Description
A herbicide composition for paddy field
The present invention relates to a herbicide composition for paddy field. More specifically the present invention relates to a herbicide composition for paddy field containing a herbicidal difluoromethanesulfonamide derivative and a certain kind of known herbicidal compound as effective components.
Difluoromethanesulfonamide derivatives represented by the formula

wherein
X represents a halogen,
Y represents CH or N,
i R1 represents hydrogen, and
R2 represents hydrogen or hydroxy, or
R1 and R2 together may form C=0 with the carbon atom to which they are bonding, are known compounds (WO-A-2005/096818). Some of these derivatives show good controlling effect against paddy field weeds. Sometimes in the practical usage,
i however, contrary to expectation, they do not show a fully satisfactory herbicidal effect and phytotoxicity to paddy rice is observed. In the practical usage, it is practically difficult to provide a single active compound with such properties as to correspond to

various kinds of usage, as there are many potential elements influencing the herbicidal effect. Particularly, depending upon the kinds of weeds to be controlled, the conditions of their developing area, etc., the effect of an active compound is different. In addition, considering the cost reduction in agricultural production, influence on environment, etc., development of an agent showing effective action with less application amount is strongly desired.
In order to fulfill such a desire, as one of the methods to improve properties of a herbicide, it is often practiced to use it after mixing it with other active compounds. By using such a mixture, however, an expected effect is not necessarily obtained quite often, due to, for example, decomposition of active compounds, antagonistic action of effects, etc.
The present inventors, found, this time, that the composition mentioned below shows an outstandingly excellent and desirable effect in terms of weed controlling in paddy field and phytotoxicity to rice.
Thus, the present invention provides a herbicide composition for paddy field characterized by comprising a combination of components (a), (b) and/or (c), wherein i (a) is one or more difluoromethanesulfonamide derivative represented by the formula
(I)
wherein 5 X represents a halogen,

Y represents CH or N,
R1 represents hydrogen, and
R2 represents hydrogen or hydroxy, or
R1 and R2 together may form C=0 with the carbon atom to which they are bonding,
(b) is one or more herbicidal compounds selected from the group consisting of pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide, benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyracionil, oxaziclomefone, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosuifuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl, orthosulfamuron, cinosulfuron, metsulfuron-methyl, penoxsulam, thiobencarb, pyributycarb, molinate, dimethametryn, simetryn, cafenstrole, quinclorac, anilofos, mefenacet, fentrazamide, pentoxazone, oxadiargyl, oxadiazon, benzobicyclon, mesotrione, AVH301 (code no.), cyhalofop-butyl, metamifop, bispyribac-sodium, pyriftalid, pyrimisulfan, pyrimenobac-methyl, chlormethoxynil (chlomethoxyfen), oxyfluorfen, dithiopyr, MCPA, MCPB, 2,4-D, dymron, cumyluron, quinoclamine and clomazone, and
(c) is, as a safener, one or more compounds selected from the group consisting of dymron, isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fenclorim, cloquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-diethyl, furilazole, R-29148 (code no.), benoxacor, dichiormid and dicyclonone as effective components.
In the following the compounds of components (a), (b) and (c) are also named compounds (a), (b) or (c), respectively. The components (a), (b) and (c) are also shortly named compound (a), (b) or (c) respectively.
By the above-mentioned composition of the present invention, surprisingly, a substantially higher herbicidal effect (synergistic effect) than the sum of the effect of each active compound by each single application is shown, compared with the case that each active compound is used each singly. As a result, in case of controlling weeds, it is possible to substantially reduce the concentration of each substance used by now. At the same time, by said composition a broad herbicidal spectrum can be obtained and the application period can be broadened. In the paddy rice culture, for

example, it shows excellent herbicidal effect when applied any time from the early stage of weed development just after the transplantation to growing period. In addition, the effect maintains for a long period. Thus, an excellent herbicidal effect with an excellent residual effect and no phytotoxicity to rice is obtained.
In the compound (a) of the formula (I) in the composition of the present invention, preferably X represents fluorine or chlorine, Y represents CH or N, R1 represents hydrogen, and R2 represents hydrogen or hydroxy, or R1 and R2 together may form C=0 with the carbon atom to which they are bonding.
As preferable examples of the compound (a) of the formula (I) in the composition of the present invention there can be mentioned the following shown in the Table A mentioned below.



