MX2007015575A - Aqueous crop protection formulations comprising asulam and synergistic herbicidal combinations thereof - Google Patents

Abstract

The present invention relates to crop protectant formulations in the form of aqueous solutions comprising asulam, at least one surfactant from among the group comprising a mixture of quaternary ammonium compounds, sodium lauryl ether sulfate, fatty alcohol polyglycerol esters and ethoxylated fatty amines. Additionally the present invention relates to synergistic herbicidal combination comprising the aqueous formulation of asulam according to the invention and further herbicidal active ingredients.

Description

AQUATIC FORMULATIONS FOR THE PROTECTION OF CROPS WHICH INCLUDE ASULAM AND HERBICIDAL COMBINATIONS SYNERGY OF THEMSELVES DESCRIPTIVE MEMORY The present invention relates to the field of crop protection formulations. In particular, the invention relates to formulations in the form of aqueous solutions comprising asulam herbicidal active ingredient and certain surfactants. The present invention also relates to a synergistic herbicidal combination and to a method of controlling the growth of weeds, comprising the aqueous formulation of asulam according to the invention and herbicidal active ingredients, preferably from the series of the sulfonylureas (e.g. trifloxysulfuron). In general, the herbicidal active ingredients are not used in pure form. Depending on the field and the type of application and the physical, chemical and biological parameters, the active ingredients are used as formulation of active ingredients in admixture with the auxiliary materials and conventional adjuvants. Combinations with other active ingredients are also known to extend this spectrum of action and / or to protect the harvest plants (for example by antifitotoxic agents, antidotes).

The formulations of herbicidal active ingredients should generally have high chemical and physical stability, good application properties and ease of handling and a broad biological action combined with high selectivity. The herbicidal active ingredient asulam is generally used as an aqueous solution, for example under the trade name Asulox®. The disadvantage of this product is the high application rate with which it is applied to the surfaces to be treated. It was an object of the present invention to provide an aqueous crop protection formulation for the active ingredient asulam having improved herbicidal activity. This object is achieved with aqueous herbicidal compositions comprising the herbicidal active ingredient asulam or its salts, such as the potassium salt or the sodium salt, and at least one surfactant selected from group B) consisting of the surfactants B1 : mixtures of quaternary ammonium compounds, B2: sodium lauryl ether sulphate, B3: polyglycerol esters of fatty alcohol and B4: ethoxylated fatty amines. An example of a mixture of quaternary ammonium compounds is Geronol® CF / AS30, see, for example, Material Safety Data Sheet by Rhodia Asia Pacific Pte. Ltd., Singapore. An example of sodium lauryl ether sulfate is Rhodapex® ESB 70 / FEA, see, for example, Material Safety Data Sheet by Rhodia Inc., E.U.A.

