JPH0930904A - Paddy field herbicide composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a herbicide composition for paddy fields, which can control important weeds of both monocotyledons and dicotyledons with a small amount of active ingredient, over a long period of time. [Structure] Formula (I) (wherein A is an S (O) _n R ¹ group (R
¹ is lower alkyl, cycloalkyl, (substituted) benzyl, (substituted amino-substituted) phenyl; n is 0 or 2 or OR ² group (R ² is (substituted) phenyl); B is halogen;
Nitro, lower alkyl, lower alkylsulfonyl; D is H, lower alkyl, lower alkoxy, lower alkoxymethyl, lower alkoxycarbonyl; E is halogen, (substituted) lower alkoxy, lower alkylthio, lower alkylsulfonyl or lower alkylsulfonyloxy) A herbicide composition for paddy fields containing the substituted benzoyl cyclic enone derivative shown and a phenoxyacetic acid compound. Embedded image

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 containing a substituted benzoyl cyclic enone derivative of a specific structure and a phenoxyacetic acid compound as active ingredients, which has little phytotoxicity to paddy rice and a small application amount. The present invention relates to a herbicide composition for paddy fields which causes weeds in paddy fields to die.

[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.
It was necessary to treat herbicides multiple times during each cultivation period in order to meet the actual requirements of paddy rice cultivation. Therefore, 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 against rice and exhibits excellent effects over a long period of time especially against weed species of the rice family.
The following general formula (I)

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, a phenoxyacetic acid type herbicide has been known for a relatively long time among conventional agents.
This group of compounds are plant hormone-like substances and are called hormonal herbicides together with benzoic acid and picolinic acid type herbicides. These are structurally derivatives of phenoxyacetic acid or similar compounds. Specifically, the following formula (II)

## STR00004 ## X--O--Y--CO--Z (II) (In the formula, X represents an optionally substituted phenyl group or an optionally substituted naphthyl group, and Y is a linear or branched lower group. Represents an alkylene, and Z has a structure represented by a hydroxyl group, an alkoxy group or an aryloxy group, or an amino group which may be substituted with a lower alkyl or a phenyl group or a mercapto group.

Commercially available phenoxyacetic acid herbicides include (1) Clomeprop (generic name; the same applies hereinafter): 2- (2,4-dichloro-3-methylphenoxy) propionanilide (hereinafter , Compound B.),

(2) Naproanilide: α-
(2-naphthoxy) propionanilide (hereinafter referred to as compound C),

(3) Phenothiol (MCPA-thioethyl):
S-ethyl (2-methyl-4-chlorophenoxy) ethanethioate (hereinafter referred to as compound D),

(4) MCPB:

(5) 4- (2-methyl-4-chlorophenoxy) butyric acid (hereinafter referred to as compound E),

(6) 2,4-D: 2,4-dichlorophenoxyacetic acid (hereinafter referred to as compound F).

Compounds B to D are each described in JP-A-57-17.
1904, JP-A-49-35533, U.S. Pat. No. 3,708,278, British Patent 758,980, etc., and they are commercially available and put into practical use.

Phenoxyacetic acid compounds are a group of herbicides having selectivity for transplanted paddy rice and show high activity against perennial broad-leaved weeds such as Urikawa. However, it is known that the effect on the millet, Cyperaceae weeds and eels with advanced leaf age is low.

[0013]

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. With a smaller amount of active ingredient, monocotyledons,
An object of the present invention is to provide a herbicide composition for paddy fields, which can control any important weeds of dicotyledons accurately and for a long time.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the combined use of a compound A represented by the general formula (I) and other herbicidally active compounds, and as a result, compound A and a phenoxyacetic acid type herbicide. The mixture of compounds shows a surprising and unexpected synergistic effect, and it can control important weeds in paddy fields with a much smaller amount than with the use of each single agent, and can control the weeds for a long time with a single treatment, and it can be applied to paddy rice. 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 harm.

That is, the present invention provides the following herbicide composition for paddy fields. 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. ] The at least 1 type of substituted benzoyl cyclic enone derivative shown by these, and at least 1 type of phenoxyacetic acid type compound which has herbicidal activity are contained as an active ingredient, The herbicide composition for paddy fields characterized by the above-mentioned.

2) The phenoxyacetic acid compound is represented by the general formula (II)

## STR00006 ## X-O-Y-CO-Z (II) (wherein all symbols have the same meanings as described above), which is a compound having herbicidal activity, and the herbicide for paddy field according to 1 above. Agent composition.

