KR100296804B1 - Weed control herbicide composition - Google Patents

Abstract

An effective amount of the anilophos (I) is compound B ₁ ) bensulfuron-methyl, B ₂ ) pyrazosulfuron ethyl, B ₃ ) cynosulfuron, B ₄ ) imazosulfuron, B ₅ ) AC 014, B ₆ ) pyrazoxifene, B ₇ ) benzophenaph (MY71), B ₈ ) dimuron, B ₉ ) benfuresate, B ₁₀ ) bromobutide, B ₁₁ ) ACN, quinoclamine, B ₁₂ ) JC 940 and B ₁₃ ) to a herbicide composition comprising at least one compound B (compound B form) selected from the group comprising phenoxaprop-ethyl or phenoxaprop-P-ethyl.

Description

Herbicide composition for weed control of rice

Anilophos is an optional rice herbicide that can be used to control annual grasses and forage of transplanted rice: Referenceicide Manual, British Prot. Council, 9th Ed., P. 36].

It was mentioned around 1981 that anilofos could be mixed with 2,4-dichlorophenoxyacetic acid (2,4-D) to broaden the herbicidal range for broadleaf weeds. This is why annuals such as Echinochloa spp. And Iscamum sp., Cyperus difformis, and Cyperus Monochoria vaginalis, Sphenocchia jalanica, as well as forages such as Cyperus iria and Fimbristylis littoralis. Light leaf species such as (Sphenochlea zeylanica) and Ludwigia octovalis (1) are well protected.

Japanese Patent Application Laid-Open No. 54 160731 (DOS 2,821,509 and UK Patent No. 2,020,978) includes a mixture of anilofos and 2,4-D, MCPB, naproanilide, dimuron and ventazone for controlling weeds of rice. When used it has been described to exhibit synergy.

On the other hand, weeds are known that cannot be sufficiently controlled even when the mixtures are used in rice in Japan and Southeast Asia. In particular, they are Sagittaria spp., Eleocharis spp., Ciliformus, Cyperus serotinus, and cypus. Weeds such as scirpus juncoides, as well as other weed species that germinate mainly from perennial organisms in the soil, which are more difficult to control than weeds germinating from seeds.

Surprisingly, in biological greenhouse experiments with a wide range of herbicidal materials, new synergistic mixtures have been found which, when used together, have very good herbicidal properties against a wide range of weeds and very good resistance to rice. They are superior to known herbicide and herbicide mixtures in activity and efficiency and can be used in smaller applications.

Another advantage of these new mixtures is that their duration of activity lasts for several weeks and there is no need to continuously apply herbicides to newly germinating weeds. The fact that only one application is sufficient to destroy weed growth makes the second application unnecessary.

The present invention relates to a herbicide composition comprising an effective amount of the following anilophos (I) together with at least one compound (B) (form B compound) selected from the group comprising compounds (B1) to (B13):

(B1) bensulfuron-methyl, methyl α- (4,6-dimethoxypyrimidin-2-ylcarbamoyl-sulfamoyl) -o-toluate,

(B2) pyrazosulfuron-ethyl, 5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate,

(B3) cynosulfuron, 3- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1- [2- (2-methoxyethoxy) -phenylsulfonyl] urea ,

(B4) imazosulfuron, 1- (2-chloroimidazo [1,2- α ] pyridin-3-yl-sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (Example No. 1 of TH-913, EP 0,238,070),

(B5) AC 014, 1- (2- (cyclopropylcarbonylphenyl) sulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea,

(B6) pyrazoxifen, 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] -acetophenone,

(B7) benzophenap (MY71), 2- [4- (2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy] -4'-methylacetophenone,

(B8) dimuron, 1- (1-methyl-1-phenylethyl) -3-p-tolylurea,

(B9) benfuresate, 2-3-dihydro-3,3-dimethylbenzofuran-5-yl-ethanesulfonate,

(B10) bromobutide, 2-bromo-3,3-dimethyl-N- (1-methyl-1-phenylethyl) butyramide,

(B11) ACN, quinoclamin, 2-amino-3-chloro-1,4-naphthoquinone,

(B12) JC 940, 1- (2-chlorobenzyl) -3- ( α , α -dimethylbenzyl) urea and

(B13) phenoxaprop-ethyl or phenoxaprop-P-ethyl, ethyl (±)-or (2R) -2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] Propionate,

