JP3289836B2 - Aqueous suspension herbicidal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a spreadable aqueous suspension herbicidal composition, particularly to an aqueous suspension herbicidal composition suitable for application to flooded paddy fields.

[0002]

2. Description of the Related Art At present, the most commonly used method of applying an aqueous suspended herbicidal composition in which fine particles of a herbicidal component which is hardly soluble in water together with a surfactant are dispersed and suspended in water is applied to a flooded paddy field. Compared to the method of spraying wettable powders and granules,
Since too little dilution water or solid carrier is used, it is advantageous in terms of drug transport and storage. In addition, in this method, it is only necessary to apply the drug locally rather than on the entire paddy field, so there is no need to walk in the paddy field, so that it is possible to prevent the growth damage of the rice and reduce the labor for spraying the drug. Actively researching and developing. Specifically, for example, Japanese Patent Application Laid-Open Nos. Sho 62-84003, 62-87501, 63-63
No. 107901 are disclosed.
However, as an aqueous suspension-type herbicidal composition, none has yet been satisfied, such as formulation stability, herbicidal effect, phytotoxicity to paddy rice, and labor saving of spraying work.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that an aqueous suspended herbicidal composition comprising a poorly water-soluble herbicidal component, a surfactant and water contains paraffinic hydrocarbons. As the composition does not stay locally, it spreads the rice water promptly, so that an even herbicidal effect can be obtained and phytotoxicity to rice can be avoided, the spraying labor can be reduced more, and the preparation can be stored for a long time. It has been found that the formulation has sufficient formulation stability.

[0004] That is, the present invention is an aqueous suspended herbicidal composition characterized by containing a herbicidal component that is hardly soluble in water, a surfactant, a paraffinic hydrocarbon and water. A herbicidal method for a paddy field, characterized in that the herbicidal composition is spread on rice paddy by dropping the herbicidal component in a paddy field impregnated with the composition so that the herbicidal component becomes 1 to 500 g per 10 ares.

