ethylene glycol 3 parts Solpol 9047K 3 parts Xanthan gum 0.075% + guar gum 0.075% aqueous solution 87.5 parts Pronal EX-150 0.5 part Surface tension 46.7 dyne / cm Average particle size 1.6μ Example 8 Compound No. 2 40 parts Ethylene glycol 4 parts Solpol 9047K 3 parts Xanthan gum 0.075% + guar gum 0.075 Aqueous solution 52.5 parts Pronal EX-150 0.5 part Surface tension 64.3 dyne / cm Average particle size 1.6μ Example 9 Compound No. 2 50 parts Ethylene glycol 4.5 parts Solpol 5073 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 4.5 parts Xanthan gum 0.075% + Guar gum 0.075% Aqueous solution 40.5 parts Pronal EX-150 0.5 parts Surface tension 38.7 dyne / cm Average particle size 1.5μ Example 10 Compound No. 2 parts 2 parts Ethylene glycol 3 parts Solpol 5073 1 part Xanthan gum 0.075% + Guar gum 0.075% Aqueous solution 93.5 parts Pronal EX-150 0.5 parts Surface tension 40.0 dyne / cm Average particle size 1.6μ Example 11 Compound No. 2 15 parts Ethylene glycol 5 parts Toxanone GR-50P [trade name, manufactured by Sanyo Chemical Industries, Ltd.] 3 Part Xanthan gum 0.15% + Guar gum 0.15% Aqueous solution 76.5 parts Pronal EX-150 0.5 parts Surface tension 41.5 dyne / cm Average particle size 1.6μ Example 12 Compound No. 2 25 parts Ethylene glycol 5 parts Sun Kiss P252 [trade name, manufactured by Sanyo Kokusaku Pulp Co., Ltd.] 5 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 64.5 parts Pronal EX-150 0.5 part Surface tension 54.0 dyne / cm Average particle size 1.6μ Example 13 Compound No. 2 25 parts Ethylene glycol 5 parts Vanilex N [trade name, manufactured by Sanyo Kokusaku Pulp Co., Ltd.] 5 parts Xanthan gum 0.15% + guar gum 0.15% Aqueous solution 64.5 parts Pronal EX-150 0.5 parts Surface tension 52.1dyne / cm Average particle size 1.7μ Implementation Example 14 Compound No. 15 10 parts Ethylene glycol 3 parts Toxanone GR-50P 3 parts Xanthan gum 0.15% + guar gum 0.15% Aqueous solution 83.5 parts Pronal EX-150 0.5 parts Surface tension 40.7 dyne / cm Average particle size 1.5μ Comparative Example 1 Compound No. .2 6 parts Ethylene glycol 5 parts Solpol 355 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 3 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 85.5 parts Pronal EX-150 0.5 part Surface tension 32.5 dyne / cm Average particle size 1.6μ Comparative Example 2 Compound No. 2 6 parts Ethylene glycol 3 parts Solpol 392 [Product name: Toho Chemical Industry Co., Ltd.] 3 parts Xanthan gum 0.075% + guar gum 0.075% aqueous solution 87.5 parts Pronal EX-150 0.5 parts Surface tension 34.5 dyne / cm Average particle size 1.5μ Comparative Example 3 Compound No. 2 6 parts Ethylene glycol 5 parts Solpol 3005X [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 3 parts Xanthan gum 0.15 % + Guar gum 0.15% aqueous solution 85.5 parts Pronal EX-150 0.5 part Surface tension 31.0 dyne / cm Average particle size 1.5μ Comparative Example 4 Compound No. 2 15 parts Ethylene glycol 5 parts Toxanone P8-L [trade name, Sanyo Chemical Industries ( Co., Ltd.] 3 parts Xanthan gum 0.15% + guar gum 0.15% Aqueous solution 76.5 parts Pronal EX-150 0.5 parts Surface tension 28.9 dyne / cm Average particle size 1.5μ Comparative Example 5 Compound No. 2 15 parts Ethylene glycol 5 parts Solpol DSN [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 3 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 76.5 parts Pronal EX-150 0.5 part Surface tension 31.8dyne / cm Average particle size 1.6μ Comparative Example 6 Compound No. 15 10 parts Ethylene glycol 3 parts Solpol 3005X 3 parts Xanthan gum 0.15% + guar gum 0.15% Aqueous solution 83.5 parts Pronal EX-150 0.5 parts Surface tension 30.8 dyne / cm Average particle size 1.6μ Comparative Example 7 Compound No.2 30 parts Ethylene glycol 5 parts Solpol 3743 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 2 parts Solpol 7465 1 part Solpol 9047K 2 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 58.5 parts Pronal EX-150 0.5 parts Nipseal NS-K 1 part Surface tension 35.8dyne / cm Average particle size 1.7μ Comparative Example 8 2,4-bis (ethylamino) -6-15 parts Methylthio-1,3,5-triazine [generic name: cimetrin, water solubility 45 0 ppm] Ethylene glycol 3 parts Sorpol 9047K 2 parts Sorpol 9838P 2 parts Xanthan gum 0.15% + guar gum 0.15% aqueous solution 77.5 parts Pronal EX-150 0.5 parts Surface tension 39.7 dyne / cm Average particle size 1.6μ Examples 15 to 16 and Comparative Example 9 Then, the same components as in Example 2 were used, and the grinding time of the four-cylinder sand grinder was changed to obtain an aqueous suspension preparation. The pulverization time, the surface tension (25 ° C) and the average particle size of the obtained aqueous suspension preparation are described below.