Except for B5 (AC 014) known from US Patent No. 5,009,699, B4 (TH-913) known from European Patent No. 0,238,070, and B12 (JC940) known from Japanese Patent Application No. J-60 087254. And all compounds of Form B are described in "The Pesticide Manual", 9th Edition, Brit, Crop Prot. Council, 1991].

Specific examples of mixtures of claimed active substances are as follows, but should not be understood to be limited to these:

Anilophos + Bensulfuron-Methyl

Anilophos + Bensulfuron-Methyl + Dimuron

Anilophos + parazosulfuron ethyl

Anilophos + parazosulfuron ethyl + dimuron

Anilofoss + Cinosulfuron

Anilofoss + Sinosulfuron + Daimuron

Anilofoss + TH 913

Anilofoss + TH 913 + Daimuron

Anilopos + AC 014

Anilofoss + AC 014 + Daimuron

In such mixtures, the use of dimuron is very advantageous in two aspects. On the one hand, Daimuron is Cyprus spy. And herbicides on grass, and on the other hand, dimuron also acts as a toxic mitigator on rice crops, reducing the potential damage that can be caused by herbicides such as, for example, sulfonylurea derivatives. The effect as a safener was also observed in the mixture of JC-940 and Anilophos.

In a similar way, anilophos has been found to have surprising toxic mitigating effects in mixtures with pyrazosulfuron. Potential damage to rice by pyrazolesulfuron itself or as a mixture with other herbicides is reduced or completely offset by anilophos. This active substance composition thus exhibits surprising new properties that go beyond the known effects and are unpredictable at all.

The herbicide composition according to the present invention has excellent herbicidal activity against a wide range of harmful plants of monocotyledonous and dicotyledonous which are economically important. Active substance compositions also work effectively against perennial weeds that germinate from difficult to control rhizomes (root stocks) and other perennial organisms. It is not a problem here whether the active substance is applied before implantation, before germination or after germination. In particular, mention may be made of several representative examples of monocotyledonous and dicotyledonous weed plant species which can be controlled with the compositions according to the invention without being limited to specific species.

Examples of weed species in which the composition acts effectively are monocotyledonous plants, echinoloclaceae and cyperus species in the annual group and perennial cyperus species in the perennial species.

The active substance mixtures according to the invention can be found under certain growing conditions of rice, for example Sagittaria, Alisma, Rotala, MonoKorea (Monochoria, water lily), Eleochais (Eleochais), Scirpus (Cyrus) and Cyperus (Cyperus) has excellent control effects against weeds.

When the herbicide composition according to the present invention is applied to the soil surface before germination, the germination of the weed seeds is completely suppressed or grows until the weeds reach the cotyledon but their growth stops, and finally 3 to 4 weeks have elapsed. After weeds die out.

If the active substance mixture is applied to the green part of the plant after germination, growth stops completely within a very short time after treatment. Since weed plants stay in the growth stage at the point of application, or die more quickly or less quickly after a certain time, in this way the application of the new herbicides according to the invention removes very early and continuously harmful grains to the grain. do.

Although the composition according to the invention has excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, the crops of rice are only insignificantly damaged or not damaged at all. For this reason, the compositions are well suited for selectively inhibiting the growth of unwanted plants in rice farming.

The active substance mixture according to the invention obtains herbicidal activity far beyond the expected effect on the basis of the activity of the individual components. This increased activity significantly reduces the application rate of the individual active substances. Mixing these herbicides can also enhance their long-term functionality or increase their rate of action. These properties are quite advantageous for the user when actually controlling weeds. These properties allow weeds to be controlled more economically, faster, with less labor, and more consistently, thus further increasing crop yields.