Examples of the herbicidal component that is hardly soluble in water used in the present invention include, for example, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-phenacyloxypyrazole (generic name: pyrazoxifene). ), 4- (2,4-
Dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl p-toluenesulfonate (generic name: pyrazolate), 4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethyl-5- (4- Methylphenacyloxy) pyrazole (generic name: benzophenap), 5
-Benzyloxy-4- (2,4-dichlorobenzoyl) -1-methylpyrazole (code No .; NC-3)
10) pyrazole compounds, such as 2,4 Jikurorofu <br/> Eniru -3 '- methoxy - 4' - nitrophenyl ether (common name: Chlomethoxynil), 2,4,6-trichlorophenyl 4 '- nitro Phenyl ether (generic name: chloronitrophen), 2,4-dichlorophenyl -3' -methoxycarbonyl- 4' -nitrophenyl ether (generic name: bifenox), 2,4-dichlorophenyl -4 '- nitrophenyl ether (common name: nitrofen), 2-chloro-4-trifluoromethyl-phenyl-4' - nitro - 3 '- (tetrahydrofuran-3-yloxy) phenyl ether (code N
o. Diphenyl ether compounds such as MT-124); S- (4-chlorobenzyl) -N, N-diethylthiocarbamate (generic name: benthiocarb); S-benzyl-N- (1,2-dimethylpropyl) -N -Ethylthiocarbamate (generic name: esprocarb), S-
(Α, α-dimethylbenzyl) -N, N-pentamethylenethiocarbamate (generic name: dimepiperate), S-
Ethyl-N, N-hexamethylenethiocarbamate (generic name: molinate), O- (3-tert-butylphenyl) -N- (6-methoxypyridin-2-yl)-
Thiocarbamate compounds such as N-methyl thiocarbamate (generic name: pyributicarb); 2-chloro-
2 ', 6'-diethyl-N- (2-propoxyethyl)
Acetanilide (generic name: pretilachlor), N-butoxymethyl-2-chloro-2 ', 6'-diethylacetanilide (generic name: butachlor), 2- (2-naphthyloxy) propionanilide (generic name: naproanilide), 2 -(2,4-dichloro-3-methylphenoxy) propionanilide (generic name: clomeprop),
2 ', 3'-dichloro-4-ethoxymethoxybenzanilide (Code No .; HW-52), cis-N-
[(2-butenooxy) methyl] -2-chloro-2 ',
6'-diethylacetanilide (generic name: butenachlor), 2-chloro-2 ', 6'-diethyl-N-[(3
-Methoxythienyl) methyl] acetanilide (code No .; NSK-850), anilide-based compounds such as N-methyl-2- (2-benzothiazolyloxy) acetanilide (generic name: mefenacet); 2-bromo-N
Amide compounds such as-(α, α-dimethylbenzyl) -3,3-dimethylbutyramide (generic name: bromobutide), N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -5- (2-chloro-2,2-
Difluoroethoxy) -3-methyl-4-isothiazolesulfonamide, 5-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonylaminosulfonyl]
-1-methylpyrazole-4-carboxylic acid ethyl ester (generic name: pyrazosulfuronethyl), 2-[(4,
6-dimethoxypyrimidin-2-yl) aminocarbonylaminosulfonylmethyl] benzoic acid methyl ester (generic name: bensulfuronmethyl), N- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl)- N '-(4,6-dimethoxy-2-pyrimidinyl) urea (code No .; TH-913), 3-
(4,6-dimethoxy-1,3,5-triazine-2-
Sulfonamide compounds such as yl) -1- [2- (2-methoxyethoxy) phenylsulfonyl] urea (generic name: sinosulfuron); 5-tert-butyl-3-
(2,4-dichloro-5-isopropoxyphenyl) -
Oxadiazone-based compounds such as 1,3,4-oxadiazol-2 (3H) -one (generic name: oxadiazone); 4,6-bis (ethylamino) -2-methylthio-
s-Triazine (generic name: simetryn), 2- (1,2
-Dimethylpropylamino) -4-ethylamino-6-
Triazine-based compounds such as methylthio-s-triazine (generic name: dimethamethrin); 2-amino-3-chloro-1,4-naphthoquinone (generic name; ACN:
ACN) and other naphthoquinone compounds; 1- (α, α-
Dimethylbenzyl) -3- (4-methylphenyl) urea (generic name: Daimulon), 3,7-dichloro-8-quinolinecarboxylic acid (generic name: quinclorac), 3-chloro-2- [4-chloro- 2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole (Code No .; S-2
75), 2,3-dihydro-3,3-dimethyl-5-benzofuranylethanesulfonate (generic name: benfresate), S, S-dimethyl 2- (difluoromethyl)
-4- (2-methylpropyl) -6- (trifluoromethyl) -3,5-pyridinedicarbothioate (generic name: dithiopyr), 1- (2-chlorobenzyl) -3-
(Α, α-dimethylbenzyl) urea (Code No .; J
C-940), exo-1-methyl-2- (2-methylbenzyloxy) -4-isopropyl-7-oxabicyclo [2.2.1] heptane (generic name: simmesulin)
In the present invention, at least one selected from this group is used.

Among them, pyrazole compounds, thiocarbamate compounds, anilide compounds, amide compounds,
Solubility of water such as naphthoquinone compounds (25
(° C) is preferably 100 ppm or less, but even if it is more than 100 ppm, it can be used as long as the desired effect is exhibited. The herbicidal component usually has a specific gravity of 1 or more and can be used as a solid or liquid at room temperature. When the herbicidal component is a solid, the herbicidal component generally has an average particle size of 0.5 to 10 μm, and preferably 0.5 to 10 μm, in order to uniformly disperse and suspend it in the formulation water, and to quickly spread it in the paddy water.
Used as fine particles of 5 μm.

The paraffinic hydrocarbons used in the present invention include saturated aliphatic hydrocarbons having 6 to 20 carbon atoms. Among them, the specific gravity is 1 or less (25 ° C.) and the boiling point is 5
Liquid at room temperature of 0 to 350 ° C. is preferred. Specifically, for example, hexane, heptane, octane, decane, undecane, tetradecane, hexadecane, icosane and the like are mentioned, and these also include those having a linear or branched fatty chain structural isomer.