An example of a fatty alcohol polyglycerol ester is Synergen® B01, which is a copolymer of glycerol, coconut fatty acid and italic anhydride and is known as CAS No. 67746-02-5. An example of an ethoxylated fatty amine (with 15 ethylene oxide units) is Rhodameen CF / 15H®, see, for example, Material Safety Data Sheet by Rhodia Gerronazzo S.p.A, Italy. The aqueous herbicidal compositions according to the invention show a markedly increased herbicidal activity compared to the aqueous compositions comprising asulam which are known to date. The aqueous herbicidal compositions according to the invention may additionally comprise defoamers and conventional adjuvants and additives, such as antifreeze agents, colorants, fragrances and preservatives. Suitable defoamers are, for example, those based on silicone, preferably Rhodorsil® 481. The antifreeze agents are those of the group consisting of ureas, diols and polyols, such as ethylene glycol and propylene glycol. Suitable preservatives, colorants and fragrances are known to the person skilled in the art. Depending on the expected effect, that is, depending on which harmful plants are to be controlled in the harvest in question, the aqueous herbicidal compositions according to the invention comprise a herbicidal active ingredient, preferably from the series of the sulfonylureas, most preferably trifloxysulfuron (eg sold as the trade name Envoke ™ herbicide). The proportion of the aqueous herbicidal compositions according to the invention (component A) and an additional herbicidal active ingredient (component B), based on the active ingredient, can vary greatly and is dependent on the additional effective herbicidal active ingredient against different weeds in different crops. Therefore (A) :( B) could be in the range of 1000: 1 to 1: 1000, preferably 600: 1 to 1: 600, particularly 400: 1 to 1: 400, most particularly 200: 1 to 1: 200. In case the additional herbicidal active ingredient is from the series of sulfonylureas, e.g. trifloxysulfuron, (A) :( B) could be in the range of 1: 1 and 1000: 1, preferably in the range of 80: 1 and 380: 1, particularly in the range of 110: 1 to 120: 1 based on in the active ingredient. In the event that the additional herbicidal active ingredient (component B) is trifloxysulfuron, e.g. In the formulation of Envoke (TM), the weight ratio of trifloxysulfuron is in the range of between 10 g and 20 g of active ingredient, per hectare, preferably in the range of 14.5 g to 17.5 g of active ingredient per hectare and the asulam ( component A), v.gr. according to formulation example No. 2, it is in a range of 1600 g to 3740 g of active ingredient per hectare, preferably in the range of 1600 g to 1800 g of active ingredient per hectare. The additional herbicidal active ingredient may be either present in the aqueous herbicidal composition according to the invention, as what is known as a prepared mixture or applied as what is known as a tank mixture by joint dilution of the components formulated separately , or in part separately. The aqueous herbicidal compositions according to the invention conventionally comprise the herbicidal active ingredient asulam; a surfactant of group B); Water; if appropriate, an antifoam; if appropriate, auxiliary materials and additives; and, if appropriate, an additional herbicidal active ingredient. In a preferred embodiment, the aqueous herbicidal compositions according to the invention comprise a) asulam of 10 to 50%, or its salts, such as the sodium salt, b) from 1 to 30% of a surfactant of group B), c) from 0 to 1% of an antifoam, d) from 0 to 10% of adjuvants and auxiliary materials, e) from 0 to 5% of an additional active herbicidal ingredient, and f) from 25 to 75% of water. Especially preferred are aqueous herbicidal compositions according to the invention comprising a) from 20 to 50% of asulam, or its salts, such as the sodium salt, b) from 5 to 25% of a surfactant of group B), c) from 0 to 1% of an antifoam, d) adjuvants and auxiliaries from 0 to 10%, e) from 0 to 5% of an additional active herbicidal ingredient, and f) from 25 to 75% of water. Very particularly preferred are aqueous herbicidal compositions according to the invention comprising a) from 25 to 40% of asulam, or its salts, such as the sodium salt, b) from 10 to 20% of a surfactant of group B) , c) from 0 to 1% of an antifoam, d) from 0 to 5% of adjuvants and auxiliary materials, e) from 0 to 3% of an additional herbicidal active ingredient, and f) from 40 to 65% of water. All percentages are by weight. In general, asulam and trifloxysulfuron are used in the form of their sodium salt; in this context, see also 'The Pesticide Manual', 13th edition (2003), The British Crop Protection Council, unless otherwise specified, the terms "asulam" and "trifloxysulfuron" in each case as the free compound and its salts, such as the potassium salt or the sodium salt for the purposes of the present application. The terms "solutions according to the invention" and "herbicidal compositions according to the invention" or "herbicidal compositions" are used interchangeably in the following. The above-mentioned auxiliary materials of formulation of groups c) and d) are known to those skilled in the art and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2a. Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2a. Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2a. Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzfláchenaktive Áthylenoxidaddukte [Ethylene oxide surfactant adducts]", Wiss. Veriagsgesell., Stuttgart 1976; Winnacker-Küchier, "Chemische Technologie [Chemical Technology]", Volume 7, C. Hauser Verlag Munich, 4a. Ed. 1986. For use, the aqueous herbicidal compositions according to the invention can be diluted in a customary manner, for example with water. It may be advantageous to add other agrochemical active ingredients (for example the building elements for tank mixtures in the form of suitable formulations) and / or customary auxiliary materials and the additives conventionally used for their use and / or fertilizers to the resulting spray mixtures. . It has been found advantageous to dilute the aqueous herbicidal compositions according to the invention with aqueous solutions of fertilizers, for example ammonium nitrate and ammonium sulfate. The present invention also relates therefore to those aqueous herbicidal compositions comprising the agrochemical active ingredients mentioned in the previous section, auxiliary materials and additives and / or fertilizers. The aqueous herbicidal compositions according to the invention have an outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. They even affect good control of perennial problematic weeds that emerge from rhizomes, underground stems or other perennial organs. In this context, according to the invention they are usually applied after their appearance. The aqueous herbicidal compositions according to the invention are distinguished by a prolonged herbicidal activity with prompt access. The combination, according to the invention, of the herbicidal active ingredients and surfactants makes it possible to substantially reduce the necessary proportion of use of the active ingredients. The aforementioned properties and advantages are useful in the practical control of harmful plants to keep agricultural crops free of undesirable plant competition and thus to ensure and / or to increase yields in terms of quality and quantity. With respect to the properties described above, these new competitions clearly exceed the prior art. Although the aqueous herbicidal compositions according to the invention have an outstanding herbicidal activity against the harmful monocotyledonous and dicotyledonous plants, the crop plants of the economically important crops, for example crops of dicotyledonous such as soybean, cotton, oilseed rape, beet , or crops of grasses such as wheat, barley, rye, oats, sorghum and millet, sugar cane, coffee, tea, cocoa, coconut, bananas or corn, suffer only a minor degree of damage or none. This is the reason why the aqueous herbicidal compositions according to the invention are highly suitable for selectively controlling undesirable vegetation in the plantations of useful agricultural crops or in ornamental plantations. Due to its herbicidal properties, the aqueous herbicidal compositions according to the invention can also be used to control harmful plants in crops of genetically modified plants that are known or are yet to be developed. In general, transgenic plants are distinguished by their specific advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to diseases in plants or pathogens that cause diseases in plants, such as certain insects or microorganisms such as fungi, bacteria or viruses.