In addition, it has been found that the active substance according to the present invention has a pronounced toxicity alleviating or detoxifying effect. That is, the phytotoxic side effects of the active substances used in crops such as, for example, rice are reduced or eliminated completely.

The proportion at which the various components are mixed can vary within wide limits. In particular, the choice of the mixing ratio depends on the components of the mixture used, the weed generation stage, the distribution range of the weeds and the climatic conditions.

The active substance mixtures according to the invention can be prepared in the usual manner by diluting the two components with water or in the form of a mixture which has been applied in granules, or in the form of a so-called tank mixture in which the separately formulated components are diluted together with water. have.

Such compounds (mixtures) can be formulated in a variety of ways depending on the biological parameters and / or chemical-physical parameters that are widely used. Suitable among the possible examples are wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) (e.g. oil-in-water emulsions or water-in-oil emulsions), spray solutions or emulsions, oils or water Dispersions, suspoemulsions, powders (DPs), seed-dressing agents, in particular, granules or water dispersible granules (WG), ULV formulations, microcapsules or waxes for soil application or spraying.

These individual types of formulations are generally known and are described, for example, in Winnacker-Kuchler, "Chemische Technologie, [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986; van Valkenburg," Pesticides Formulation, "Marcel Dekker NY, 2nd Ed. 1972-73; K. Martens," Spray drying Handbook ", 3rd Ed. G. Goodwin Ltd. London.

Necessary formulation aids such as inerts, surfactants, solvents and other additives are also known and are described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J; H.v. Olphen, "Interoduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley Sons, N.Y .; Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ, Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N. Y, 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-Active Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie" [Chemical techology], Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.

Also based on the above formulations, compositions of these active substances with other agrochemically active substances such as other herbicides, fungicides or insecticides as well as fertilizers and / or growth regulators are for example readymixes or tank mixtures. It may be prepared in the form of.

Wetting powders are uniformly dispersed in water and in addition to the active substances wetting agents such as, for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols or fatty amines, alkanes or alkylbenzenesulfonates, and examples Containing dispersants such as sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyl naphthalenesulfonate or sodium oleoylmethyltaurate together with diluents or inerts It is a formulation.

Emulsifiable concentrates are prepared by dissolving the active substance with one or more emulsifiers in an organic solvent (such as butanol, cyclohexanone, dimethylformamide, xylene or other high boiling aromatic compounds or hydrocarbons). As emulsifiers, for example, the following may be used: calcium salts of alkylarylsulfonic acids such as calcium dodecylbenzenesulfonate, or fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, for example Nonionic emulsifiers such as propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Powders are prepared by grinding the active material together with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Granules may be sprayed onto an adsorbent granulating inert material, or the active material concentrate may be sand, kaolinite or granulated inert material using an adhesive such as polyvinyl alcohol, sodium polyacrylate or other mineral oil. It can be prepared by applying to the surface of the carrier such as. In addition, suitable active substances can also be granulated in the usual manner for preparing fertilizer granules, optionally as a mixture with fertilizers.

In general, the agrochemical formulations comprise from 0.1 to 99% by weight, in particular from 2 to 95% by weight of active substance A or B. The concentrations of the active substances A and B in the formulation can be different.

For example, for wettable powders, the active substance concentration is approximately 10 to 95 weight percent and the balance relative to 100 weight percent consists of conventional formulation components. For emulsifiable concentrates, the active substance concentration can be approximately 1 to 85% by weight, preferably 5 to 80% by weight. Formulations in powder form contain 1 to 25% by weight, usually 5 to 20% by weight of active material, and the spray solution contains approximately 0.2 to 25% by weight, preferably 2 to 20% by weight of active material. In the case of granules such as water-dispersible granules, the active substance content depends in part on whether the active compound is in liquid or solid form and which granulation aids and fillers are used. Generally, the water-dispersible granules contain 5 to 90% by weight of the active ingredient, and the spraying granules contain 1 to 50%, preferably 2 to 25% of the active material.

In addition, the aforementioned active substance formulations, where appropriate, include conventional adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.