The surfactant used in the present invention imparts hydrophilicity to the herbicidal component. Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene phenyl alkyl aryl ether, polyoxyethylene alkyl aryl ether, and polyoxyethylene styryl phenyl. Ether, polyoxyethylene sorbitan alkylate,
Nonionic surfactants such as polyoxyalkylene glycol, sorbitan alkylate, oxyethylene / oxypropylene block polymer, acetylene glycol; alkyl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene phenyl alkyl aryl ether sulfate, polyoxy Ethylene phenyl alkyl aryl ether phosphate, polyoxyethylene alkyl aryl ether sulfate, alkyl aryl sulfate, alkyl aryl phosphate, alkyl aryl sulfonate, polystyrene sulfonate, lignin sulfonate, naphthalene sulfonate, oxyethylated polyaryl phenol phosphate Triethanolamine salt, β-naph Examples include anionic surfactants such as lensulfonic acid sodium salt formalin condensate and polycarboxylic acid special polymer activator. In the present invention, at least one selected from this group is used. .

The aqueous suspension herbicidal composition of the present invention can be easily produced by adding a paraffinic hydrocarbon to a composition such as a conventional aqueous suspension herbicidal composition. It can be easily produced directly by an ordinary method. For example, a herbicidal component, a surfactant, a paraffin-based hydrocarbon and water are mixed at the same time, and the mixture is wet-pulverized if necessary. And water can be uniformly mixed, and if necessary, can be produced by wet pulverization. However, in industrial practice, generally, a method of simultaneously mixing and wet-pulverizing the four components is simple and advantageous. This wet pulverization is usually performed using a rigid medium having a particle size of 0.1 to 5 mm and using a pulverizer such as a sand mill or a sand grinder. In the production of the herbicidal composition, the types of surfactants and paraffinic hydrocarbons vary depending on the type of herbicidal components, the blending ratio of each component in the whole preparation, etc. You only have to select.

The proportion (weight) of the herbicidal composition differs depending on the purpose of use, the scene of use, the type of each component and the like, and cannot be specified unconditionally.
Part preferably 2 to 35 parts, surfactant 1 to 10 parts desirably 2 to 8 parts, paraffinic hydrocarbon 10 to 40 parts desirably 15 to 40 parts, water 20 to 85 parts desirably 25 to 70 parts. Department. On the other hand, the herbicidal composition of the present invention contains a water-soluble polymer compound such as gum arabic, xanthan gum, carboxymethylcellulose and the like in order to further stabilize the dispersion and suspension of the herbicidal component in the preparation; bentonite, white carbon, calcium carbonate , A solid carrier such as magnesium aluminum silicate; and ethylene glycol to prevent freezing of the preparation under low temperature conditions;
An antifreezing agent such as propylene glycol, glycerin, and urea may be appropriately contained. The herbicidal composition can maintain a state in which the herbicidal component is well dispersed and suspended in the formulation water for a long period of time. Even if it is separated into an oil layer, an aqueous layer, and a solid layer during storage, it can be uniformly dispersed / suspended again by applying a slight vibration, so that there is no problem in applying the drug.

