JPH0952807A - Herbicide composition for paddy field - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of expanding the herbicidal spectrum of a substituted benzoyl cyclic enone derivative and surely controlling major weeds for a long time with a small amount of the derivative by using the derivative with another herbicidal compound in combination. SOLUTION: This herbicidal composition is obtained by compounding a substituted benzoyl cyclic enone derivative of formula I [A is S(O)2 R<1> (R<1> is an alkyl, a cycloalkyl, benzyl, etc.), etc.; B is a halogen, nitro, alkyl, etc.; D is H, an alkyl, an alkoxy, etc.; E is a halogen, an alkoxy, etc.] with a halogen- substituted phenoxy derivative having herbicidal activity. As the halogen- substituted phenoxy derivative, a compound of formula II [X is Cl or F; Y<1> is H, formula III or formula IV; Y<2> is a halogen; Z is an alkyl, a cycloalkyl or a formula V (R<3> is H, an alkyl, etc.)] is preferable. As the compound of formula II, 2,4-dichlorophenyl 4-nitrophenyl ether, etc., is especially preferable. The composition scarcely causes the chemical injury against Oryza sativa.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a herbicide composition for paddy fields, which uses two kinds of herbicidally active compounds in combination. More specifically, it is a pharmaceutical composition showing a synergistic action effect, which comprises a substituted benzoyl cyclic enone derivative having a specific structure and a halogen-substituted phenoxy derivative such as a halogen-substituted diphenyl ether as an active ingredient, and has little phytotoxicity to paddy rice and a small amount. The present invention relates to a herbicide composition for paddy fields which causes the weeds in the paddy fields to die with an applied amount of.

[0002]

2. Description of the Related Art As herbicides for paddy fields, various compounds and admixtures such as phenoxyacetic acid type, diphenyl ether type, carbamate type, heterocyclic type and urea type are known.
However, these herbicides require a relatively large amount of the active ingredient in order to exert a wide and sufficient effect on various kinds of weeds to be applied, and the treatment time, residual efficacy, etc.
In order to meet the demands of paddy rice cultivation in practice, multiple herbicide treatments were required every cultivation season. For this reason,
There are many problems in terms of herbicide cost and labor. The present inventors have previously shown that, when used as a herbicide for paddy fields, it is highly safe for rice, and particularly exhibits excellent effects over a long period of time on weed species of the rice family, the following general formula (I):

[0003]

Embedded image A substituted benzoyl cyclic enone derivative (hereinafter, referred to as “compound A”) represented by (the symbols in the formula have the same meanings as described below) was proposed (JP-A-6-25144).
However, the compound represented by the general formula (I) may not always be expected to have a sufficiently satisfactory effect on the perennial broad-leaved weeds and the millet that have grown.

On the other hand, halogen-substituted phenoxy derivatives such as halogen-substituted diphenyl ethers have been developed as herbicides having high activity against annual weeds before germination and early germination. These are the following formula (II)

[Chemical 6] [In the formula, X represents a chlorine atom or a fluorine atom, and Y ¹
Is a hydrogen atom or

[Chemical 7] Represents a group represented by, Y ² represents a hydrogen atom or a halogen atom, Z represents a lower alkyl group, a cycloalkyl group, or the following formula:

Embedded image (In the group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkyloxycarbonyl group. ) Is represented. ]
It has a structure shown by.

Commercially available herbicide components represented by the general formula (II) include (1) nitrophen (Nitrofen): 2,4-dichlorophenyl-4-nitrophenyl ether (hereinafter referred to as compound B), 2) Chlomethoxynil: 5- (2,
4-dichlorophenoxy) -2-nitroanisole (hereinafter referred to as compound C), (3) chloronitrofen: 4-nitrophenyl-2,4,6-trichlorophenyl ether (hereinafter referred to as compound D) , (4) Bifenox: Methyl 5- (2,4)
-Dichlorophenoxy) -2-nitrobenzoate (hereinafter referred to as compound E), (5) Oxadiazon: 5-tert-butyl-
3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2 (3H) -one (hereinafter referred to as compound F), (6) Pentaxazone: 3N. -(2-Fluoro-4-cyclopentyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (hereinafter referred to as compound G) and the like are known.

Compounds BG are each described in US Pat.
No. 80225, Japanese Patent Publication No. 48-20294, The Pesticide Manual (1
0th Edition) p.185-186, Japanese Patent Publication No. 48-43609, U.S. Pat. No. 3,358,682, and Japanese Patent Laid-Open No. 62-167713. The compound of the general formula (II) is a herbicide showing high activity against annual weeds before and during germination of weeds. The effect on perennial weeds such as that described above is insufficient, the suitable treatment period is narrow, and the residual effect is short, and phytotoxicity to paddy rice is often found. Especially when compounds B to E are used as herbicides for paddy rice, a relatively high dose of 1500 to 2700 g / ha is required,
Lower doses will not give the expected herbicidal activity. As described above, the active compounds of the compound A and the compounds B to G represented by the general formula (I) each have excellent properties, but on the other hand, when used alone, a sufficiently satisfactory herbicidal effect may not be expected. Weeds cannot be completely controlled.

[0007]

In view of the present situation of weed control in paddy rice cultivation, the present invention expands the herbicidal activity spectrum of the compound represented by the general formula (I) proposed by the present inventors. At the same time, it is an object of the present invention to provide a herbicide composition for paddy fields, which can control monocotyledonous and dicotyledonous important weeds accurately and for a long time with a smaller amount of active ingredient.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies on the combined use of the compound A represented by the general formula (I) and other herbicidally active compounds, and as a result, the compound A and the compounds B to G, etc. The mixture with the above compounds showed unexpected and unexpected synergistic effect, and the application of much smaller amount than the use of each single agent could control the important weeds in the paddy field accurately and in a single treatment for a long period of time. The present invention has been completed by finding that it can be used in a wide range of treatment times from the occurrence of weeds to the growing season without causing any damage to the above.

That is, the present invention is: 1) General formula (I)

Embedded image [In the formula, A is an S (O) _n R ¹ group (in the group, R ¹ is (i) an optionally substituted lower alkyl group, (ii) a cycloalkyl group, or (iii) an optionally substituted A good benzyl group, or
(iv) represents a phenyl group which may be substituted with a substituted amino group, and n is 0 or 2. ) Or an OR ² group (wherein R ² represents an optionally substituted phenyl group); B represents a halogen atom, a nitro group, a lower alkyl group or a lower alkylsulfonyl group;
Represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxymethyl group or a lower alkoxycarbonyl group; E represents a halogen atom, an optionally substituted lower alkoxy group, a lower alkylthio group, a lower alkylsulfonyl group or a lower alkyl. Represents a sulfonyloxy group. ] At least one substituted benzoyl cyclic enone derivative represented by and at least one halogen-substituted phenoxy derivative having herbicidal activity are contained as active ingredients, a herbicide composition for paddy fields,

2) The halogen-substituted phenoxy derivative is represented by the general formula (II)

Embedded image [In the formula, X represents a chlorine atom or a fluorine atom, and Y ¹
Is a hydrogen atom or

Embedded image Represents a group represented by, Y ² represents a hydrogen atom or a halogen atom, Z represents a lower alkyl group, a cycloalkyl group, or the following formula:

[Chemical 12] (In the group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkyloxycarbonyl group. ) Is represented. ]
The herbicide composition for paddy field according to 1 above, which is a compound having a herbicidal activity represented by:

3) The compound represented by the general formula (II) is 2,4-dichlorophenyl.4-nitrophenyl ether, 5- (2,4-dichlorophenoxy) -2-nitroanisole, 4-nitrophenyl.2. , 4,6-Trichlorophenyl ether, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, 5-tert-
Butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazole-2 (3
H) -one, 3N- (2-fluoro-4-cyclopentyloxyphenyl) -5-isopropylidene-1,3-
The above-mentioned 1 selected from oxazolidine-2,4-dione
The paddy field herbicidal composition described in 1.

The first active ingredient contained in the paddy herbicide composition of the present invention is a substituted benzoyl cyclic enone derivative represented by the above general formula (I). In the general formula (I), when A represents a —S (O) _n R ¹ group, R ¹
Is any of the following (i) to (iv).