3) The phenoxyacetic acid compound is (RS)
-2- (2,4-Dichloro-m-tolyloxy) -propionanilide, N-phenyl-2- (2-naphthoxy) propionamide, S-ethyl-4-chloro-o-
Trilyl thiothioacetate, 4- (4-chloro-o-
The herbicide composition for paddy fields according to 1 above, which is selected from tolyloxy) butyric acid and 2,4-dichlorophenoxyacetic acid.

The first component contained in the herbicide composition for paddy field of the present invention is a substituted benzoyl cyclic enone derivative represented by the above general formula (I). General formula (I)
In the case where 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) 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)

[In the formula, A ′ is a —S (O) nR ¹¹ group (in the group,
R ¹¹ represents an unsubstituted phenyl group or a phenyl group substituted with 1 to 5 halogen atoms or 1 to 3 alkyl groups having 1 to 4 carbon atoms, and 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 to 3 carbon atoms which may be substituted by 1 to 3 fluorine atoms. Represents a lower alkylsulfonyl group. ] 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 compound), (2) 3- (2-chloro-4-methylsulfonylbenzoyl) -4- (3-methylphenylthio) Bicyclo [3.2.1] oct-3-en-2-one (Formula (II
I), 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 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- (CH3 ) 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)-
In bicyclo [3.2.1] oct-3-en-2-one (Formula (III), A = 3- ClC 6 H 4 S, B '= Cl,
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- (CH3) 2 C 6} H 3 S, B '= NO 2,
D '= H, E' compounds of _{= CH 3 SO 2), (} 7) 3-
(2-Nitro-4-methylsulfonylbenzoyl) -4
-(2,6-dichlorophenylthiobicyclo)-[3.
2.1] Oct-3-en-2-one (in the formula (III), A
_{= 2,6- (Cl) 2 C 6} H 3 S, B '= NO 2, D'
= H, E '= a compound of _{CH 3 SO 2), (8} ) 3- (2-
Nitro-4-methylthiobenzoyl) -4- (3-chlorophenylthiobicyclo)-[3.2.1] oct-3
- en-2-one (Formula (III), A = 3- ClC 6 H 4
_{S, B '= NO 2,} D' = H, compounds of the _{E '= CH 3 S),} (9) 3- (2- chloro-4-methylsulphonyl benzoyl) -4- (2,6-dichlorophenyl Ji Obi cyclo )-[3.2.1] Oct-3-en-2-one (in formula (III), A = 2,6- (Cl) 2 C ₆ H ₃ S,
B '= Cl, D' = H, E '= a compound of CH ₃ SO _2).

These compounds can be synthesized by the method described in JP-A-6-25144. The second component contained in the composition of the present invention is at least one phenoxyacetic acid compound having herbicidal activity. Such a phenoxyacetic acid compound is represented by the above general formula (II). Specifically, the above compounds B to F can be mentioned.

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 Colby SR herbicide combinations "Weed" 15: 20-22, 19
See 67. )

[0026]

[Equation 1] E = α + β−α · β / 100 α: Inhibition rate when the herbicide A is applied in an amount of akg / ha β: Inhibition rate when the herbicide B is applied in an amount of bkg / ha E : Herbicide A is akg / ha, Herbicide B is bkg / ha
Inhibition rate when used in combination with

If the actual suppression rate 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. Further, application of only one of the components has a small effect, and a large amount of a drug is required to achieve a sufficient effect, and as a result, phytotoxicity to rice is inevitable. When the composition is used, a sufficient effect can be obtained with an application rate that does not substantially cause phytotoxicity to rice.