Even when the herbicidal composition of the present invention is dropped on a flooded paddy field, its specific gravity (25 ° C.) is usually 1 or less, preferably 1 to 0.94, and the surface tension is low, for example, 20 to 90. 60 dyne / cm, desirably 20 to 35 dy
Ne / cm (25 ° C.), the substance does not settle or stay at the dropping point of the drug, does not adhere to obstacles such as rice seedlings and weed pieces, and does not adhere to the water surface or It is possible to quickly expand underwater. Then, the herbicidal components are uniformly dissolved in the water or settled on the soil surface and uniformly dispersed. In the present invention, when the herbicidal composition is dropped into a flooded paddy field so that the herbicidal component is 1 to 500 g, preferably 3 to 400 g per 10 ares, an excellent herbicidal effect can be obtained without damaging the rice plant. Can be
For dropping the drug, use a container that discharges a fixed amount, and drop the drug along the ridge or 10 to 100 m ^{2 in} size.
For example, 0.3 to 2 liters and preferably 0.5 to 1.5 liters are applied per 10 ares by dropping each time. Accordingly, the present invention generally relates to a method in which the leaf age of a weed is before germination
The most favorable effect is obtained when applied at the 3 leaf stage, but it is applied to other use periods and use situations unless there is any particular problem in the formulation, medicinal effects, phytotoxicity, spraying work, etc. You can also.

[0012]

EXAMPLES (Formulation Examples) The components used in each formulation example and their abbreviations are described below. The amount of each component used is expressed on a weight basis.

Herbicidal component (A) A-1: 4- (2,4-dichlorobenzoyl) -1,3
-Dimethyl-5-phenacyloxypyrazole A-2: 2-chloro-2 ', 6'-diethyl-N- (2
-Propoxyethyl) acetanilide A-3: 2-chloro-2 ', 6'-diethyl-N-
[(3-methoxythienyl) methyl] acetanilide A-4: 2,3-dihydro-3,3-dimethyl-5-benzofuranylethanesulfonate A-5: 2-amino-3-chloro-1,4-naphthoquinone A-6: 2-Promo-N- (α, α-dimethylbenzyl) -3,3-dimethyl-butyramide A-7: S, S-dimethyl 2- (difluoromethyl)
-4- (2-Methylpropyl) -6- (trifluoromethyl) -3,5-pyridinecarbothioate A-8: O- (3-tert-butylphenyl) -N
-(6-methoxypyridin-2-yl) -N-methyl
Thiocarbamate

Surfactant (B) B-1: polyoxyethylene styryl phenyl ether and alkylaryl sulfonate (trade name, Sorp)
ol-355: manufactured by Toho Chemical Industry) B-2: Oxyethylated polyarylphenol phosphate salt with triethanolamine (trade name,
Soprophor-FL: manufactured by Rhone Poulin) B-3: Acetylene glycol (trade name, Surfin)
B-4: A mixture of alkyl aryl sulfonate, polyoxyethylene alkyl aryl ether sulfate, phosphate, inorganic carbonate, and white carbon (trade name, Sorpol-5146: manufactured by Toho Chemical Industry) B-5 ： Calcium lignin sulfonate

Paraffin hydrocarbon (C) C-1: Isoparaffinic hydrocarbon (trade name, IP Solvent 1620: Idemitsu Petrochemical Co., Ltd.-specific gravity 0.762;
(Flash point: 52 ° C.) C-2: n-hexane C-3: isoparaffinic hydrocarbon (trade name, IP Solvent 2028: Idemitsu Petrochemical Manufacturing Co., specific gravity 0.790;
(Flash point 90 ° C.) C-4: isoparaffinic hydrocarbon (trade name, IP Solvent 2835: Idemitsu Petrochemical Manufacturing Co., specific gravity 0.8820,
(Flash point 140 ° C) C-5: n-paraffinic hydrocarbon (trade name, normal paraffin N-14: manufactured by Nippon Mining Co., Ltd.-specific gravity 0.7)
67, flash point 30 ° C)

Others (D) D-1: Ethylene glycol D-12: Water D-3: Bentonite D-4: Calcium carbonate D-5: Propylene glycol D-6: Magnesium aluminum silicate (Veegum: Vanderbilt) Company manufacture)

Formulation Example 1 Herbicidal component A-1 19.1 parts and A-2 4.8 parts, surfactant B-1 3.0 parts and B-3 1.0 part, paraffinic hydrocarbon C-1 A mixture composed of 25.0 parts and 4.0 parts of the other components D-1 and 43.1 parts of D-2 was mixed with a Dino mill (horizontal ball mill, grinding medium: glass beads having a diameter of 18 mm, filling rate: 80%, Circumferential speed: 15
(m / sec) for 15 minutes to obtain an aqueous suspension. It has a specific gravity of 0.988 and a surface tension (Kyowa CBVP surface tension meter: Kyowa Science Co., Ltd.)
Production) was 28.6 dyne / cm, and the average particle size of the herbicidal component was 1 to 3 μm. It had good storage stability and maintained a uniform dispersion state.