These compounds can be used each singly or in combination of two kinds or more.
In the composition of the present invention, the herbicidal compounds (b) used in combination with the compound (a) of the above-mentioned formula (I) are as aforementioned, and as their preferable examples there can be mentioned (b-1) aniiofos, (b-2) pretiiachlor, (b-3) cafenstrole, (b-4) cyhalofop-butyl, (b-5) penoxsulam, (b-6) pyraclonil, (b-7) bispyribac-sodium, (b-8) fentrazamide, (b-9) mefenacet, (b-10) oxaziclomefone, (b-11) benfuresate, (b-12)bensulfuron-methyl, (b-13) ethoxysulfuron, (b-14) bromobutide and (b-15) AVH301.
The above-mentioned herbicidal compounds (b) can be used, each singly or in combination of two kinds or more, as a mixture with a compound (a) of the formula (I).
The compounds (c) as safener used in combination with the compound (a) of the above-mentioned formula (I) according to the present invention are as aforementioned, and as their preferable examples there can be mentioned (c-1) dymron, (c-2) mefenpyr-diethyl, (c-3) isoxadifen and (c-4) isoxadifen-ethyl.

The above-mentioned compounds (c) as safener can be used, each singly or in combination of two kinds or more, as a mixture with a compound (a) of the formula (I).
The above-mentioned herbicidal compounds (b) and the compounds (c) as safener are described in, for example, The Pesticide Manual, 13th edition (published by British Crop Protection Council, 2003) or "Compendium of Pesticide Common Names" accessible e.g. from the Internet. The compound having the code number AVH 301 is a herbicide having the chemical name 2-{2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy)-rnethyl]-benzoyl}- cyclohexan-1,3-dione, also known under the common name "tefuryltrione". The compound having the code number R-29148 is a safener having the chemical name 3-(dichloroacetyl)-2,2,5-trimethyl-oxazolidine known from DE-A-02350800.
In the composition of the present invention, the mixing ratio of a compound (a) of the formula (I) and a herbicidal compound (b) can be varied in a relatively wide range according to the kind, application period, application place, application method, etc. of said composition. Generally, at least one herbicidal compounds (b) in the range of 0.05-200 parts by weight, preferably 0.1-100 parts by weight can be used to 1 part by weight of a compound (a) of the formula (I). Specifically, as good examples of individual usage ratio of herbicidal compounds (b) to 1 part by weight of a compound (a) of the formula (I) there can be mentioned the following.
Anilofos (b-1): 0.5-50 parts by weight, preferably 1-20 parts by weight, Pretilachlor (b-2): 0.5-50 parts by weight, preferably 1-20 parts by weight, Cafenstrole (b-3): 0.5-50 parts by weight, preferably 1-20 parts by weight, Cyhalofop-butyl (b-4): 0.3-30 parts by weight, preferably 0.5-10 parts by weight, Penoxsulam (b-5): 0.2-10 parts by weight, preferably 1-5 parts by weight, Pyraclonil (b-6): 0.5-50 parts by weight, preferably 1-20 parts by weight, Bispyribac-sodium (b-7): 0.1-10 parts by weight, preferably 0.2-5 parts by weight, Fentrazamide (b-8): 0.5-50 parts by weight, preferably 1-20 parts by weight, Mefenacet (b-9): 2-200 parts by weight, preferably 5-50 parts by weight, Oxaziclomefone (b-10): 0.2-10 parts by weight, preferably 1-5 parts by weight,