(I) an optionally substituted lower alkyl group. The alkyl backbone preferably contains 1 to 4 carbon atoms. Suitable substituents include lower alkoxycarbonyl groups having 2 to 3 carbon atoms. (ii) Cycloalkyl group, preferably a cycloalkyl group having 3 to 6 carbon atoms. (iii) an optionally substituted benzyl group. Suitable substituents include halogen atoms, methyl groups and nitro groups. Of these substituents, a benzyl group in which 1 to 3 hydrogen atoms are substituted with the same or different groups is preferable. (iv) A phenyl group which may be substituted with a substituted amino group.
Suitable substituted amino groups include 1 to 5 halogen atoms, 1 to 3 lower alkyl groups having 1 to 4 carbon atoms, lower alkoxy groups having 1 to 4 carbon atoms, halomethyl group, nitro group, cyano group. And an amino group substituted with a C1 to C2 alkyl group or an alkylsulfonyl group.

In the general formula (I), when A represents an OR ² group, R ² is an optionally substituted phenyl group. R
Suitable substituents for ² include 1 to 5 halogen atoms and / or lower alkyl groups having 1 to 3 carbon atoms. In general formula (I), B is a halogen atom, a nitro group, a lower alkyl (preferably having 1 to 2 carbon atoms) or a lower alkylsulfonyl group (preferably having 1 to 2 carbon atoms).

D is a hydrogen atom, lower alkyl (preferably having 1 to 2 carbon atoms), lower alkoxy (preferably having 1 to 4 carbon atoms), lower alkoxymethyl (preferably having 1 to 3 carbon atoms) or lower alkoxycarbonyl. A group (preferably having 2 to 5 carbon atoms). E is a halogen atom, optionally substituted lower alkoxy, lower alkylthio (preferably having 1 to 3 carbon atoms), lower alkylsulfonyl or lower alkylsulfonyloxy group (preferably having 1 to 3 carbon atoms), and lower alkoxy and The lower alkylsulfonyl preferably has 1 to 3 carbon atoms and may be substituted with 1 to 3 fluorine atoms.

Among the compounds represented by the above general formula (I), herbicidal activity, herbicidal spectrum, selectivity, water solubility, soil permeability, fish toxicity, balance between stability and disintegration in soil, etc. From the following formula (III)

Embedded image [In the formula, A'is a -S (O) nR ¹¹ group (in the group, R ¹¹ is an unsubstituted phenyl group or 1 to 5 halogen atoms or 1 to 3 carbon atoms of 1 to 4) Represents a phenyl group substituted by an alkyl group, n is 0 or 2); B'represents a halogen atom or a nitro group; D'represents a hydrogen atom; E'represents a halogen atom or 1 ~ Represents a lower alkylsulfonyl group having 1 to 3 carbon atoms, which may be substituted by 3 fluorine atoms. ] The compound represented by the above is particularly preferable.

Specific examples of preferable compounds are as follows. (1) 3- (2-chloro-4-methylsulfonylbenzoyl) -4-phenylthio-bicyclo [3.2.1] oct-3-en-2-one (in the formula (III), A ′ = C ₆ H ₅
S, B '= Cl, D' = H, E '= CH ₃ SO ₂ compound), (2) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (3-methylphenylthio) bicyclo [3.2.1] Oct-3-en-2-one (Formula (III)
_{In, A '= 3-CH 3} C 6 H 4 S, B' = Cl, D '=
H, a compound of E ′ = CH ₃ SO ₂ ), (3) 3- (2-chloro-4-methylsulfonylbenzoyl) -4-phenylsulfonyl-bicyclo [3.2.1] oct-3-ene-2 -ON (in the formula (III), A ′ = C ₆ H ₅ SO ₂ , B ′
= Cl, D '= H, E' = CH ₃ SO ₂ compound),
(4) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (2,6-dimethylphenylthio) -bicyclo [3.2.1] oct-3-en-2-one (formula (II
In I), A '= 2,6- ( CH 3) 2 C 6 H 3 S, B'
= Cl, D '= H, E' = CH ₃ SO ₂ compound),

(5) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (3-chlorophenylthio)-
Bicyclo [3.2.1] at oct-3-en-2-one (Formula (III), A '= 3 -ClC 6 H 4 S, B' = C
l, D '= H, E ' = a compound of _{CH 3 SO 2), (6} ) 3-
(2-Nitro-4-methylsulfonylbenzoyl) -4
-(2,6-Dimethylphenylthiobicyclo) [3.
2.1] Oct-3-en-2-one (in the formula (III),
_{A '= 2,6- (CH 3)} 2 C 6 H 3 S, B' = N
O ₂ , D ′ = H, E ′ = CH ₃ SO ₂ ), (7)
3- (2-nitro-4-methylsulfonylbenzoyl)
-4- (2,6-dichlorophenylthiobicyclo)-
[3.2.1] Oct-3-en-2-one (Formula (III)
In, A '= 2,6- (Cl) 2 C 6 H 3 S, B' = NO
₂ , D ′ = H, E ′ = CH ₃ SO ₂ compound), (8) 3
-(2-Nitro-4-methylthiobenzoyl) -4-
(3-Chlorophenylthiobicyclo)-[3.2.1]
Oct-3-en-2-one (in formula (III), A ′ = 3-
ClC ₆ H ₄ S, B '= NO ₂ , D' = H, E '= CH
₃ Compound of S), (9) 3- (2-chloro-4-methylsulphonyl benzoyl) -4- (2,6-dichlorophenyl Ji Obi cyclo) - [3.2.1] oct-3-ene -
2-one (in formula (III), A ′ = 2,6- (Cl) ₂ C _{6
H 3 S, B '= Cl} , D' = H, compounds of the _{E '= CH 3 SO 2)} . These compounds can be synthesized by the method described in JP-A-6-25144.

The second active ingredient contained in the composition of the present invention is at least one halogen-substituted phenoxy derivative compound having herbicidal activity. Examples of such halogen-substituted phenoxy derivative compounds include compounds having the herbicidal activity represented by the general formula (II). Specific examples include the above compounds B to G.

The herbicide composition for paddy fields according to the present invention is a mixture of the above-mentioned first component and second component. In general, a synergistic effect is that the herbicidal activity by mixing drug compounds is greater than the simple sum of the activities of the individual compounds (expected activity). The activity expected for a particular combination of two herbicides can be calculated as follows (calculation of synergistic and antagonistic responses of the Colby SR herbicide combination "Weed" 15: 20-22. See page 1967.).

[0021]

E = α + β−α · β ÷ 10 α: evaluation value of inhibition when herbicide A is applied at an amount of akg / ha β: evaluation value of inhibition when herbicide B is applied at an amount of bkg / ha Value E: Inhibition evaluation value expected when herbicide A is used in an amount of akg / ha and herbicide B is used in an amount of bkg / ha.

If the actual suppression evaluation value is larger than the theoretical value E calculated by the above formula, it means that the effect is more than the mere sum of the individual herbicidal activities. That is, it can be said that a synergistic effect due to the combination is recognized. As will be described later, the weed suppression rate of the composition of the present invention is larger than the theoretical value for various weeds, and a synergistic herbicidal effect on a wide variety of weeds is recognized. Also,
Even when the application of only one of the components is small, the effect is small, and a large amount of the drug is required to obtain a sufficient effect, and as a result, phytotoxicity to rice is inevitable,
When the composition of the present application is used, a sufficient effect can be obtained at an application rate that does not substantially cause phytotoxicity to rice.

The combination of the substituted benzoyl cyclic enone derivative (first component) and the harrigen-substituted phenoxy derivative compound (second component) in the composition of the present invention is a novel one not described in the literature, and of course its specific There is no literature that mentions potentiation. The synergism according to the invention is observed over a wide range of mixing ratios. 0.5 parts of the second component compound is added to 1 part by weight of the first component compound represented by the general formula (I).
˜20 parts by weight, preferably 1: 1 to 1:10 parts by weight, can be mixed to obtain useful herbicides. Each of the first component and the second component may be a single type of compound or a combination of a plurality of compounds.

The herbicidal composition of the present invention is generally used by formulating it into a form convenient for use according to a conventional method for agricultural chemicals. That is, each of the above active ingredients is mixed with an appropriate inert carrier and, if necessary, together with an auxiliary in an appropriate ratio and dissolved, separated, suspended, mixed, impregnated, adsorbed or adhered, or Mixed with an appropriate propellant, etc., in an appropriate dosage form, for example, a suspension, an emulsion, a solution, a wettable powder,
It can be formulated into powders, granules, tablets, flowables, aerosols and the like. The auxiliary agent may contain a necessary amount of a surfactant, an inert carrier, a binder, a decomposition inhibitor, a colorant, various agricultural chemicals, and the like. These components are not particularly limited as long as they are used in the conventional agricultural chemical formulation field.