Other specific properties have to do with, for example, the harvest with respect to quantity, quality, storage capacity, to the formulation and specific ingredients. Thus, transgenic plants are known with an increasing content of starch or a modified quality of starch, or those with different formulation of fatty acids from the harvest. The use of the aqueous herbicidal compositions according to the invention is preferred in the economically important transgenic crops of ornamental and useful plants, for example gramineous crops such as wheat, barley, rye, oats, sorghum and millet, rice and corn, or beet crops, cotton, soybeans, oilseed rape, potato, tomato, peas and other vegetables. The aqueous herbicidal compositions according to the invention can preferably be used as herbicides in crops of useful plants that are resistant, or that have become resistant by means of genetic engineering, to the phytotoxic effects of the herbicidal active ingredients. When the aqueous herbicidal compositions according to the invention are applied to transgenic crops, effects that are specific for use in the transgenic crop in question are often observed, for example a modified or specifically expanded weed spectrum that can be controlled, Modified application rates that can be used for the application, preferably a good combination ability with the herbicides to which the transgenic crop is resistant, and an effect on the growth and yield of the transgenic harvest plants, in addition to the effects , against harmful plants, which can be observed in other crops. The present invention also relates moreover to a method for controlling the growth of undesirable plants, preferably in crops of plants such as cereals (for example wheat, barley, rye, oats, rice, corn, sorghum and millet), beet, sugarcane, oilseed rape, cotton and soybeans, particularly preferably in monocotyledonous crops such as cereals, for example wheat, barley, rye, oats, their hybridization products such as triticale, rice, corn, sorghum and millet, one or more aqueous herbicidal compositions according to the invention that are being applied to harmful plants, the parts of the plant, seeds of the plant or the area in which the plants grow, for example the area in culture. Plant crops may also have been genetically modified or have been obtained by mutation selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors. The aqueous herbicidal compositions according to the invention are prepared in the manner with which the person skilled in the art is familiar, for example by mixing the individual constituents; see, in this context, Winnacker-Küchier, "Chemische Technologie", volume 7, C. Hauser Verlag Munich, 4a. edition, 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Sparay Drying" handbook, 3a. edition, 1979, G. Goodwin Ltd. London. The following examples illustrate the invention. The surfactants and adjuvants used in this context mean: Geronol® CF / AS30 = mixture of quaternary ammonium compounds, supplier: Rhodia. Rhodapex® ESB 70 / FEA = sodium lauryl ether sulphate (solution in water with 70% concentration), supplier: Rhodia. Synergen® B01 = fatty alcohol polyglycerol ester (glycerol copolymer, coconut fatty acid and italic anhydride), supplier: Clariant. Rhodorsil® 481 = antifoam based on silicone, supplier: Rhodia. Rhodameen CF / 15H® = ethoxylated fatty amines, manufacturer: Rhone-Poulenc Geronazzo SpA, Div. De Rhone-Poulenc S.A EXAMPLE OF FORMULATION 1 34.30 g of asulam (in the form of a sodium salt), 13.57 g of Rhodapex® ES B70, 0.03 g of Rhodorsil® 481 and 52.10 g of water were stirred to give a homogeneous solution.