Benfuresate (b-11): 0.5-50 parts by weight, preferably 1-20 parts by weight, Bensulfuron-methyl (b-12): 0.1-10 parts by weight, preferably 0.2-5 parts by weight, Ethoxysulfuron (b-13): 0.1-10 parts by weight, preferably 0.2-5 parts by weight, Bromobutide (b-14): 2-200 parts by weight, preferably 5-50 parts by weight, AVH301 (b-15): 0.5-50 parts by weight, preferably 1-30 parts by weight.
In the composition of the present invention, the mixing ratio of a compound (a) of the formula (I) and a compound (c) as safener can be varied in a relatively wide range according to the kind, application period, application place, application method, etc. of said composition. Generally, at least one compounds (c) as safener in the range of 0.05-200 parts by weight, preferably 0.2-100 parts by weight can be used to 1 part by weight of a compound (a) of the formula (I). Specifically, as good examples of individual usage ratio of compounds (c) to 1 part by weight of a compound (a) of the formula (I) there can be mentioned the following.
Dymron (c-1): 0.5-100 parts by weight, preferably 1-20 parts by weight, Mefenpyr-diethyl (c-2): 0.05-10 parts by weight, preferably 0.5-5 parts by weight, Isoxadifen (c-3): 0.05-10 parts by weight, preferably 0.5-5 parts by weight, Isoxadifen-ethy! (c-4): 0.05-10 parts by weight, preferably 0.5-5 parts by weight.
The composition of the present invention shows a strong controlling effect against paddy field weeds and therefore said composition can be used as a herbicide composition for paddy field, particularly a selective herbicide for paddy rice.
An object of the invention'is thus the use of a combination of herbicide (a) and herbicide (b) or safener (c) or a combination of components (a) + (b) + (c) for controlling weeds in a paddy field, optionally in the presence of a crop of useful plants, particularly rice plants. The components can be applied to the paddy field and its weed plants in sequential manner or simultaneously. Another object of the invention is thus the method wherein the components (a), (b) and/or (c) are applied accordingly.
The composition of the present invention can be used against various kinds of

weeds developing in the paddy field. As their examples there can be mentioned the following:
Dicotyledonous plants of the following Genera: Polygonum, Rorippa, Rotala, Lindemia, Bidens, Dopatrium, Eclipta, Elatine, Gratiola, Lindemia, Ludwigia, Oenanthe, Ranunculus, Deinostema, etc.
Monocotvledonous plants of the following Genera: Echinochloa, Panicum, Poa, Cyperus, Monochoria, Fimbristyiis, Sagittaria, Eleocharis, Scirpus, Alisma, Aneilema, Blyxa, Eriocaulon, Potamogeton, etc.
The composition of the present invention can be used, more specifically for example, in relation to the following typical paddy field weeds.
Dicotyledonous plants Rotala indica Koehne Lindemia procumbens Philcox Ludwigia prostrata Roxburgh Potamogeton distinctus A. Benn Elatine tn'andra Schk Oenanthe javanica Monocotvledonous plants Echinochloa oryzicola Vasing Monochoria vaginalis Presl Eleocharis acicularis L. Eleocharis Kuroguwai Ohwi Cyperus difformis L Cyperus serotinus Rottboel Sagittaria pygmaea Miq Aiisma canaliculaturn A. Br. et Bouche Scirpus juncoides Roxburgh

The use of the composition of the present invention, however, should not be restricted to these weeds in any way, but can be applied against other weeds in the same manner.
The composition of the present invention can be made into customary formulation forms in case of using for control of paddy field weeds. As such formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, suspensions, powders, soluble powders, granules, suspo-emulsion concentrates, solid formulations (jumbo formulations), floating granules, microcapsules in polymer substance, etc.
These formulations can be prepared according to per se known methods. The formulations according to the present invention can be prepared, for example, by mixing the aforementioned compound (a) of the formula (I), herbicidal compound (b) and/or compound (c) with extenders, namely liquid diluents and/or solid diluents, and, in case of necessity, by using surfactants, namely emulsifiers and/or dispersants and/or foam-forming agents.
In case of using water as extender, for example, organic solvents can be used as auxiliary solvent. As liquid diluents there can be mentioned, for example, organic solvents such as aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions, mineral oils, vegetable oils, etc.)], alcohols (for example, butanol, glycols, etc. and their ethers, esters, etc.) ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), and water.
As solid diluents there can be mentioned, for example, ammonium salts, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, rnontmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example,