The combination of the substituted benzoyl cyclic enone derivative (first component) and the phenoxyacetic acid compound (second component) in the composition of the present invention is a novel one not described in the literature, and of course, its specific potentiation of efficacy. There is no document that mentions. The synergism according to the invention is observed over a wide range of mixing ratios. It is useful to mix 1 part by weight of the first component compound represented by the general formula (I) with 0.1 to 50 parts by weight of the second component compound, preferably 1: 0.03 to 1:20 parts by weight. Herbicide can be obtained. 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. As the auxiliary agent, a necessary amount of a surfactant, a carrier, a binder, a decomposition inhibitor, a colorant, various agricultural chemicals and the like can be contained. 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 include lignin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, alkyl allyl sulfonate, polyoxyethylene alkyl allyl ether sulphate, polyoxyethylene styryl phenyl. Ether sulfate, lauryl sulfate,
Anionic surfactants such as polycarboxylic acid type polymer surfactants, polyoxyethylene alkyl allyl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene nonyl phenyl ethers Examples thereof include nonionic surfactants such as tellurium, polyoxyethylene sorbitan alkylate, 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 which can be used in the present invention may be either solid or liquid, and examples of the material which can be a solid carrier include soybean flour, cereal flour, wood flour and bark flour. , Sawdust, tobacco stem flour, walnut flour, bran, fiber powder, plant powder such as residue after extraction of plant extract; fiber products such as paper, cardboard, sifure; synthetic polymer such as crushed synthetic resin; clay (Eg kaolin, bentonite, acid clay), talc (eg talc, hirophyllite), 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 capable of serving as a liquid carrier is selected from those having solvent ability per se, and those having no solvent ability but capable of dispersing an 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.

Other auxiliary agents include the following. 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. For improving the fluidity of solid products, 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 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 is 0 as the active ingredient amount of the mixture.
It can be used in a wide range from 01 kg to 5 kg / 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 from before the emergence of weeds to the growing season, and high effects 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 and plant growth regulators, soil conditioners or fertilizers. Of course, it is also possible to prepare a mixed preparation 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.

[0036]

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 phenoxyacetic acid compound. Compounds A-No. 1 to A-No. 6 shown in Table 1 below were used as the first component compounds. The compounds BF described above were used as the second component compounds. In addition, “parts” means parts by weight.

[0037]

[Table 1]

Formulation Example 1: Wettable powder

The Table 2] Table 2 Ingredients ratio Compound A-No.1 10 parts Compound B 10 parts alkylbenzenesulfonate sodium 2.0 parts naphthalenesulfonic acid formalin condensate sodium salt 3.0 parts of white carbon 3.0 parts Clay 72 parts The above ingredients A wettable powder was obtained by uniformly mixing and pulverizing.

Formulation Example 2: Wettable powder

Table 3 The Table 2 Ingredient ratio Compound A-No.2 5 parts Compound C 20 parts alkylbenzenesulfonate sodium 2.0 parts of naphthalenesulfonic acid formalin condensate sodium 3.0 parts of white carbon 3.0 parts Clay 67 parts The above ingredients uniformly The mixture was pulverized to obtain a wettable powder.

Formulation Example 3: Granule

TABLE 4 uniform Table 4 Ingredient Percentage Compound A-No.1 2 parts Compound B 2 parts Bentonite 30 parts Clay 62.5 parts sodium dioctyl sulfosuccinate 0.5 parts polycarboxylic acid type polymer-active agent 3.0 parts The above ingredients After mixing and pulverizing, the mixture was mixed with a small amount of water, kneaded with stirring, kneaded, granulated by an extrusion-type granulator, and dried to give granules.

Formulation Example 4: Granules

TABLE 5 uniform Table 5 Ingredient Percentage Compound A-No.2 1 part Compound C 10 parts Bentonite 30 parts Clay 55.5 parts sodium dioctyl sulfosuccinate 0.5 parts polycarboxylic acid type polymer-active agent 3.0 parts The above ingredients After mixing and pulverizing, the mixture was mixed with a small amount of water, kneaded with stirring, kneaded, 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 B 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-milled, and 15 g of a 2% xanthan gum aqueous solution was added to this suspension and mixed with stirring to obtain 100 g of a suspension composition.

Formulation 6: Suspension

Table 7 were mixed Table 7 Ingredients Percentage Compound A-No.4 3 parts Compound D 2 parts of polyoxyethylene styryl phenyl ether 3 parts sodium dioctyl sulfosuccinate 0.5 parts modified silicone 0.3 parts Water 76.2 parts The above ingredients The product was wet-milled, and 15 g of a 2% xanthan gum aqueous solution was added to this suspension and mixed with stirring to obtain 100 g of a suspension composition.