Surfactants, for example, serve the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compounds. Specific examples thereof include lignin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, alkyl aryl sulfonate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene. Anionic surfactants such as styrylphenyl ether sulphate, lauryl sulfate, polycarboxylic acid type polymer surfactants, polyoxyethylene alkylallyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene Alkyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan alkylate
And nonionic surfactants such as polyoxyethylene polyoxypropylene block polymer, sucrose fatty acid ester, and polyethylene glycol. These surfactants may be used alone or in combination of two or more, and the mixing ratio in that case can be arbitrarily selected.

The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include, for example, soybean flour, cereal flour, wood flour, bark flour, saw powder, tobacco stem flour, walnut flour, bran, fiber powder, plant powder such as residue after extraction of plant extract, and the like. Fiber products such as paper, cardboard, sieving; synthetic polymers such as crushed synthetic resins; clays (eg kaolin, bentonite, acid clay), talcs (eg talc, hirophyllite), silicas (eg diatomaceous earth, Quartz sand, mica,
White carbon [Synthetic high-dispersion silicic acid which is also called hydrous fine silicon powder or hydrous silicic acid. Some products contain calcium silicate as a main component depending on the product. ]), Activated carbon, sulfur powder, pumice, calcined diatomaceous earth, brick crushed material, fly ash, sand, calcium carbonate, calcium phosphate, inorganic mineral powders such as pearlite; sodium carbonate, sodium hydrogen carbonate, calcium carbonate, sodium sulfate, citric acid And water-soluble powders such as succinic acid, fumaric acid, lactose, fructose, and glucose; and chemical fertilizers such as ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, and salt ammonium, and compost. These may be used alone or in the form of a mixture of two or more kinds.

The material which can be a liquid carrier is selected from those having solvent ability per se, and those having no solvent ability but capable of dispersing the active ingredient compound with the aid of an auxiliary agent. Water, alcohols (eg ethanol, methanol, isopropanol, butanol, ethylene glycol), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone). Ethers (eg ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran), aliphatic hydrocarbons (eg gasoline, mineral oil), aromatic hydrocarbons (eg benzene, toluene, xylene, solvent naphtha, alkylnaphthalene) , Halogenated hydrocarbons (eg dichloroethane, chlorinated benzene, chloroform, carbon tetrachloride), esters (eg ethyl acetate, dibutyl phthalate, diisopropyl phthalate, dioctyl phthalate), acid amides (eg dimethylformamide, diethylformamide dimethylacetamide) ), Nitriles (for example, acetonitrile), dimethyl sulfoxide, and the like. These may be used alone or in the form of a mixture of two or more kinds.

The following may be mentioned as other auxiliary agents. These auxiliary agents are used depending on the purpose. For the purpose of dispersion stabilization, adhesion and / or binding of active ingredient compounds, the following may be used, for example: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine root. Oil, sugar oil, bentonite, lignin sulfonate and the like can be mentioned.

To improve the fluidity of the solid product, for example, waxes, stearates, alkyl phosphates and the like can be used. As the peptizer for the suspension product, for example, naphthalenesulfonic acid condensate, condensed phosphoric acid and the like can be used. It is also possible to add an antifoaming agent such as silicone oil.

In the composition of the present invention, the compounding amount of the active ingredient can be adjusted according to need. In the case of powder or granules, as the total amount of the first component and the second component, usually,
0.2 to 20% by weight, and 0.1 to 50% by weight is suitable when it is used as an emulsion or wettable powder. The application rate of the mixture thus obtained is 0 as the active ingredient amount of the mixture.
It can be used in a wide range of 01kg-5kg / ha,
Standard use is preferably in the range of 0.05 to 1 kg / ha. The herbicidal composition according to the present invention can be applied at any time in a wide range of the growing season before the occurrence of weeds, and a high effect can be obtained. The herbicidal composition according to the present invention can be used in combination with one or more other herbicides, pesticides such as insecticides, fungicides, plant growth regulators, soil improvement materials or fertilizers. Of course, it is also possible to co-formulate with these, and in some cases, a synergistic effect can be expected. In particular, it may be desirable to use other herbicides together in order to further improve the effect of the herbicide.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples (formulation examples, test examples), but the compounds, dosage amounts, dosage forms and the like in the present invention are not limited thereto. In the following description, the first component compound means a substituted benzoyl cyclic enone derivative represented by the general formula (I), and the second component compound means a halogen-substituted phenoxy derivative compound. Compounds A-No. 1 to A-No. 6 shown in Table 1 below were used as the first component compounds. The compounds BG described above were used as the second component compound. In addition,
“Parts” all mean parts by weight.

[0032]

[Table 1]

Formulation Example 1: Wettable powder

The Table 2] Table 2 Ingredients ratio Compound A-No.1 10 parts Compound E 30 parts alkylbenzenesulfonate sodium 2.0 parts naphthalenesulfonic acid formalin condensate sodium salt 3.0 parts of white carbon 3.0 parts Clay 52 parts The above ingredients A wettable powder was obtained by uniformly mixing and pulverizing.

Formulation 2: wettable powder

TABLE 3 uniformly to Table 3 Ingredient ratio Compound A-No.2 10 parts Compound F 20 parts alkylbenzenesulfonate sodium 2.0 parts of naphthalenesulfonic acid formalin condensate sodium 3.0 parts of white carbon 3.0 parts Clay 62 parts The above ingredients The mixture was pulverized to obtain a wettable powder.

Formulation Example 3: Granule

TABLE 4 uniform Table 4 Ingredient Percentage Compound A-No.1 1 part compound G 0.9 parts Bentonite 33 parts Clay 61.6 parts sodium dioctyl sulfosuccinate 0.5 parts polycarboxylic acid type polymer-active agent 3.0 parts The above ingredients The mixture was mixed and pulverized, and then a small amount of water was added, and the mixture was kneaded with stirring, granulated by an extrusion-type granulator, and dried to give granules.

Formulation Example 4: Granule

TABLE 5 uniform Table 5 Ingredient Percentage Compound A-No.2 1 part Compound E 4 parts Bentonite 30 parts Clay 61.5 parts sodium dioctyl sulfosuccinate 0.5 parts polycarboxylic acid type polymer-active agent 3.0 parts The above ingredients The mixture was mixed and pulverized, and then a small amount of water was added, and the mixture was kneaded with stirring, granulated by an extrusion-type granulator, and dried to give granules.

Formulation Example 5: Suspending agent

[Table 6] were mixed Table 6 Ingredient Percentage Compound A-No.4 1 part Compound G 1 parts of polyoxyethylene styryl phenyl ether 3 parts sodium dioctyl sulfosuccinate 0.5 parts modified silicone 0.3 parts Water 79.2 parts The above ingredients The product was wet pulverized, 15 g of a 2% xanthan gum aqueous solution was added to this suspension, and the mixture was stirred and mixed to obtain 100 g of a suspension composition.

Formulation 6: Suspension

Table 7 were mixed Table 7 Ingredients Percentage Compound A-No.4 1 part compound E 1.5 parts of polyoxyethylene styryl phenyl ether 3 parts sodium dioctyl sulfosuccinate 0.5 parts modified silicone 0.3 parts Water 78.7 parts The above ingredients The product was wet pulverized, 15 g of a 2% xanthan gum aqueous solution was added to this suspension, and the mixture was stirred and mixed to obtain 100 g of a suspension composition.