highly dispersed silicic acid, alumina, silicates, etc.) etc. As solid carriers for powders there can be used, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.
As emulsifiers and/or foaming agents there can be mentioned nonionic or anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (for example, alkylaryl poiyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, etc.)], albumin hydrolysis products, etc.
As dispersants, for example, lignin sulfite waste liquor, methyl cellulose, etc. are adequate.
Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetates, etc.) natural phospholipids (for example, cephalins or recithins), synthetic phospholipids, etc. Further, as additives, mineral oils and vegetable oils can be used.
Colorants can also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further traces nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.
The formulations can contain the total of the compound of the formula (I) (a), herbicidal compound (b) and/or compound (c) at a concentration in the range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight.
The composition of the present invention can be used for controlling weeds as

themselves or in their formulation forms. It is also possible to do tank mixing at the time of application and further to contain other known active compounds, particularly active compounds generally used in the paddy field, for example, fungicides, insecticides, plant growth regulators, plant nutrients, soil improving agents, etc.
The composition of the present invention can be used as such or in their formulation forms or in application forms prepared by further diluting said formulations, for example, in the forms of ready-to-use solutions, emulsifiable concentrates, suspensions, powders, wettable powders or granules. Formulations of these forms can be applied to paddy field by usual methods, for example, watering, spraying, atomizing, dusting, granule spreading, etc.
The composition of the present invention can be applied to the paddy field before, at the time and after the transplantation. The amount of said composition to be applied can be varied in a substantial range. The amount can be in the range of, for example, 0.01-5 kg/ha, preferably 0.06-4.5 kg/ha as the total amount of the compound of the formula (I) (a), herbicidal compound (b) and/or compound (c).
Excellent results of the composition of the present invention will be described more specifically by the following examples. The present invention, however, should not be restricted only to them in any way.
Biological test examples and formulation examples

Component (a) (a-1): compound No. 1 (ref: the aforementioned Table A)
(a-2): compound No. 3 (same as above)
(a-3): compound No. 11 (same as above) Component (b) the aforementioned (b-1) - (b-15) Component (c) the aforementioned (c-1) - (c-3) Preparation of test agents> Carrier: Acetone 5 parts by weight Surfactant: Benzyloxy polyglycol ether 1 part by weight

The above-mentioned carrier and surfactant and 1 part by weight of active compounds(component (a) and component (b) or component (c)) are mixed and the obtained formulations are diluted with water to prepare the test agents of the prescribed chemicals amount (preparations).
Test example 1: Test of effect of the herbicide composition against paddy field weeds
In a green house, seeds or tubers of Monochoria vaginalis Presl, annual broad-leaves (Lindernia procumbens Philcox, Rotala indica Koehne, Elatine triandra Schk, Ammannia multiflora Roxb., etc.), Cyperus serotinus Rottboel, and Sagittaria pygmaea Miq were inoculated to paddy field soil filled in a 500cm2 pot and brought to a submerged condition of about 2-3 cm. At 1.5 - 2 leafstage of each weed prescribed diluted solution of preparation of each active compound and each herbicide in the following table was applied on water surface each singly or simultaneously. After the treatment, the submerged condition of 3 cm was maintained and the herbicidal effect was studied 3 weeks after the treatment. The herbicidal effect was evaluated as 100% in case of complete death and 0% in case of no effect.
Results are shown in Table 1 -Table 3. In the tables, MOOVP represents Monochoria vaginalis Presl, BBBBB represents annual broad-leaves, CYPSE represents Cyperus serotinus Rottboel and SAGPY represents Sagittaria pygmaea Miq.

Test example 2: Test of effect of phytotoxicity reduction
In a green house, paddy rice of 2 - 2.5 leafstage was transplanted to paddy field soil filled in a 1000cm2 pot to 2cm depth and brought to a submerged condition of about 2 - 3cm. Five days after the transplantation, prescribed diluted solution of preparation of each active compound and each herbicide in the following table was applied on water surface each singly or simultaneously. After the treatment, the submerged condition of 3cm was maintained and the grade of phytotoxicity to paddy rice was studied 2 weeks after the treatment. The phytotoxicity was evaluated as 100% in case of complete death and 0% in case of no phytotoxicity. Results are shown in Table 4.