EXAMPLE OF FORMULATION 2 34.30 g of the asulam (in the form of a sodium salt), 13.97 g of Geronol® CF / AS30, 0.03 g of Rhodorsil® 481 and 51.70 g of water were stirred to give a homogeneous solution.

EXAMPLE OF FORMULATION 3 34.30 g of the asulam (in the form of a sodium salt), 13.57 g of Rhodameen CF / 15H®, O.03 g of Rhodorsil® 481 and 52.10 g of water were stirred to give a homogeneous solution.

EXAMPLE OF FORMULATION "V" which is known from the prior art, prepared for comparative purposes 3. 80 g of the asulam (in the form of sodium salt) and 56.20 g of water to give a homogeneous solution.

BIOLOGICAL EXAMPLE 1. Post-emergence herbicidal action against harmful plants Seeds of harmful monocotyledonous and dicotyledonous plants are placed in cardboard pots containing sandy loam, covered with soil and cultivated in the greenhouse under good growth conditions. Two to three weeks after seeding, the test plants, which are in the three-leaf stage, are treated with the aqueous herbicidal compositions according to the invention and, for comparison reasons, with a herbicidal composition of the prior art. The herbicidal spray formulations are applied on the surface of the green parts of the plants in various dosages at a water application rate of 600 to 800 l / ha (converted). After the test plants have been allowed to stand in the greenhouse for 3 to 4 weeks under optimum growth conditions, the effect of the aqueous herbicidal compositions according to the invention is evaluated. The abbreviations indicate: CYNDA Cynodon dactylon DIGSA Digitaria sanguinalis PANDI Panicum dichotomiflorum PANRA Panicum ramosum PESGL Pennisetum glaucum SORHA Sorghum halepense i. to. Active ingredient, asulam in each case in the three tables TABLE 1 TABLE 2 The results of tables 1 and 2 show that, in the same application rate, the aqueous herbicidal compositions according to the invention have better herbicidal activity against different harmful plants than the one known in the prior art. In another experiment, 120 g of ammonium sulfate (AMS) per hectare were used in each case when applying the aqueous herbicidal compositions 1 and 2 according to the invention.

TABLE 3 The results in Table 3 show that the aqueous herbicidal compositions according to the invention, which comprise the ammonium sulfate fertilizer, have an even greater herbicidal activity. 2. Synergistic combination of herbicides comprising the formulation of asulam according to the invention and other herbicidal active ingredients A synergistic effect of herbicides is always present when the activity against the weeds of the combination of herbicides exceeds the total of the activities of the herbicides when apply individually. The expected activity for a given combination of two active compounds can be calculated according to SR Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 15, (1967), 20-22) as follows: If X is the percentage of inhibition of growth by herbicide A at an application rate of mg / ha, Y is the percentage of inhibition of growth by herbicide B at an application rate of ng / ha, and E is the expected growth as a percentage of the control with the herbicides A + B by applying the active compounds A and B in the application rates of m and ng / ha, then E = 100 - (X + Y - XY / 100). The efficiency is calculated as a percentage of the control (%): 0% is an efficiency that corresponds to that of the untreated control, while an efficiency of 100% means that no growth is observed. If the actual activity against the weeds of the herbicide combination exceeds the calculated value, then the activity of the combination is extraordinarily additive, ie there is a synergistic effect. In this case, the effectiveness that was actually observed must be greater than the value for the expected efficiency (E) calculated from the formula mentioned above. TABLE 4 Abbreviations: Efficiency as a percentage of control; A + NIS = asulam plus the nonionic surfactant (NIS) as known to the person skilled in the art as in formulation example No. 2 applied with 4.66 l / ha; B + NIS = trifloxysulfuron as formulation of Envoke ™ plus nonionic surfactant (NIS) as known to the person skilled in the art applied with 0.073 I / ha; TM = tank mix of formulation example No. 2 of asulam plus the Envoke ™ formulation of trifloxysulfuron (A + NIS + B) in the aforementioned dosages; E1 = (efficiency B + efficiency A - ((efficiency BX efficiency A of B) / 100), where E1 = expected efficiency if the components of the tank mixture are additive; TM-E1 = difference between the expected additive effect and the Actual effect of the tank mixture (values greater than zero indicate synergy).