Test Example 1: Flooded soil treatment pot test (weeds
Pre-occurrence treatment) Wagner pot of 1/2000 aal is filled with alluvial soil,
The water depth was kept at 3 cm after the water entry. The next day, after embedding Kurogui and Urikawa tubers to a depth of 3 cm,
Mixed seeds of Thai barley and firefly were sown at a depth of 1 cm from the soil surface layer, and eel seeds and Cyperus tuber tubers were placed on the soil surface. Furthermore, rice plant seedlings (cultivar Koshihikari) at the 2.5 leaf stage were transplanted at a depth of 3 cm by one plant per plant. In the chemical treatment, a predetermined amount of the wettable powder manufactured according to Formulation Example 1 was diluted to 2 ml of water 3 days after sowing, and the water surface was dropped with a pipette so as to be uniform in the pot. Water leakage of 3 cm per day was performed for 3 days from the day after the treatment. The test was performed in a glass greenhouse at 23 to 30 ° C. In the survey, general conditions were observed 30 days after the drug treatment, and the herbicidal effect and phytotoxicity were evaluated. The results are shown in Tables 9 to 16. The criteria for determining the herbicidal effect and the phytotoxicity in the table and the meanings of the abbreviations are as follows. The theoretical value is Colb
It is a value calculated by the formula of y. Criteria for herbicidal effect and phytotoxicity:

[0040]

Table 8 Table 8 Numerical herbicidal effect crop phytotoxicity 10 Yasomosomo Kusaritsu 96% or more damage rate of 96% or more 9 〃 86-95% 〃 86-95% 8 〃 76-85% 〃 76-85% 7 〃 66 to 75% 〃 66 to 75% 6 〃 56 to 65% 〃 56 to 65% 5 〃 46 to 55% 〃 46 to 55% 4 〃 36 to 45% 〃 36 to 45% 3 〃 26 to 35% 〃 26 to 35 % 2 〃 16-25% 〃 16-25% 1 〃 6-15% 〃 6-15% 0 〃 5% or less Harmless

Abbreviations in Tables 9 to 16: E. C. : Tainubie, S. J. : Firefly, M.
V. : Konagi, C.I. S. : Mizugayatsuri, E. K. :
Kurogwai, S.K. P. : Urikawa, ABL: Annual broadleaf weed, O. S. : Transplanted rice.

[0042]

[Table 9]

[0043]

[Table 10]

[0044]

[Table 11]

[0045]

[Table 12]

[0046]

[Table 13]

[0047]

[Table 14]

[0048]

[Table 15]

[0049]

[Table 16]

Test Example 2: Flooded soil treatment pot test (weeds
Growing season treatment) Alluvial soil was filled in a Wagner pot of 1/2000 aal, and the water depth was kept at 3 cm after water-filling. Next day, tubers of Kurokawai and Urikawa were embedded at a depth of 3 cm, and Tainubie and firefly were mixed-layer sown to a depth of 1 cm from the soil surface layer, and eel seeds and Spodoptera litura tubers were placed on the soil surface. Further, four 2.5-leaf rice seedlings (variety Koshihikari) were transplanted at a depth of 3 cm per plant. The chemical treatment was carried out 7 days after sowing, with a prescribed amount of the wettable powder produced in accordance with Formulation Examples 1 and 2 at the time of 1.5 leaf stage of the seaweed, 2 ml of water.
The mixture was diluted with water, and the water was added dropwise to the surface of the pot with a pipette. Water leakage of 3 cm per day was performed for 3 days from the day after the treatment. On the 30th day after the drug treatment, the herbicidal effect and the phytotoxicity were generally observed according to the criteria shown below.
The test was performed in a glass greenhouse at 23 to 30 ° C.
The results are shown in Tables 17 to 24 (the criteria for the herbicidal effect and the phytotoxicity and the meanings of the abbreviations in Tables 9 to 1 are shown.
6 Same as table).

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

[Table 19]

[0054]

[Table 20]

[0055]

[Table 21]

[0056]

[Table 22]

[0057]

[Table 23]

[0058]

[Table 24]

Test Example 3: Flooded soil treatment field test (from weeds)
(Prenatal treatment) The paddy field was divided into 1 m ² square sections with a plastic plate, and seeds were sown at the same time as shavings.
After the leveling of the rice field, five Kurowai and Urikawa tubers were placed on the soil surface at a depth of 3 cm. One week later, rice seedlings of the 2.5 leaf stage (variety: Koshihikari) were planted as two plants per strain. 3 days after rice planting,
A predetermined amount of the granules produced according to Formulation Example 4 was sprayed from the time before the emergence of weeds to the time of 0.5 leaf stage of Laminaria. The test site was in the northeastern part of Kan, the soil type was clay loam, and the water depth was 1.5 cm / day. The test was conducted from the beginning of May. Survey 3 after drug treatment
The amount of residual grass was measured on the 0th day and the 56th day, the ratio of untreated plots was determined, and the above-mentioned criteria were evaluated. The results are shown in Tables 25 to 28 (the criteria for the herbicidal effect and phytotoxicity and the meanings of the abbreviations in the tables are the same as those in Tables 9 to 16).

[0060]

[Table 25]

[0061]

[Table 26]

[0062]

[Table 27]

[0063]

[Table 28]

[0064]

[Table 29]

[0065]

[Table 30]

[0066]

[Table 31]

[0067]

[Table 32]

Test Example 4: Flooded soil treatment test (field test) The paddy field was divided into 1 m ² squares by a plastic plate, and seeds of the genus Nubie and firefly were sown at the same time as the substituting.
After the leveling of the field, five tubers of Kurokawai, Urikawa, and Shizui were placed on the soil surface at a depth of 3 cm. One week later, rice seedlings (cultivar Koshihikari) at the 2.5 leaf stage were planted as two rice plants per strain. One week after rice planting, a predetermined amount of the suspension prepared according to Formulation Example 6 at the time of the leaf-ear (Nobie) 1.5-2 leaf stage was uniformly dropped into the test plots with a pipette. The test site was in the northeastern part of Kanto, the soil type was clay loam, and the water depth was 1.5 cm / day. The test was conducted in the middle of June. In the survey, the amount of residual grass was measured 30 days after the chemical treatment, the ratio of untreated plots was calculated, and the above-mentioned criteria were evaluated. The results are shown in Tables 29 to 32. Further, the state of suppression of growth of weeds on the 56th day after the chemical treatment is described in the column of the 56th day in the table (the criteria for the herbicidal effect and the phytotoxicity and the meaning of the abbreviations in the table are the same as those in Tables 9 to 16). .

[0069]

[Table 33]

[0070]

[Table 34]

[0071]

[Table 35]

[0072]

[Table 36]

[0073]

[Table 37]

[0074]

[Table 38]

[0075]

[Table 39]

[0076]

[Table 40]

As shown in the above Test Examples 1, 2, 3, and 4, the herbicidal composition according to the present invention was able to produce perennial weeds in a wide range from before rice planting to the weed growth period without damaging rice. We were able to control the important weeds of the paddy field including the rice field accurately. That is, in the herbicidal composition of the present invention, the herbicidal spectrum is expanded by the complementary action of the mixture.
Further, from these results, a mixture containing at least one kind of the compounds represented by the general formula (I) and a halogen-substituted phenoxy derivative compound-based herbicide component,
It can be seen that the effects of each single drug show a significant synergistic effect that is unexpected. That is, the herbicidal effect is superior to that of each single agent, and as a result of exhibiting such a synergistic effect, a smaller dose than in the case of using each compound alone to obtain an equivalent effect It can be used. Furthermore, the herbicidal composition according to the present invention shows a remarkable effect even when applied at any time from the weed development stage to the weed growth period, and almost completely controls important weeds in paddy fields by one treatment. Yes, for 8 weeks (5
(6 days) or longer, showing a weed-control effect.

[0078]

The paddy field herbicidal composition of the present invention has a broad range of herbicidal spectrum including monocots, dicots, annuals and perennials. In addition, due to the synergistic effect of the drug components, the target weeds can be properly weeded by using a small amount without causing phytotoxicity to rice. Moreover, by extending the residual effect period, weed control can be realized throughout a period important for rice growth by one application. Therefore, labor and cost required for spraying the herbicide can be greatly reduced. Also,
In recent years, along with the spread of herbicide for weed control type paddy field, transition of paddy field weed species has occurred, and the occurrence expansion of difficult-to-control weeds resulting from this has been reported in various places, but the herbicidal composition of the present invention is ,
Since it has a broad spectrum of weeding and can control important weeds accurately over a long period of time, it can contribute to solving the problems caused by the transition of such weed species.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 13, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Title of invention Herbicidal composition for paddy field

[Claims]

Embedded image [In the formula, A is an S (O) _n R ¹ group (in the group, R ¹ is (i) an optionally substituted lower alkyl group, (ii) a cycloalkyl group,
(iii) optionally substituted benzyl group, or (iv) substituted amino group, phenyl optionally substituted with 1 to 5 halogen atoms or 1 to 3 alkyl groups having 1 to 4 carbon atoms Represents a group, and n is 0 or 2. )
Or an OR ² group (in which R ² represents an optionally substituted phenyl group); B represents a halogen atom, a nitro group, a lower alkyl group or a lower alkylsulfonyl group; and D represents a hydrogen atom, Represents a lower alkyl group, a lower alkoxy group, a lower alkoxymethyl group or a lower alkoxycarbonyl group; E represents a halogen atom, an optionally substituted lower alkoxy group, a lower alkylthio group, a lower alkylsulfonyl group or a lower alkylsulfonyloxy group; Represent. ] At least one kind of substituted benzoyl cyclic enone derivative and at least one kind of halogen-substituted phenoxy derivative having herbicidal activity (provided that 3N- (2-fluoro-4-cyclopentyloxyphenyl) -5-isopropylidene-1) , 3-oxazolidine-2,4-dione) is contained as an active ingredient in the herbicide composition for paddy field.