Example 15 Grinding time 30 minutes Surface tension 40.2 dyne / cm Average particle size 4.5 μ Example 16 Grinding time 10 hours Surface tension 39.9 dyne / cm Average particle size 0.9 μ Comparative example 9 Grinding time 10 min Surface tension 40.3 dyne / cm Average Particle size 7.3μ Comparative Example 10 Compound No.15 10 parts, Kunilite [trade name, manufactured by Kunimine Industry Co., Ltd.] 87.3 parts, Neoperex [trade name, manufactured by Kao Atlas Co., Ltd.] 1.35 parts and Solpol 800A [trade name] Name, manufactured by Toho Chemical Industry Co., Ltd.] and pulverized together with 1.35 parts to obtain a 10% wettable powder.

Comparative Example 11 Compound No. 2 10 parts, xylene 80 parts, and solpol
It was mixed and dissolved with 10 parts of 800A to obtain a 10% emulsion.

Comparative Example 12 Compound No. 2 3.5 parts, bentonite 30 parts, talc 60.5
Section, 2 parts Solpol 9047K, 2 parts Solpol 5160 [trade name, manufactured by Toho Chemical Industry Co., Ltd.] and 355 Solpol
After mixing and pulverizing 2 parts, add 10 parts of water and stir uniformly, extrude through a sieve hole with a diameter of 0.7 mm, and dry 1-2 mm.
To obtain 3.5% granules.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Examples 17 to 32 and Comparative Examples 13 to 24 The paddy soil in the substituting state was put in a plastic container having an area of 1836 cm ² (31 × 56 cm) to a depth of 7 cm from the bottom, and a 2-leaf stage paddy rice seedling (variety: Nipponbare) was placed at 1 cm. 9 plants were planted at a depth of 1 each. The next day, 3 cm of water was poured. Three days after transplanting the rice seedlings, the stock solutions of the aqueous suspension preparations prepared in Examples 1 to 16 and Comparative Examples 1 to 8 and the emulsions prepared according to Comparative Example 10 were used as the second leaf blades of each rice seedling. Each drop was dropped by a pipette into the center and the base of the leaf blade. At this time, the adherence of the drug to the leaf blade was observed according to the following criteria.

Adherence status of chemicals Evaluation criteria Adhesion status No adherence No adherence Slightly adhered, mostly dropped Small adhered Small a little About half adhered Large majority to all adhered After treating each chemical, avoid watering the foliage in the greenhouse. It was grown with the water depth kept at 3 cm. After 3 weeks from the chemical treatment, the chemical damage to paddy rice was evaluated by observation according to the following criteria. Table 1 shows the evaluation results and the state of attachment of the chemicals to the rice leaf blades during chemical treatment.