Test Example 1: Flooded soil treatment pot test (weeds
Pre-emergence treatment) A Wagner pot of 1/2000 aal was filled with alluvial soil, and the water depth was kept 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. 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 3 days after seeding, by diluting a predetermined amount of the wettable powder produced in accordance with Formulation Examples 1 and 2 into 2 ml of water, and dropping it on the surface of the water with a pipette so that it was even in the pot. It was Water leakage of 3 cm per day was carried out for 3 days from the day after the treatment, and the herbicidal effect and phytotoxicity were observed on the 30th day after the treatment by the criteria shown below. The test is 23 ~ 30 ℃
In a glass greenhouse. The results are shown in Tables 9 to 14. The criteria for determining the herbicidal effect and the phytotoxicity in the table and the meanings of the abbreviations are as follows. Also, the theoretical value is
It is the value calculated by Colby's formula. Criteria for herbicidal effect and phytotoxicity:

[0045]

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 12: E. C. : Tainubie, S. J. : Firefly, M.
V. : Konagi, C.I. S. : Mizugayatsuri, E. K. :
Kurogwai, S.K. P. : Urikawa, O.I. S. : Transplanted rice.

[0047]

[Table 9]

[0048]

[Table 10]

[0049]

[Table 11]

[0050]

[Table 12]

[0051]

[Table 13]

[0052]

[Table 14]

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. 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. Furthermore, rice plant seedlings (cultivar Koshihikari) at the 2.5 leaf stage were transplanted at a depth of 3 cm by 4 plants per plant. The treatment with the drug was carried out by diluting a predetermined amount of the wettable powder produced according to the formulation examples 1 and 2 into 2 ml of water at the time of 1.5 leaf stage of Tainubie 7 days after seeding, and making it uniform in the pot with a pipette. Dropping treatment was performed on the water surface. 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 15 to 20 (determination criteria for herbicidal effect and phytotoxicity and meanings of abbreviations in Table are the same as those in Tables 9 to 14).

[0054]

[Table 15]

[0055]

[Table 16]

[0056]

[Table 17]

[0057]

[Table 18]

[0058]

[Table 19]

[0059]

[Table 20]

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 21 to 24 (the criteria for determining the herbicidal effect and phytotoxicity and the meanings of the abbreviations in the tables are the same as those in Tables 9 to 14).

[0061]

[Table 21]

[0062]

[Table 22]

[0063]

[Table 23]

[0064]

[Table 24]

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 hemlock and firefly were sown at the same time as substituting.
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 (cultivar Koshihikari) at the 2.5 leaf stage were planted as two rice plants per strain. Formulation example 4 at the time of 1.5 to 2 leaf stage after 1 week from rice planting
A predetermined amount of the granules produced according to the above was sprayed. 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 investigation, the amount of residual grass was measured 30 days and 8 weeks after the drug treatment (56th day), and the ratio of the untreated plot to the untreated plot was obtained and evaluated according to the aforementioned criteria. Result 25th
The results are shown in Tables and Tables 26 (the criteria for the herbicidal effect and phytotoxicity and the meanings of the abbreviations in the tables are the same as in Tables 9 to 14).

[0066]

[Table 25]

[0067]

[Table 26]

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 planting to the weed growing season without damaging the 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 or more of the compounds represented by the general formula (I) and a phenoxyacetic acid herbicide component cannot be predicted from the effect of each single agent. It can be seen that a synergistic effect is exhibited. 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. In addition, the weed control effect is shown over a long period of 8 weeks (56 days) or more.

[0069]

The paddy field herbicidal composition of the present invention has a broad range of herbicidal spectrum including monocots, dicots, annuals and perennials. Moreover, due to the synergistic effect of the component drugs, the target weeds are properly weeded with a small amount of use that does not cause 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 heavy weeds accurately over a long period of time, it can also contribute to solving the problems caused by such changes in 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 at least 1 type of substituted benzoyl cyclic enone derivative shown by these, and at least 1 type of phenoxyacetic acid type compound which has herbicidal activity are contained as an active ingredient, The herbicide composition for paddy fields characterized by the above-mentioned. 2. A phenoxyacetic acid-based compound is represented by the general formula (II): X-O-Y-CO-Z (II) (wherein, X is phenyl which may be substituted or may be substituted). Represents a good naphthyl group, Y represents a linear or branched lower alkylene, Z represents a hydroxyl group, an alkoxy group or an aryloxy group, or an amino group or a mercapto group which may be substituted with a lower alkyl or a phenyl group. The herbicidal composition for paddy fields according to claim 1, which is a compound having a herbicidal activity represented by 3. A phenoxyacetic acid compound is (RS)-
2- (2,4-dichloro-m-tolyloxy) -propionanilide, N-phenyl-2- (2-naphthoxy)
The paddy field according to claim 1, which is selected from propionamide, S-ethyl-4-chloro-o-tolyloxythioacetate, 4- (4-chloro-o-tolyloxy) butyric acid, and 2,4-dichlorophenoxyacetic acid. Herbicide composition.