Formulation Example 1
To a mixture of 3 parts by weight of the active compound (a-1), 4 parts by weight of the active compound (b-1), 32 parts by weight of bentonite (montmorillonite), 58 parts by weight of talc and 3 parts by weight of ligninsulfonate salt, 25 parts by weight of water were added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.
Formulation Example 2
96 Parts by weight of clay mineral particles having particle diameter distribution in the range of 0.2-2mm are put in a rotary mixer. While rotating it, 2 parts by weight of the active compound (a-1) and 2 parts by weight of the active compound (b-2) are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.
Formulation Example 3
A mixture of 4 parts by weight of the active compound (a-1), 4 parts by weight of the active compound (b-3), 10 parts by weight of ethylene glycol, 3 parts by weight of polyoxyalkylene tristyrylphenyl ether, 10 parts by weight of xanthan gum, 0.5 parts by weight of 14% silicone oil emulsion and 68.5 parts by weight of water is well stirred and then crushed with a crusher (Dyno-Mill Type KDL) to obtain water suspension formulation.
Formulation Example 4
5 Parts by weight of the active compound (a-1), 15 parts by weight of the active compound (b-4), 30 parts by weight of sodium ligninsulfonate, 15 parts by weight of parts bentonite and 35 parts by weight of calcined diatomaceous earth powder are well mixed, added with water, well kneaded, extruded with 0.3mm screen and dried to obtain water dispersible granules. [Industrial applicability]
The herbicide composition for paddy field of the present invention shows, as shown in the aforementioned test examples, precise controlling effect against various kinds of paddy field weeds and an excellent residual effect.

Patent Claims
1. A herbicide composition for paddy field characterized by comprising a
combination of components (a), (b) and/or (c), wherein
(a) is one or more difluoromethanesulfonamide derivatives represented by the
formula (I),
wherein
X represents a halogen,
Y represents CH or N,
R1 represents hydrogen, and
R2 represents hydrogen or hydroxy, or
R1 and R2 together form C=0 with the carbon atom to which they are bonding,
(b) is one or more herbicidal compounds selected from the group consisting of
pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide,
benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyraclonil,
oxaziclomefone, bensulfuron-methyl, azimsulfuron, imazosulfuron,
pyrazosulfuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl,
orthosulfamuron, cinosulfuron, metsuifuron-methyl, penoxsulam, thiobencarb,
pyributycarb, molinate, dimethametryn, simetryn, cafenstrole, quinclorac, anilofos,
mefenacet, fentrazamide, pentoxazone, oxadiargyl, oxadiazon, benzobicyclon,
mesotrione, AVH301, cyhalofop-butyl, metamifop, bispyribac-sodium, pyriftalid,
pyrimisulfan, pyrimenobac-methyl, chlormethoxynii, oxyfluorfen, dithiopyr, MCPA,
MCPB, 2,4-D, dymron, cumyluron, quinoclamine and clomazone, and
(c) is, as a safener, one or more compounds selected from the group consisting
of dymron, isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fenclorim,

cloquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-diethyl, furilazole, R-29148, benoxacor, dichlormid and dicyclonone as effective components.
2. A composition according to claim 1, characterized in that
X represents fluorine or chlorine,
Y represents CH or N,
R1 represents hydrogen, and
R2 represents hydrogen or hydroxy, or
R1 and R2 together form C=0 with the carbon atom to which they are bonding,
in the formula (I).
3. A composition according to claim 1 or 2, characterized in that it comprises one or more herbicidal compounds (b) in the range of 0.05-200 parts by weight to 1 part by weight of the compound (a).
4. A composition according to any one of claims 1 to 3, characterized in that it comprises one or more compounds (c) as a safener in the range of 0.05-200 parts by weight to 1 part by weight of the compound (a).
5. Method for controlling weeds in a paddy field which comprises applying to the
weeds, parts of the weeds, weed seeds or their habitat, optionally in the presence of a
crop, a combination of
a herbicide (a) and a herbicide (b), or
a herbicide (a) and a safener (c), or
a herbicide (a), a herbicide (b) and a safener (c),
wherein the components (a), (b) and (c) of the specific combination are applied
simultaneously or sequentially, and wherein the components are defined as in any one
of claims 1 to 4.
6. Method as claimed in claims 5, wherein the crop is rice.

7. Use of a combination of components (a), (b) and/or (c) as defined in any of
claims 1 to 4 for controlling weeds in a paddy field, optionally in the presence of a crop.
8. The use as claimed in claim 7, wherein the crop is rice.