Embedded image [In the formula, X represents a chlorine atom or a fluorine atom, and Y ¹
Is a hydrogen atom or

Embedded image Represents a group represented by, Y ² represents a hydrogen atom or a halogen atom, Z represents a lower alkyl group, a cycloalkyl group, or the following formula:

Embedded image (In the group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkyloxycarbonyl group. ) Is represented. ]
The herbicidal composition for paddy fields according to claim 1, which is a compound having a herbicidal activity represented by:

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a herbicide composition for paddy fields, which uses two kinds of herbicidally active compounds in combination. More specifically, it is a pharmaceutical composition showing a synergistic action effect, which comprises a substituted benzoyl cyclic enone derivative having a specific structure and a halogen-substituted phenoxy derivative such as a halogen-substituted diphenyl ether as an active ingredient, and has little phytotoxicity to paddy rice and a small amount. The present invention relates to a herbicide composition for paddy fields which causes the weeds in the paddy fields to die with an applied amount of.

[0002]

2. Description of the Related Art As herbicides for paddy fields, various compounds and admixtures such as phenoxyacetic acid type, diphenyl ether type, carbamate type, heterocyclic type and urea type are known.
However, these herbicides require a relatively large amount of the active ingredient in order to exert a wide and sufficient effect on various kinds of weeds to be applied, and the treatment time, residual efficacy, etc.
In order to meet the demands of paddy rice cultivation in practice, multiple herbicide treatments were required every cultivation season. For this reason,
There are many problems in terms of herbicide cost and labor. The present inventors have previously shown that, when used as a herbicide for paddy fields, it is highly safe for rice, and particularly exhibits excellent effects over a long period of time on weed species of the rice family, the following general formula (I):

[0003]

Embedded image A substituted benzoyl cyclic enone derivative (hereinafter, referred to as "compound A") represented by (the symbols in the formula have the same meanings as described below) was proposed (JP-A-6-25144).
However, the compound represented by the general formula (I) may not always be expected to have a sufficiently satisfactory effect on perennial broad-leaved weeds and noviae that have advanced in growth.

On the other hand, halogen-substituted phenoxy derivatives such as halogen-substituted diphenyl ethers have been developed as herbicides having high activity against annual weeds before germination and early germination. These are the following formula (II)

[Chemical 6] [In the formula, X represents a chlorine atom or a fluorine atom, and Y ¹
Is a hydrogen atom or

[Chemical 7] Represents a group represented by, Y ² represents a hydrogen atom or a halogen atom, Z represents a lower alkyl group, a cycloalkyl group, or the following formula:

Embedded image (In the group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkyloxycarbonyl group. ) Is represented. ]
It has a structure shown by.

Commercially available herbicide components represented by the general formula (II) include (1) Nitrofen: 2,4-dichlorophenyl-4-nitrophenyl ether (hereinafter referred to as compound B), ( 2) Chlomethoxynil: 5- (2,4)
-Dichlorophenoxy) -2-nitroanisole (hereinafter referred to as compound C), (3) chloronitrofen: 4-nitrophenyl-2,4,6-trichlorophenyl ether (hereinafter referred to as compound D), (4) Bifenox: Methyl 5- (2,4-
Dichlorophenoxy) -2-nitrobenzoate (hereinafter referred to as compound E), (5) Oxadiazon: 5-tert-butyl-
3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2 (3H) -one (hereinafter referred to as compound F) and the like are known.

Compounds BF are described in US Pat.
080,225, Japanese Patent Publication No. 48-20294, The Pesticide Manual
(10th Edition) p.185-186, Japanese Patent Publication No. 48-43609, and U.S. Pat. No. 3,385,862. The compound of the general formula (II) is a herbicide showing high activity against annual weeds before and during the initial germination of weeds. The effect on perennial weeds such as the above is not sufficient, the suitable treatment period is narrow, and the residual effect is short, and phytotoxicity to paddy rice is often found. Especially when compounds B to E are used as herbicides for paddy rice, 1500 to 2700
It requires a relatively high dose of g / ha, and lower doses do not provide the expected herbicidal activity. Thus, the compound A and compounds B to F represented by the general formula (I)
Each active compound of, while having excellent characteristics, respectively,
When used alone, it may not be possible to expect a fully satisfactory herbicidal effect, and it is not possible to completely control all weeds.

[0007]

In view of the present situation of weed control in paddy rice cultivation, the present invention expands the herbicidal activity spectrum of the compound represented by the general formula (I) proposed by the present inventors. At the same time, it is an object of the present invention to provide a herbicide composition for paddy fields, which can control monocotyledonous and dicotyledonous important weeds accurately and for a long time with a smaller amount of active ingredient.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the combined use of the compound A represented by the general formula (I) and other herbicidally active compounds, and as a result, have shown that the compound A and the compounds B to F, etc. The mixture with the above compounds showed unexpected and unexpected synergistic effect, and the application of much smaller amount than the use of each single agent could control the important weeds in the paddy field accurately and in a single treatment for a long period of time. The present invention has been completed by finding that it can be used in a wide range of treatment times from the occurrence of weeds to the growing season without causing any damage to the above.

That is, the present invention is: 1) General formula (I)

Embedded image [In the formula, A is an S (O) _n R ¹ group (in the group, R ¹ is (i) an optionally substituted lower alkyl group, (ii) a cycloalkyl group,
(iii) optionally substituted benzyl group, or (iv) substituted amino group, phenyl optionally substituted with 1 to 5 halogen atoms or 1 to 3 alkyl groups having 1 to 4 carbon atoms Represents a group, and n is 0 or 2. )
Or an OR ² group (in which R ² represents an optionally substituted phenyl group); B represents a halogen atom, a nitro group, a lower alkyl group or a lower alkylsulfonyl group; and D represents a hydrogen atom, Represents a lower alkyl group, a lower alkoxy group, a lower alkoxymethyl group or a lower alkoxycarbonyl group; E represents a halogen atom, an optionally substituted lower alkoxy group, a lower alkylthio group, a lower alkylsulfonyl group or a lower alkylsulfonyloxy group; Represent. ] At least one kind of substituted benzoyl cyclic enone derivative and at least one kind of halogen-substituted phenoxy derivative having herbicidal activity (provided that 3N- (2-fluoro-4-cyclopentyloxyphenyl) -5-isopropylidene-1) , 3-oxazolidine-2,4-dione) and as an active ingredient, a herbicide composition for paddy field,

2) The halogen-substituted phenoxy derivative is represented by the general formula (II)

Embedded image [The symbols in the formulas have the same meanings as described above. ] The herbicide composition for paddy fields according to 1 above, which is a compound having herbicidal activity,

3) The compound represented by the general formula (II) is 2,4-dichlorophenyl-4-nitrophenyl ether, 5- (2,4-dichlorophenoxy) -2-nitroanisole, 4-nitrophenyl-2, 4,6-Trichlorophenyl ether, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3 The paddy field herbicide composition as described in 2 above, which is selected from 4,4-oxadiazol-2 (3H) -one.

The first active ingredient contained in the paddy herbicide composition of the present invention is a substituted benzoyl cyclic enone derivative represented by the above general formula (I). In formula (I), when A represents -S (O) _n R ¹ groups, R ¹ is either following the (i) ~ (iv).

The first active ingredient contained in the paddy herbicide composition of the present invention is a substituted benzoyl cyclic enone derivative represented by the above general formula (I). In formula (I), when A represents -S (O) _n R ¹ groups, R ¹ is either following the (i) ~ (iv).

(I) an optionally substituted lower alkyl group. The alkyl backbone preferably contains 1 to 4 carbon atoms. Suitable substituents include lower alkoxycarbonyl groups having 2 to 3 carbon atoms. (ii) Cycloalkyl group, preferably a cycloalkyl group having 3 to 6 carbon atoms. (iii) an optionally substituted benzyl group. Suitable substituents include halogen atoms, methyl groups and nitro groups. Of these substituents, a benzyl group in which 1 to 3 hydrogen atoms are substituted with the same or different groups is preferable. (iv) Substituted amino group, 1 to 5 halogen atoms or 1
A phenyl group which may be substituted with an alkyl group having 3 to 4 carbon atoms. Suitable substituted amino groups include 1 to 5 halogen atoms, 1 to 3 carbon atoms of 1 to 4
A lower alkyl group, a lower alkoxy group having 1 to 4 carbon atoms, a halomethyl group, a nitro group, a cyano group, and / or an amino group substituted with an alkyl group having 1 to 2 carbon atoms or an alkylsulfonyl group. .