The results in Table 4 show that a good unexpected synergistic effect increased with respect to each of all the weeds tested using the tank mixture (TM = A + B + NIS). In another experiment, the formulations according to the invention shown in the Example No. 1 together with trifloxysulfuron after the appearance at several harmful plants. Again it was shown that good effects are obtained unexpected synergies. Although the invention has been described with reference to preferred embodiments and examples thereof, the scope of the present invention is not is limited only to those modalities described. As will be evident to those skilled in the art, adaptations and modifications may be made to the invention described above without departing from the spirit and scope of the invention, which is defined by the following claims.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. An aqueous herbicidal composition comprising a) the herbicidal active ingredient asulam or its salts, preferably the sodium salt, b) at least one surfactant of group B) consisting of the surfactants B1. mixtures of quaternary ammonium compounds, B2. Sodium lauryl ether sulfate, B3. polyglycerol esters of fatty alcohol and B4. ethoxylated fatty amines.

2. The aqueous herbicidal composition according to claim 1, further characterized in that the surfactant of group B) is selected from Geronol® CF / AS30, Rhodapex® ESB 70 / FEA, Rhodameen CF / 15H® and Synergen® B01.

3. The aqueous herbicidal composition according to claim 1, further characterized in that it additionally comprises c) an antifoam.

4. The aqueous herbicidal composition according to claim 1, further characterized in that it additionally comprises d) auxiliary materials and adjuvants from the group of antifreeze agents, colorants, fragrances and preservatives.

5. - The aqueous herbicidal composition according to claim 1, further characterized in that it additionally comprises e) an additional herbicidal active ingredient.

6. The aqueous herbicidal composition according to claim 1, further characterized in that it comprises a) from 10 to 50% of asulam, or its salts, preferably the sodium salt, b) from 1 to 30% of a surfactant of the group B), c) from 0 to 1% of an antifoam, d) from 0 to 10% of adjuvants and auxiliary materials, e) from 0 to 5% of an additional active herbicidal ingredient, and f) from 25% to 75% of water.

7. The aqueous herbicidal composition according to claim 1, further characterized in that it comprises a) from 20 to 50% of asulam, or its salts, preferably the sodium salt, b) from 5 to 25% of a surfactant of the group B), c) from 0 to 1% of an antifoam, d) from 0 to 10% of adjuvants and auxiliary materials, e) from 0 to 5% of an additional herbicidal active ingredient, and f) from 25 to 75% of Water.

8. The aqueous herbicidal composition according to claim 1, further characterized in that they comprise a) 25 to 40% asulam, or its salts, preferably the sodium salt, b) 10 to 20% of a group B surfactant. ), c) from 0 to 1% of an antifoam, d) from 0 to 5% of adjuvants and auxiliary materials, e) from 0 to 3% of an additional active herbicidal ingredient, and f) from 40 to 65% of water.

9. The aqueous herbicidal composition according to any of claims 5 to 8, further characterized in that the additional herbicidal active ingredient is trifloxysulfuron or its salts, preferably the sodium salt.

10. The aqueous herbicidal composition according to claim 1, further characterized in that it additionally comprises fertilizer.

11. The aqueous herbicidal composition according to claim 10, further characterized in that the fertilizer is ammonium sulfate or ammonium nitrate.

12. A method for controlling undesirable vegetation, wherein an effective amount of the ingredients a) and b) of an aqueous herbicidal composition as claimed in claim 1 is applied to the plants, parts of the plants, the seed or the surface on which the plants grow.

13. The use of an aqueous herbicidal composition as claimed in claim 1 to control undesirable vegetation.