Evaluation criteria for rice rice phytotoxicity Evaluation degree of phytotoxicity − Harmless ± Minor harm + Minor harm Medium harm Major harm × Death Examples 33 to 58 and Comparative Examples 25 to 65 After cultivating paddy fields and substituting them, they were divided into 4 m ² (2 × 2 m) using a board and a ridge board, and seeds of Novier seeds were sown. 2 paddy rice seedlings (variety: Nihonbare) at the leaf stage at a depth of 1 cm
18 plants were planted each. The next day, water was flooded to 2-3 cm. 3 days after transplanting rice seedlings and 1.5 leaf stage of Novier
After a day), a predetermined amount of each drug was treated. The treatment was carried out by the method described below for each formulation.

Aqueous suspension formulations (Examples 33-58 and Comparative Examples 25-32, 48-5
4) A predetermined amount of the stock solution of the aqueous suspension preparations prepared in Examples 1 to 16 and Comparative Examples 1 to 8 was dropped onto the surface of the rice field with a pipette at substantially equal intervals. At that time, 6 drops out of a predetermined amount of the stock solution were dropped by 2 drops so that the stock solution contacted 3 strains of rice seedlings.

Wettable powder (Comparative Examples 33 to 36 and 55 to 57) After diluting a predetermined amount of the wettable powder prepared according to Comparative Example 10 into 200 ml of water (equivalent to 50 per 10 ares to be sprayed), Dropping was performed on the entire surface of the rice field.

Emulsion (1) (Comparative Examples 37 to 39, 58 and 59) A predetermined amount of the emulsion prepared according to Comparative Example 11 was diluted with 200 ml of water and then added dropwise to the entire surface of the rice field.

Emulsion (2) (Comparative Examples 40 to 42, 60 and 61) A predetermined amount of the emulsion prepared according to Comparative Example 11 was dropped onto the water surface of the rice field with a pipette at substantially equal intervals. At that time, 6 drops out of the predetermined amount of the stock solution were dropped in 2 drops so that the stock solution contacted 3 strains of the rice seedlings.

Granules (Comparative Examples 43 to 46 and 62 to 64) A predetermined amount of the granules prepared according to Comparative Example 12 was sprayed on the surface of the rice field at substantially equal intervals. Incidentally, Comparative Example 45
About the commercially available "MO granules" (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., 7% of herbicidal active compound No. 15 as an active ingredient)
contains. ) Was used.

Each drug treatment maintained a water depth of 2-3 cm.

One month after the chemical treatment, the herbicidal effect and the chemical damage to paddy rice were evaluated by observation. The herbicidal effect was evaluated according to the following criteria, and the chemical damage to paddy rice was evaluated according to the above criteria. The results of the 3-day post-treatment of paddy rice seedlings are shown in Table 2, and the results of the 1.5 leaf stage treatment of Novier are shown in Table 3.

Criteria for evaluation of herbicidal effect Evaluation 5 100% control (residual amount 0%) 4 80% control (residual amount 20%) 3 60% control (residual amount 40%) 2 40% control (residual amount 60%) 1 20% control (80% of residual grass) 0% control (100% of residual grass) Examples 59 to 64 and Comparative Examples 66 to 69 Paddy soil in a substituting state was placed in a plastic container having an area of 1836 cm ² (31 × 56 cm) to a depth of 7 cm from the bottom, and seeds of Novier were sown on the entire surface of the soil. The next day, 3 cm of water was flooded and allowed to stand in the greenhouse. After 3 days, a predetermined amount of each drug was dropped by a pipette onto the water surface of the above-mentioned plastic container at substantially equal intervals.

The day after the chemical treatment, the water in the plastic container was extracted using a siphon and discarded, and a section where a new 3 cm of water was flooded and a section where the chemical treatment was continued and the area was grown were provided.

After that, the plastic container was allowed to stand in a greenhouse and watered at appropriate times.

The herbicidal effect was investigated by observation one month after the drug treatment. The herbicidal effect was evaluated according to the above criteria, and the results are shown in Table 4.