In the general formula (I), when A represents an OR ² group, R ² is an optionally substituted phenyl group. R ²
Suitable examples of the substituent include a halogen atom having 1 to 5 atoms and / or a lower alkyl group having 1 to 3 carbon atoms. In general formula (I), B is a halogen atom, a nitro group, a lower alkyl (preferably having 1 to 2 carbon atoms) or a lower alkylsulfonyl group (preferably having 1 to 2 carbon atoms).

D is a hydrogen atom, lower alkyl (preferably having 1 to 2 carbon atoms), lower alkoxy (preferably having 1 to 4 carbon atoms), lower alkoxymethyl (preferably having 1 to 3 carbon atoms) or lower alkoxycarbonyl. A group (preferably having 2 to 5 carbon atoms). E is a halogen atom, optionally substituted lower alkoxy, lower alkylthio (preferably having 1 to 3 carbon atoms), lower alkylsulfonyl or lower alkylsulfonyloxy group (preferably having 1 to 3 carbon atoms), and lower alkoxy and The lower alkylsulfonyl preferably has 1 to 3 carbon atoms and may be substituted with 1 to 3 fluorine atoms.

Among the compounds represented by the above general formula (I), herbicidal activity, herbicidal spectrum, selectivity, water solubility, soil permeability, fish toxicity, balance between stability and disintegration in soil, etc. From the following formula (III)

Embedded image [In the formula, A ′ represents a —S (O) _n R ¹¹ group (in the group, R ¹¹ represents an unsubstituted phenyl group or 1 to 5 halogen atoms or 1 to 3 carbon atoms of 1 to 4). Represents a phenyl group substituted by an alkyl group, n is 0 or 2); B'represents a halogen atom or a nitro group; D'represents a hydrogen atom; E'represents a halogen atom or 1 ~ Represents a lower alkylsulfonyl group having 1 to 3 carbon atoms, which may be substituted by 3 fluorine atoms. ] The compound represented by the above is particularly preferable.

Specific examples of preferable compounds are as follows. (1) 3- (2-chloro-4-methylsulfonylbenzoyl) -4-phenylthio-bicyclo [3.2.1] oct-3-en-2-one (in formula (III), A ′ = C ₆ H
₅ S, B '= Cl, D' = H, E '= CH ₃ SO ₂ ),

(2) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (3-methylphenylthio) bicyclo [3.2.1] oct-3-en-2-one (formula (II
In I), A '= 3- CH 3 C 6 H 4 S, B' = Cl, D '=
H, compounds of the _{E '= CH 3 SO 2)} ,

(3) 3- (2-chloro-4-methylsulfonylbenzoyl) -4-phenylsulfonyl-bicyclo [3.2.1] oct-3-en-2-one (formula (III)
Where A ′ = C ₆ H ₅ SO ₂ , B ′ = Cl, D ′ = H, E ′
= CH ₃ SO ₂ compound),

(4) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (2,6-dimethylphenylthio)-
In bicyclo [3.2.1] oct-3-en-2-one (Formula (III), A '= 2,6- (CH 3) 2 C 6 H 3 S, B' = C
1, D ′ = H, E ′ = CH ₃ SO ₂ compound),

(5) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (3-chlorophenylthio) -bicyclo [3.2.1] oct-3-en-2-one (formula (II
In I), A '= 3- ClC 6 H 4 S, B' = Cl, D '=
H, compounds of the _{E '= CH 3 SO 2)} ,

(6) 3- (2-nitro-4-methylsulfonylbenzoyl) -4- (2,6-dimethylphenylthio)-
Bicyclo [3.2.1] at oct-3-en-2-one (Formula (III), A '= 2,6- (CH 3) 2 C 6 H 3 S, B' = N
O ₂ , D ′ = H, E ′ = CH ₃ SO ₂ compound),

(7) 3- (2-nitro-4-methylsulfonylbenzoyl) -4- (2,6-dichlorophenylthio)-
Bicyclo [3.2.1] oct-3-en-2-one (in formula (III), A ′ = 2,6- (Cl) ₂ C ₆ H ₃ S, B ′ = N
O ₂ , D ′ = H, E ′ = CH ₃ SO ₂ compound),

(8) 3- (2-Nitro-4-methylthiobenzoyl) -4- (3-chlorophenylthio) -bicyclo [3.2.1] oct-3-en-2-one (Formula (III)
_{In, A '= 3-ClC 6} H 4 S, B' = NO 2, D '=
H, E ′ = CH ₃ S compound),

(9) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (2,6-dichlorophenylthio)-
In bicyclo [3.2.1] oct-3-en-2-one (Formula (III), A '= 2,6- (Cl) 2 C 6 H 3 S, B' = C
1, D ′ = H, E ′ = CH ₃ SO ₂ ). These compounds can be synthesized by the method described in JP-A-6-25144.

The second active ingredient contained in the composition of the present invention is at least one halogen-substituted phenoxy derivative compound having herbicidal activity. Examples of such halogen-substituted phenoxy derivative compounds include compounds having the herbicidal activity represented by the general formula (II). Specific examples include the above compounds B to F.

The herbicide composition for paddy fields according to the present invention is a mixture of the above-mentioned first component and second component. In general, a synergistic effect is that the herbicidal activity by mixing drug compounds is greater than the simple sum of the activities of the individual compounds (expected activity). The expected activity of a particular combination of two herbicides can be calculated as follows (calculation of synergistic and antagonistic responses of the Colby SR herbicide combination "Weed" 15: 20-22. , 1967
See year. ).

[0029]

[Equation 1] E = α + β−α · β / 10 α: Inhibition evaluation value when the herbicide A is applied in an amount of akg / ha β: Inhibition evaluation when the herbicide B is applied in an amount of bkg / ha Value E: Evaluation value of inhibition expected when the herbicide A is used in an amount of akg / ha and the herbicide B is used in an amount of bkg / ha.

If the actual suppression evaluation value is larger than the theoretical value E calculated by the above formula, it means that the effect is more than the mere sum of the individual herbicidal activities. That is, it can be said that a synergistic effect due to the combination is recognized. As described below, the weed suppression evaluation value by the composition of the present invention shows a value larger than the theoretical value for various weeds, and a synergistic herbicidal effect is recognized for weeds of a wide range of species. Also, the effect is small when only one of the components is applied,
Even when a large amount of a drug is required to achieve a sufficient effect and, as a result, phytotoxicity to rice is unavoidable, when the composition of the present application is used, the phytotoxicity to rice is substantially reduced. A sufficient effect can be achieved with an application rate that does not bring about.

The combination of the substituted benzoyl cyclic enone derivative (first component) and the halogen-substituted phenoxy derivative compound (second component) in the composition of the present invention is a novel one not described in the literature, and of course its specific There is no literature that mentions potentiation. The synergism according to the invention is observed over a wide range of mixing ratios. To 1 part by weight of the first component compound represented by the general formula (I), 0.2 parts of the second component compound is added.
5 to 20 parts by weight, preferably 1 to 10 parts by weight can be mixed to obtain a useful herbicide. Each of the first component and the second component may be a single type of compound or a combination of a plurality of compounds.

The herbicidal composition of the present invention is generally used by formulating it into a form convenient for use according to a conventional method for agricultural chemicals. That is, each of the above active ingredients is mixed with an appropriate inert carrier and, if necessary, together with an auxiliary in an appropriate ratio and dissolved, separated, suspended, mixed, impregnated, adsorbed or adhered, or Mixed with an appropriate propellant, etc., in an appropriate dosage form, for example, a suspension, an emulsion, a solution, a wettable powder,
It can be formulated into powders, granules, tablets, flowables, aerosols and the like. The auxiliary agent may contain a necessary amount of a surfactant, an inert carrier, a binder, a decomposition inhibitor, a colorant, various agricultural chemicals, and the like. These components are not particularly limited as long as they are used in the conventional agricultural chemical formulation field.