For use, formulations in the commercial form are optionally diluted in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of spray solutions as well as powders and granules for soil application or spraying are usually no longer diluted with inert materials prior to use.

The required rate of application of such mixtures varies depending on external conditions such as temperature, humidity and type of herbicide used.

The following examples are intended to illustrate the invention.

A. Formulation Examples

(a) 10 parts by weight of the active substance mixture according to the invention is mixed with 90 parts by weight of talc as an inert substance and then the mixture is ground in a hammer mill to obtain a powder.

(b) 5 parts by weight of the active substance mixture, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant, and then the mixture is Grinding in a pinned-disk mill yields a wettable powder that can be easily dispersed in water.

(c) 20 parts by weight of the active substance mixture 6 parts by weight of an alkylphenol polyglycol ether ( ^R Triton × 207), 3 parts by weight of isotridecanol polyglycol ether (8EO) and paraffin mineral oil (eg, approximately 255 to 277 ° C.) And 71 parts by weight and the resulting mixture is ground in a ball mill to a powder of less than 5 microns to give a dispersion concentrate which can be easily dispersed in water.

(d) An emulsifiable concentrate is obtained from 15 parts by weight of the active substance mixture, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

(e) the following components are mixed and the resulting mixture is ground in a pin fixed-disk mill and then the powder obtained is sprayed on water as granulation liquid in a fluidized bed to give water-dispersible granules:

Active substance mixture, 75 parts by weight

Calcium ligninsulfonate, 10 parts by weight

Sodium lauryl sulfate, 5 parts by weight

Polyvinyl alcohol, and 3 parts by weight

Kaolin 7 parts by weight

(f) preliminary milling by homogenizing in the colloid mill, the resulting mixture is milled on a bead mill, and then the resulting suspension is refined and dried in a spray tower using a single-material nozzle to produce water-dispersible Obtain granules.

25 parts by weight of active substance mixture

Sodium 2,2'-Danaphthylmethane-6,6'-

5 parts by weight of disulfonate

Sodium oleoylmethyltaurate, 2 parts by weight

Polyvinyl alcohol, 1 part by weight

Calcium carbonate and 17 parts by weight

50 parts by weight of water

Biological Example

1. Effect of germination on weeds

Seeds or root pieces of monocotyledonous and dicotyledonous weed plants were sown in specification soil in a plastic pot 9 cm in diameter and covered with sand. Weeds appearing in the cultivation of rice were grown in submerged soil and filled with pots of water such that the water reached the surface of the soil or exceeded a few millimeters. The active substance mixtures according to the invention formulated as wettable powders or emulsifiable concentrates and the individual active substances similarly formulated in corresponding experiments are then subjected to 300 to 600 liters of water / ha in the form of an aqueous suspension or emulsion (conversion). At the application rate of), it was applied to the surface of the soil in various amounts, or in the case of rice, it was poured into related water. After treatment, the pot was placed in a greenhouse and then maintained under good growth conditions for weeds. After 3-4 weeks of the test period, the test plants were germinated and scored by visually comparing the undamaged effects on damage or germination to the untreated controls. The herbicide compositions according to the invention exhibited good germinated herbicidal activity against a wide range of weeds and mining weeds.

In all cases, there was a difference between the calculated activity in the composition and the measured activity. The theoretically predicted calculated activity of the mixture is described in S.R. Colby's equation: measured according to "Calculation of synergistic and antagonistic responses of herbicide combinations", Weeds 15 (1967), pages 20-22.

In the case of a two-component mixture, the formula in the literature is as follows;

Thus, for a mixture of three active substances:

In the above formulas,

X is the percent damage by herbicide A at the application rate of x kg / ha,

Y is the percent damage by herbicide B at the application rate of y kg / ha,

Z is the percent damage by herbicide C at the application rate of z kg / ha,

E is the predicted damage rate by herbicide A + B (or A + B + C) at an application rate of x + y (or x + y + z, respectively) kg / ha.

If the actual damage rate exceeds the numerically predicted damage rate, the action of the mixture is additive. That is, there is synergy.