Examples 65 to 70 and Comparative Examples 70 to 77 After paddy fields were cultivated and substituting, paddy rice seedlings (variety: Nihonbare) at the 3-leaf stage were transplanted using a rice transplanter. After that, a 25 m ² (5 × 5 m) section was created using the ridge board, and the Novier seeds were sown on the entire surface of the section. The next day, water was flooded to 2-3 cm. A predetermined amount of each drug was treated 3 days after transplanting rice seedlings and 1.5 leaf stage of Novier (9 days after transplanting rice seedlings). The treatment was performed by dropping a predetermined total amount of each drug from the height of 1 m at a time to the central part of each compartment. Then, the water depth of 2-3 cm was maintained. In the investigation, one month after the drug treatment, the herbicidal effect and the phytotoxicity to paddy rice were evaluated by observation according to the above-mentioned criteria. The results of the 3-day post-treatment of paddy rice seedlings are shown in Table 5, and the results of the Novier 1.5 leaf stage treatment are shown in Table 6.

[Effects of the Invention] As is clear from the above Examples and Comparative Examples, when the composition of the present invention is used, a sufficient herbicidal effect can be exhibited even when the amount of the active ingredient applied to the same area is smaller than that of granules. .
Wettable powders or emulsions diluted with 50 to 100 water per 10 ares or 3 kg to 4 per 10 ares
It is possible to reduce the amount of spray per 10 ares compared to the granules that spray the formulation of kg, and the merit of reducing the spraying labor is great. It is also advantageous in terms of transportation and storage.

The composition of the present invention has a solubility in water of 100 p
Since the active ingredient of herbicide of pm or less is used, stable herbicidal effect is exhibited without problems such as runoff of active ingredient due to water leakage in paddy field or runoff of active ingredient into river due to dissolution in paddy water of paddy field. .

Further, the composition of the present invention, the average particle size of the herbicidally active compound is 0.
When the composition of the present invention is blended in a range of 5 to 5 μ, and the composition of the present invention is directly applied to the submerged sewage paddy field without further diluting it, the water surface and the water are rapidly spread. It is possible to settle and to exert a sufficient herbicidal effect on weeds on the entire surface of the paddy field. Furthermore, for emulsions sprayed with undiluted solution and aqueous suspension formulations with surface tension of less than 36 dyne / cm (25 ° C), when sprayed without further dilution with water,
Since the undiluted solution of the drug causes tremendous phytotoxicity when it adheres to the paddy rice leaf blade, it cannot be sprayed after transplanting rice, but in the composition of the present invention, even if spraying of the drug is carried out after transplanting rice, it will still be applied to paddy rice. It causes very little chemical damage and has practically no problem.

As described above, the composition of the present invention has many excellent characteristics and is highly practical.

 ─────────────────────────────────────────────────── --Continued from the front page Judgment panel for referee Judge Yasuda Wada Judge Akiko Hanaoka Judge Misao Taniguchi (56) References JP55-36458 (JP, A) JP55-79303 (JP, A) ) JP-A-60-214701 (JP, A) JP-B-52-39725 (JP, B2) Tetsuo Takematsu "Latest Chemical Weeding Law" Paddy Field and Paddy Liner Edition (Revised Supplementary Edition) Published September 1, 1937 , P .; 115-119 Proc. So. Weed Sci. S oc. , 29; 439-441 (1976)

Claims (2)

[Claims] 1. A herbicidally active compound having an average particle size of 0.5 to 5 μm and a solubility in water of 100 ppm or less (25 ° C.) of 1 to 60.
%, 30-95% water, the main component of the residue is a surfactant, and the surface tension is 36-65 dyne / cm (25 ℃). Aqueous suspension formulation composition. 2. A herbicidally active compound having an average particle size of 0.5 to 5 μm and a solubility in water of 100 ppm or less (25 ° C.) is 1 to 60.
%, Water 30-95%, the main component of the residue is a surfactant, and the surface tension is 36-65 dyne / cm (25 ° C). A method of spraying a herbicide, which comprises spraying directly onto a flooded paddy field.