For example, the surfactant is used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound. Specific examples thereof include lignin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, alkylaryl sulfonate, polyoxyethylene alkylaryl ether sulfate, polyoxyethylene styryl phenyl ether sulfate, and lauryl sulfate. Anionic surfactants such as salts and polycarboxylic acid type polymer surfactants, polyoxyethylene alkylaryl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene nonyl phenyl ethers, polyoxyethylene sorbitan al Nonionic fields such as chelate, polyoxyethylene polyoxypropylene block polymer, sucrose fatty acid ester, polyethylene glycol It can be mentioned such as an active agent. These surfactants may be used alone or in combination of two or more, and the mixing ratio in that case can be arbitrarily selected.

The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, sawdust powder, tobacco stem flour, walnut shell flour, bran, fiber powder, plant extracts such as residue after extraction of plant extracts. Powders; fiber products such as paper, cardboard, sifter; synthetic polymers such as crushed synthetic resins; clays (eg kaolin, bentonite, acid clay), talcs (eg talc, pyrophyllite), silicas (eg diatomaceous earth, silica sand) ,mica,
White carbon [Synthetic high-dispersion silicic acid which is also called hydrous fine silicon powder or hydrous silicic acid. Some products contain calcium silicate as a main component depending on the product. ]), Activated carbon, sulfur powder, pumice, calcined diatomaceous earth, brick crushed material, fly ash, sand, calcium carbonate, calcium phosphate, inorganic mineral powders such as pearlite; sodium carbonate, sodium hydrogen carbonate, calcium carbonate, sodium sulfate, citric acid And water-soluble powders such as succinic acid, fumaric acid, lactose, fructose, and glucose; and chemical fertilizers such as ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, and salt ammonium, and compost. These may be used alone or in the form of a mixture of two or more kinds.

The material which can be a liquid carrier is selected from those having solvent ability per se, and those having no solvent ability but capable of dispersing the active ingredient compound with the aid of an auxiliary agent. Water, alcohols (eg ethanol, methanol, isopropanol, butanol, ethylene glycol), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone), ethers (eg ethyl ether, dioxane, cellosolve, dipropyl ether) , Tetrahydrofuran), aliphatic hydrocarbons (eg gasoline, mineral oil), aromatic hydrocarbons (eg benzene, toluene, xylene, solvent naphtha, alkylnaphthalene), halogenated hydrocarbons (eg dichloroethane) Chlorinated benzene, chloroform, carbon tetrachloride), esters (eg, ethyl acetate, dibutyl phthalate, diisopropyl phthalate, dioctyl phthalate), acid amides (eg, dimethylformamide, diethylformamide, dimethylacetamide), nitriles (eg, acetonitrile), Dimethyl sulfoxide and the like. These may be used alone or in the form of a mixture of two or more kinds.

The following may be mentioned as other auxiliary agents. These auxiliary agents are used depending on the purpose. For the purpose of dispersion stabilization, adhesion and / or binding of the active ingredient compounds, for example, the following may be used: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine Examples include oil, kerosene, bentonite, and lignin sulfonate.

To improve the fluidity of the solid product, waxes, stearates, alkyl phosphates, etc. can be used. As the peptizer for the suspension product, for example, naphthalenesulfonic acid condensate, condensed phosphoric acid and the like can be used. It is also possible to add an antifoaming agent such as silicone oil.

In the composition of the present invention, the amount of the active ingredient compounded may be adjusted as necessary. In the case of powder or granules, as the total amount of the first component and the second component, usually,
0.2 to 20% by weight, and 0.1 to 50% by weight is suitable when the emulsion or wettable powder is used. The application rate of the mixture thus obtained can be used in a wide range of 0.01 to 5 kg / ha as the amount of the active ingredient of the mixture, but it is normally in the range of 0.05 to 1 kg / ha. Use is preferred. The herbicidal composition according to the present invention can be applied at any time in a wide range of the growing season before the occurrence of weeds, and a high effect can be obtained. The herbicidal composition according to the present invention,
One or more other herbicides, insecticides, fungicides, pesticides such as plant growth regulators, soil improvers, fertilizers, etc. can be mixed and used, and mixed preparations with them It is also possible, and in some cases a synergistic effect can be expected. In particular, it may be desirable to use other herbicides together in order to further improve the effect of the herbicide.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples (formulation examples, test examples).
The dosage amount, dosage form, etc. are not limited to these. In the following description, the first component compound means a substituted benzoyl cyclic enone derivative represented by the general formula (I), and the second component compound means a halogen-substituted phenoxy derivative compound. As the first component compound, compounds A1 to A5 shown in Table 1 below were used. The compounds BF described above were used as the second component compounds. In addition, “parts” means parts by weight.

[0040]

[Table 1]

Formulation Example 1: Wettable powder

TABLE 2 uniformly mixed and pulverized to Table 2 Ingredient proportion Compound A1 10 parts Compound E 30 parts alkylbenzenesulfonate sodium 2.0 parts naphthalenesulfonic acid formalin condensate sodium salt 3.0 parts of white carbon 3.0 parts Clay 52 parts The above ingredients To obtain a wettable powder.

Formulation 2: wettable powder

TABLE 3 by the Table 3 Ingredient proportion Compound A2 10 parts Compound F 20 parts alkylbenzenesulfonate sodium 2.0 parts of naphthalenesulfonic acid formalin condensate sodium 3.0 parts of white carbon 3.0 parts Clay 62 parts The above ingredients were uniformly mixed and ground It was used as a wettable powder.

Formulation Example 3: Granule

TABLE 4 uniformly mixing and grinding the Table 4 Ingredient Percentage Compound A2 1 part Compound E 4 parts Bentonite 30 parts Clay 61.5 parts 0.5 part of sodium dioctylsulfosuccinate polycarboxylic acid type polymeric activator 3.0 parts The above ingredients After that, a small amount of water was added, and the mixture was kneaded with stirring, kneaded, granulated with an extrusion-type granulator, and dried to give granules.

Formulation Example 4: Suspension

TABLE 5 a mixture of Table 5 Ingredient Percentage Compound A4 1 part compound E 1.5 parts of polyoxyethylene styryl phenyl ether 3 parts sodium dioctyl sulfosuccinate 0.5 parts modified silicone 0.3 parts Water 78.7 parts The above ingredients wet grinding Then, 15 g of a 2% xanthan gum aqueous solution was added to this suspension and mixed by stirring to obtain 100 g of a suspension composition.

Test Example 1: Flooded soil treatment pot test (weeds
Pre-emergence Treatment) A 1/2000 ares Wagner pot was filled with alluvial soil, and the water depth was maintained at 3 cm after the water entry was scraped. next day,
After embedding the tubers of Kurogwai and Urikawa to a depth of 3 cm, Tainubie and firefly were mixed-layer sown to a depth of 1 cm from the soil surface layer, and eel seeds and Cyperus tuber tubers were placed on the soil surface. Furthermore, rice plant seedlings (cultivar Koshihikari) at the 2.5-leaf stage were planted at a depth of 3 cm by 4 plants at a depth of 3 cm. In the chemical treatment, a predetermined amount of the wettable powder manufactured according to Formulation Example 1 was diluted to 2 ml of water 3 days after sowing, and the water surface was dropped with a pipette so as to be uniform in the pot. Water leakage of 3 cm per day was carried out for 3 days from the day after the treatment, and the herbicidal effect and the phytotoxicity were observed on the 30th day after the treatment with the criteria shown below. The test is 23-30
It was carried out in a glass greenhouse at ℃. The results are shown in Tables 7 to 12
It is shown in the table. The criteria for determining the herbicidal effect and the phytotoxicity in the table and the meanings of the abbreviations are as follows. The theoretical value is a value calculated by the Colby equation described above.

[0046]

[Table 6] Table 6 : Criteria for determining herbicidal effect and phytotoxicity Herbicidal effect Crop phytotoxicity 10 Weed control rate 96% or more Damage rate 96% or more 9〃 86-95% 〃 86-95% 8 〃 76-85% 〃 76-85% 7 〃 66-75% 〃 66-75% 6 〃 56-65% 〃 56-65% 5 〃 46-55% 〃 46-55% 4 〃 36-45% 〃 36-45% 3 〃 26-35% 〃 26-35% 2 〃 16-25% 〃 16-25% 1 〃 6-15% 〃 6-15% 0 〃 5% or less Harmless

Abbreviations in Tables 7 to 12: E. C. : Tainubie, S. J. : Firefly, M.
V. : Konagi, C.I. S. : Mizugayatsuri, E. K. : Kurogwai, S.K. P. : Urikawa, ABL: Annual broadleaf weed, O. S. : Transplanted rice.