Formulation Examples 2 to 17 The aqueous suspensions prepared according to Formulation Example 1 are shown in Table 1, and the specific gravity and surface tension of each are shown in Table 2. Each of the agents has good storage stability. A uniform dispersion was maintained. The average particle size of the herbicidal components was 1 to 3 μm.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

Comparative Formulation Example Herbicidal component A-1 10.1 parts, other component D-32
5.0 parts, 61.9 parts of D-4, and 1.5 parts of powdered surfactant B-4 were pulverized and mixed.
Kneading water containing 5 parts is added and kneaded and mixed. The kneaded material is extruded and granulated through a 0.8 mm screen, dried, and sized to obtain granules.

[0024] (Test Example) The aqueous paddy field caused tillage in Test Example 1 tractors, granular compound fertilizer as basal _{(N-P 2 O 5 -K} 2 O: 14-10-13) 10
20 kg was applied per a. After that, water was introduced, the tractor was used for scratching, and the two-leaf stage rice seedling (variety: Nipponbare) that had been box-raised was mechanically transplanted. Then, a test section of 3.5 mx 2 m was provided in a continuous manner using a plastic sheet. At the end of the test plot, three tubers of germinated sphagnum moss were planted per plot. Other weeds were spontaneously generated, but all were high.

The depth of flooding was adjusted to 5 to 7 cm, and the aqueous suspension prepared in the above formulation example was added to the center of the test plot at a rate of 1 per 10a.
Liters were dropped. In the comparison section, corresponding to the suspending agent,
Granules prepared by a conventional preparation method (according to the comparative preparation example) were evenly applied to 3 kg per 10a. The leaf age of each weed at the time of chemical treatment was 1-1.2 leaf stage for Nobie, 1-1.5 leaf stage for fireflies and pupae, and 1 leaf stage for Azena and Sphagnum. On the 21st, 35th and 45th days after the chemical treatment, the growth status of paddy rice and weeds was visually observed, and the degree of growth inhibition of the weeds and the degree of phytotoxicity were expressed by the following criteria, and the results in Table 3 were obtained.

Evaluation criteria Degree of growth suppression

Degree of chemical damage Growth rate of paddy rice (compared to untreated plot)

[0028]

[Table 5]

As can be seen from the results of this test, the aqueous suspension of the present invention shows a high herbicidal effect as a whole in the central treatment (local treatment) as well as the uniform treatment of the granules in the comparative section, and shows phytotoxicity to rice. Was not recognized.

Test Example 2 Paddy rice fields were mechanically transplanted by adjusting a paddy field in the same manner as in Test Example 1, and 5 × 6 with a plastic sheet.
The test plot of m. was established, and the tubers of the germinated Spodoptera litura were planted and other weeds spontaneously developed. Flooding depth 5-7cm
And adjusted for drug treatment. In the test plot of the present invention, the aqueous suspension prepared in Formulation Examples 1 and 4 was dropped at a rate of 1 liter per 10a along the central part of each test plot or along a sheet of 5 m on one side. 3kg per 10a of granules prepared by the conventional formulation method corresponding to the suspension
Sprayed uniformly to each. The leaf age of each weed at the time of the chemical treatment was 1.3 to 1.5 leaf stage for the barnyard grass, 1 leaf stage for the corn and 1.5 leaf stage for the horned beetle. On the 30th day after the chemical treatment, the growth status of paddy rice and weeds was visually observed, and the degree of growth inhibition of the weeds and the degree of phytotoxicity were expressed on the same basis as in Test Example 1 above, and the results in Table 4 were obtained.