The active substance mixtures according to the invention have greater herbicidal activity than predicted using the Colby's formula based on the observed effects of the individual components when applied individually. Thus, active substance compositions exhibit synergistic behavior.

2. Effect after germination on weeds

Seeds or rhizome flakes of monocotyledonous and dicotyledonous weeds were sown in soil specification in plastic pots and covered with soil, and then grown under favorable growth conditions in a greenhouse. Weeds appearing in the cultivation of rice were grown in pots poured with water to 2 cm depth of soil surface and grown during the test phase. Three weeks after sowing, weeds were treated in the 3-leaf state.

The active substance mixtures according to the invention formulated as wettable powders or emulsifiable concentrates and the individual active substances similarly formulated in the corresponding experiments were applied to the green part of the plant at an application rate of 300 to 600 liters of water / ha (conversion). After spraying in varying amounts and maintaining for approximately 3-4 weeks under optimal growth conditions of the test plants in the greenhouse, the effect of the formulation was visually compared to the untreated control. In the case of rice or weeds that may appear during the cultivation of rice, the active substance is also added directly to the relative hand (similar to the so-called granulation application), or sprayed on plants and the related hand. The compositions according to the invention also had good post-germination herbicidal activity against broad and economically important weeds and broadleaf weeds. The results analyzed by Colby's formula show that the compositions according to the invention have synergism.

Examples of Toxicity Mitigation Activities of Dimuron (B8) and JC940 (B12) Against Anilophos

In the greenhouse, rice crops were transplanted into specification soil in plastic pots and grown to 2.5-leaf state. Water was kept to overflow 3 cm from the soil surface over the entire experimental period.

Subsequently the substances according to the invention were used individually and in the form of a mixture and poured into the potted water in the form of a suspension or emulsion in water.

After about three weeks, the phytotoxic damage to rice was measured by measuring the live weight of the shoots of the test crop.

The table below shows the values predicted by the measured experimental data and Colby's formula. The values shown in the table below show that both Daimuron and JC-940 have a very pronounced effect in reducing phytotoxic damage to rice caused by Anilophos. In other words, these figures show that both herbicides have a pronounced toxic effect on anilophos. For all variants of this mixture, the value predicted by Colby's formula is substantially lower than the measured value.

Calculation of synergistic and antagonistic action of herbicides using Colby's formula:

E = H1 * H2 / 100

Wherein H1 and H2 are the activity of the herbicide in percent.

Claims (8)

A herbicidal composition comprising an effective amount of anilophos and at least one compound (B) (form B compound) selected from the group consisting of the following compounds (B1) to B (5), B (8) and (B12). (1) anilofoss (B1) bensulfuron-methyl, (B2) pyrazosulfuron-ethyl, (B3) cynosulfuron, (B4) imazosulfuron, (B5) AC 014, 1- (2- (cyclopropylcarbonylphenyl) -sulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea, (B8) Daimuron, (B12) JC 940, 1- (2-chlorobenzyl) -3- ( α , α -dimethylbenzyl) urea The method of claim 1, A composition comprising 1 to 99% by weight of the composition of claim 1 and a conventional formulation adjuvant.  The composition as claimed in claim 1 or 2 is characterized in that the wettable powder, emulsifiable concentrate, aqueous solution, emulsion, spray solution (tank mix), dispersion based on oil and water, suspoemulsion, powder, seed -Formulating similarly to conventional crop protection formulations selected from the group comprising dressing agents, granules for soil application or spreading, water dispersible granules, ULV formulations, microcapsules or waxes. A method of controlling unwanted plants, comprising applying an effective amount of the composition claimed in claim 1 to 2 unwanted plants or their habitat, The method of claim 4, wherein A method of selectively controlling weeds among crops. The method of claim 5, Wherein said crop is rice. A method of protecting crops against phytotoxic side effects of herbicides, comprising applying anilophos to the plant, the seed of the plant, or the farmland together with the compound of Form B as claimed in claim 1. The method of claim 7, wherein How to use Anilophos with Daimuron or JC-940.