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

[0051]

[Table 10]

[0052]

[Table 11]

[0053]

[Table 12]

Test Example 2: Flooded soil treatment pot test (weeds
Growing season treatment) 1/2000 ares Wagner pots were filled with alluvial soil, and the water depth was kept at 3 cm after water-filling. The next day, after embedding Kurowai and Urikawa tubers to a depth of 3 cm, tainubie (Nobie) and firefly were removed from the soil surface layer 1
The seeds were mixed and seeded to a depth of cm, and the seeds of the pupae and the tuber of the sedge were placed on the soil surface. In addition, 2.5 seedling rice seedlings (cultivar Koshihikari) are planted one by one to produce a depth of 3 cm.
Strain transplanted. 7 days after sowing, the drug treatment was 1.5.
A predetermined amount of the wettable powder produced according to Formulation Example 1 was diluted with 2 ml of water at the leaf stage, and a dropping treatment was performed on the water surface with a pipette so that the water was evenly distributed in the pot. 3 days after processing
Leakage operation of 3 cm per day was performed every day. On the 30th day after the drug treatment, the herbicidal effect and the phytotoxicity were generally observed according to the criteria shown below. The test was performed in a glass greenhouse at 23 to 30 ° C. The results are shown in Tables 13 to 19 (the criteria for determining the herbicidal effect and phytotoxicity and the meanings of the abbreviations in the table are the same as those in Tables 7 to 12).

[0055]

[Table 13]

[0056]

[Table 14]

[0057]

[Table 15]

[0058]

[Table 16]

[0059]

[Table 17]

[0060]

[Table 18]

[0061]

[Table 19]

Test Example 3: Flooded soil treatment field test (from weeds)
(Prenatal treatment) The paddy field was divided into 1 m ² square sections with a plastic plate, and seeds were sown at the same time as shavings.
After the leveling of the field, five Kurowai and Urikawa tubers were placed at a depth of 3 cm, and eel seeds and Cyperus tuber tubers were placed on the soil surface. One week later, rice planting was carried out using two rice seedlings (cultivar Koshihikari) at the 2.5-leaf stage as one strain. Three days after rice planting, a predetermined amount of the granules produced according to Formulation Example 3 was sprayed before the emergence of weeds and at the time of 0.5 leaf stage of Tainubie. The test site is northern Kanto and the soil is clay loam. In the survey, the amount of residual grass was measured on the 28th day after the chemical treatment, the ratio of untreated plots was calculated, and the above-mentioned criteria were evaluated. Also, 42 after drug treatment
The situation of suppression of weed generation on day was also evaluated in the same manner.
The results are shown in Tables 20 to 22 (the criteria for determining the herbicidal effect and phytotoxicity and the meanings of the abbreviations in the tables are Tables 7 to 1).
2 Same as table).

[0063]

[Table 20]

[0064]

[Table 21]

[0065]

[Table 22]

Test Example 4: Flooded soil treatment test (field test) The paddy field was divided into squares of 1 m ² by a plastic plate, and the seeds of Noubier and firefly were sown at the same time as the subsiding.
After the leveling of the field, five Kurowai and Urikawa tubers were placed at a depth of 3 cm, and eel seeds and Cyperus tuber tubers were placed on the soil surface. One week later, rice planting was carried out using two rice seedlings (cultivar Koshihikari) at the 2.5-leaf stage as one strain. One week after rice planting, a predetermined amount of the granules produced in accordance with Formulation Example 3 was sprayed at the time of the Noubie 1.5-2 leaf stage. The test site is northern Kanto and the soil is clay loam. In the survey, the amount of residual grass was measured on the 28th day after the chemical treatment, the ratio of untreated plots was calculated, and the above-mentioned criteria were evaluated. Also, 42 after drug treatment
The situation of suppression of weed generation on day was also evaluated in the same manner.
The results are shown in Tables 23 to 24 (the criteria for determining the herbicidal effect and phytotoxicity and the meanings of the abbreviations in Tables are Tables 1 to 1).
2 Same as table).

[0067]

[Table 23]

[0068]

[Table 24]

As shown in Test Examples 1 to 4 above, the herbicidal composition according to the present invention was used for paddy fields containing perennial weeds in a wide range from before planting to the weed growing season without damaging the rice. It was possible to control important weeds accurately. That is, in the herbicidal composition of the present invention, the herbicidal spectrum is expanded by the complementary action of the mixture. Further, from these results, it can be expected from the effect of each single drug by using the mixture containing at least one kind of the compounds represented by the general formula (I) and the halogen-substituted phenoxy derivative compound-based herbicide component. It can be seen that there is a marked synergy that cannot be achieved. That is, the herbicidal effect is superior to that of each single agent, and as a result of exhibiting such a synergistic effect, a smaller dose than in the case of using each compound alone to obtain an equivalent effect It can be used. Furthermore, the herbicidal composition according to the present invention comprises
Even when applied at any time from the time of weed development to the growth period of weeds, it shows remarkable effects, and it is possible to control important weeds in paddy fields almost completely by one treatment, and for 6 weeks (42 days)
The weed control effect is shown over the long term.

[0070]

The paddy field herbicidal composition of the present invention has a broad range of herbicidal spectrum including monocots, dicots, annuals and perennials. In addition, due to the synergistic effect of the drug components, the target weeds can be properly weeded by using a small amount without causing phytotoxicity to rice. Moreover, by extending the residual effect period, weed control can be realized throughout a period important for rice growth by one application. Therefore, labor and cost required for spraying the herbicide can be greatly reduced. Also,
In recent years, along with the spread of herbicide for weed control type paddy field, transition of paddy field weed species has occurred, and the occurrence expansion of difficult-to-control weeds resulting from this has been reported in various places, but the herbicidal composition of the present invention is ,
Since it has a broad spectrum of weeding and can control important weeds accurately over a long period of time, it can contribute to solving the problems caused by the transition of such weed species.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Jin Torii 2-1-1 Midorigahara, Tsukuba-shi, Ibaraki Pref. Inside SDS Biotech Tsukuba Research Laboratories (72) Inventor Akihiko Fujita 2-chome Midorigahara, Tsukuba-shi, Ibaraki 1st SDS Biotech Tsukuba Research Institute (72) Inventor Tadashi Sato 2-1-1 Midorigahara, Tsukuba-shi, Ibaraki Pref. SDS Biotech Tsukuba Research Institute (72) Inventor Sekino Keisuke 2-1-1 Midorigahara, Tsukuba, Ibaraki Pref. SDS Biotech Tsukuba Research Laboratories

Claims (3)

[Claims] 1. A compound of the general formula (I) [In the formula, A is an S (O) _n R ¹ group (in the group, R ¹ is (i) an optionally substituted lower alkyl group, (ii) a cycloalkyl group, or (iii) an optionally substituted A good benzyl group, or
(iv) represents a phenyl group which may be substituted with a substituted amino group, and n is 0 or 2. ) Or an OR ² group (wherein R ² represents an optionally substituted phenyl group); B represents a halogen atom, a nitro group, a lower alkyl group or a lower alkylsulfonyl group;
Represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxymethyl group or a lower alkoxycarbonyl group; E represents a halogen atom, an optionally substituted lower alkoxy group, a lower alkylthio group, a lower alkylsulfonyl group or a lower alkyl. Represents a sulfonyloxy group. ] The paddy field herbicide composition containing at least 1 type of substituted benzoyl cyclic enone derivative shown by these, and at least 1 type of halogen-substituted phenoxy derivative which has herbicidal activity as an active ingredient. 2. A halogen-substituted phenoxy derivative is represented by the general formula (II): [In the formula, X represents a chlorine atom or a fluorine atom, and Y ¹
Is a hydrogen atom or the following formula Wherein Y ² represents a hydrogen atom or a halogen atom, Z represents a lower alkyl group, a cycloalkyl group, or a compound represented by the following formula: (In the group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkyloxycarbonyl group. ) Is represented. ]
The herbicidal composition for paddy fields according to claim 1, which is a compound having a herbicidal activity represented by: 3. The compound represented by the general formula (II) is 2,4
-Dichlorophenyl-4-nitrophenyl ether, 5
-(2,4-dichlorophenoxy) -2-nitroanisole, 4-nitrophenyl-2,4,6-trichlorophenyl ether, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, 5 -Tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2 (3H) -one, 3N- (2-fluoro-4-cyclopentyloxyphenyl) ) -5-Isopropylidene-1,3-oxazolidine-2,4-dione is selected from the herbicide composition for paddy fields according to claim 1.