[0031]

[Table 6]

As can be seen from the results of this test, the aqueous suspension of the present invention showed a high herbicidal effect as a whole in both the central part treatment and the one-side treatment (topical treatment) as well as the uniform treatment of the granules in the control group, and showed phytotoxicity to rice. Was also not recognized.

Test Example 3 The paddy field was adjusted in the same manner as in Test Example 1, and rice seedlings were mechanically transplanted.
m test plots (FIG. 1 described later) were provided, and each weed was naturally generated. The immersion depth was adjusted to 5 to 7 cm, and the aqueous suspension prepared in the above Formulation Example was placed along a sheet of 3 m on one side of the test plot on one side.
One liter per 0a was dropped. The leaf age of each weed at the time of the chemical treatment was as follows: fireflies were in the 1.2 leaf stage, Azena and konagi were at the beginning of development, and Krogwai was in an ungerminated state. On the 41st day after the chemical treatment, the growth status of paddy rice and weeds at the three points X, Y and Z in FIG. 1 was visually observed, and the degree of growth inhibition of weeds and the degree of phytotoxicity were the same as in Test Example 1. And the results in Table 5 were obtained.

[0034]

[Table 7]

As can be seen from the results of this test, the aqueous suspension of the present invention showed a high herbicidal effect on the entire test plot only by one-side treatment (local treatment) of the test plot, and no phytotoxicity to rice was observed.

Test Example 4 A wooden frame test section (FIG. 2) having a length of 6.25 m and a width of 0.75 m and a height of 20 cm was provided in a greenhouse, and paddy soil was uniformly spread on the bottom of the test section. , And two days later, two rows of rice seedlings (variety: Nipponbare) at the two-leaf stage were transplanted at 30 cm between lines. After that, the flooding depth 2-3c
m, and 1.5 min.
When the two-leaf stage is reached, the aqueous suspension prepared in the above Formulation Example is applied dropwise from one side (0.75 m side) of the test plot to a position of 0.25 m at a rate of 1 liter per 10a along the 0.75 m side. did. On the 21st day after the chemical treatment, the growth status of paddy rice and weeds was visually observed at regular intervals from the chemical treatment point, and the degree of growth inhibition of the weeds and the degree of chemical damage were represented by the same criteria as in Test Example 1 above, and were shown in Table 6. The result was obtained.

[0037]

[Table 8]

As can be seen from the results of the tree test, the aqueous suspension of the present invention showed a high herbicidal effect on the entire test plot only by one-side treatment (local treatment) of the test plot, and no phytotoxicity to rice was observed.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a 3 × 17 m paddy field test plot, in which wavy lines indicate locations where chemicals were treated, and X, Y and Z indicate locations where weed growth was visually observed.

FIG. 2 shows a wooden frame test section of 6.25 m in length, 0.75 m in width, and 20 cm in height, and a wavy line shows a point where a drug was treated.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Kazuyuki Maeda 2-3-1 Nishi-Shibukawa, Kusatsu City, Shiga Prefecture Inside the Central Research Laboratory, Ishihara Sangyo Co., Ltd. (72) Yasuhide Kuriyama 2-Chome Nishi-Shibukawa, Kusatsu City, Shiga Prefecture No.3-1 Inside Ishihara Sangyo Co., Ltd. Central Research Laboratory (72) Inventor Hiroshi Yoshii No.3-1 Nishi-Shibukawa 2-chome, Kusatsu-shi, Shiga Prefecture Inside Ishihara Sangyo Co., Ltd. Central Research Laboratory (56) References JP-A-62- 42901 (JP, A) JP-A-55-36458 (JP, A) JP-A-3-173801 (JP, A) JP-B-52-6343 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 25/04 102 A01N 25/00 102

Claims (1)

(57) [Claims] 1. A herbicidal component which is hardly soluble in water, 2 to 40 weights
% , Surfactant 1 to 10% by weight , isoparaffin-based charcoal
Contains 15 to 40% by weight of hydrogen fluoride and 20 to 85% by weight of water
Aqueous herbicidal composition to be applied dropwise to a flooded paddy field .