KR20080056712A - 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

Aqueous crop protection formulations comprising asulam and synergistic herbicidal combinations according to the present invention.

The present invention relates to the area of crop protectant formulations. In particular, the present invention relates to a preparation in the form of an aqueous solution comprising asulam and certain surfactants as herbicidal active ingredients. The present invention also provides a synergistic agent comprising the asulam water-soluble agent according to the invention and additional herbicidal active ingredients, preferably herbicidal active ingredients selected from the family of sulfonylureas (eg trifloxysulfuron). It relates to a synergistic herbicidal combination and a method of regulating weed growth.

In general, herbicidal active ingredients are not applied in the form of the ingredients themselves. Depending on the area of application and the type and the physical, chemical and biological parameters, the active ingredients are applied in active ingredient formulations in admixture with conventional auxiliaries and adjuvants. It is also known to combine additional active ingredients (eg safeners, antidote) to broaden the activity spectrum and / or to protect crop plants.

Formulations of the herbicidal active ingredients should generally have high chemical and physical stability, good application quality and userliness and high selectivity while at the same time having a wide biological activity. The herbicidal active ingredient asulam is generally applied in aqueous solution, for example sold under the trade name Asulox®. The disadvantage of this product is the high application rate that must be applied in the area to be treated.

It is an object of the present invention to provide a water soluble crop protection preparation of the active ingredient Ashlam with improved herbicidal activity.

This object is achieved by a water-soluble herbicidal composition comprising the herbicidal active ingredient asulam or a salt thereof, for example a potassium salt or a sodium salt, and at least one surfactant selected from group B) consisting of the following surfactants:

B1: mixture of quaternary ammonium compounds,

B2: sodium lauryl ether sulfate,

B3: fatty alcohol polyglycerol esters and

B4: ethoxylated fatty amine.

An example of a mixture of quaternary ammonium compounds is Geronol® CF / AS30, for example Rhodia Asia Pacific Pte. See Material Safety Data Sheet of Ltd., Singapore.

An example of sodium lauryl ether sulfate is Rhodapex® ESB 70 / FEA, see, for example, the Material Safety Data Sheet from Rhodia Inc., USA.

An example of a fatty alcohol polyglycerol ester is Synergen® B01, which consists of a copolymer of glycerol, coconut fatty acid and phthalic anhydride, which is a CAS No. Known as 67746-02-5.

An example of an ethoxylated fatty amine (with 15 ethylene oxide units) is Rhodameen CF / 15H®, see for example the Safety Data Sheet of Rhodia Gerronazzo S.p.A, Italy.

The water soluble herbicidal compositions according to the present invention exhibit markedly increased herbicidal activity compared to the asulam-containing water soluble compositions known to date.

The water-soluble herbicidal composition according to the present invention may additionally include antifoams and additives such as conventional adjuvant and antifreeze agents, colorants, fragrances and preservatives.

Suitable antifoams are, for example, silicone-based antifoams, preferably Rhodorsil® 481.

Suitable anticoagulants are selected from the group consisting of urea, diols and polyols, such as ethylene glycol and propylene glycol. Suitable preservatives, colorants and fragrances are known to those skilled in the art.

Depending on the intended purpose, ie depending on the harmful plants to be controlled in the crop, the water-soluble herbicidal composition according to the invention additionally further comprises a herbicidal active ingredient, preferably selected from the family of sulfonylureas, more Preferably trifloxysulfuron (e.g., marketed under the herbicide trade name Envoke ™).

The proportion of the water soluble herbicidal composition (composition A) and the additional herbicidal active ingredient (composition B) according to the invention can vary widely based on the active ingredient, depending on the activity of the additional herbicidal active ingredient against various weeds of various crops. have. Therefore, (A) :( B) may range from 1000: 1 to 1: 1000, preferably 600: 1 to 1: 600, more preferably 400: 1 to 1: 400, even more preferably Is from 200: 1 to 1: 200.

If the additional active ingredient is of the sulfonylurea series, for example triplexulfuryfuron, (A) :( B) may range from 1: 1 to 1000: 1 based on the active ingredient, preferably 80 It may range from 1: 1 to 380: 1, more preferably from 110: 1 to 120: 1.

If the additional herbicidal active ingredient (composition B) is a formulation of triplexulfuryfuron, for example Envoke ™, the weight ratio of the triplexylfuranfuron is in the range of 10 g to 20 g active ingredient per hectare, preferably Preferably in the range of 14.5 g to 17.5 g active ingredient per hectare, and in the range of 1600 g to 3740 g active ingredient per hectare according to the formulation of Ashlam (composition A), for example 2, preferably Is in the range of 1600 g to 1800 g active ingredient per hectare.

The additional herbicidal active ingredient may be present in the water-soluble herbicidal composition according to the invention as known as a "ready mix" and as a "tank mix", a joint dilution of the formulations which have been formulated separately or partially separated. May be applied by

Water-soluble herbicidal compositions according to the invention are typically asulam, the herbicidal active ingredient; Surfactant selected from group B); Antifoam if necessary; Auxiliary and additive additives, if necessary; And, if necessary, additional herbicidal active ingredients.

In a preferred embodiment, the water soluble herbicidal composition according to the invention

a) 10-50% of asulam, or salts thereof, eg sodium salt,

b) 1 to 30% of a surfactant selected from group B),

c) 0-1% antifoam,

d) 0-10% of adjuvant and adjuvant,

e) 0-5% additional herbicidal active ingredient, and

f) 25 to 75% water.

More preferably, the water-soluble herbicidal composition according to the present invention

a) 20-50% asulam, or salts thereof, eg sodium salt,

b) 5 to 25% of a surfactant selected from group B),

c) 0-1% antifoam,

d) 0-10% of adjuvant and adjuvant,

e) 0-5% additional herbicidal active ingredient, and

f) 25 to 75% water.

Even more preferred water-soluble herbicidal compositions according to the present invention

a) 25 to 40% asulam, or salts thereof, eg sodium salt,

b) from 10 to 20% of a surfactant selected from group B),

c) 0-1% antifoam,

d) 0-5% adjuvant and adjuvant,

e) 0 to 3% additional herbicidal active ingredient, and

f) those containing 40 to 65% water.

All percentages are by weight.

As a result, the asulam and the triplelocsulfuron are used in their sodium salt form; In this regard also see "The Pesticide Manual", 13th edition (2003), The British Crop Protection Council. Unless otherwise indicated, the terms “asulam” and “triflocfurfuron” should be understood in each case to mean the free base compound and its salts, such as potassium salts or sodium salts, as desired in the present application. .

The terms "solution according to the present invention" and "herbicidal composition according to the present invention" or "herbicidal composition" are used interchangeably herein.

nfeldt, "Grenzfl

chenaktive

thylenoxidaddukte [Surface-active ethylene oxide adducts]", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-K

chler, "Chemische Technologie [Chemical technology]", Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986에 개시되어 있다.Formulation aids of the aforementioned groups c) and d) are known to those skilled in the art, for example in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Sch

nfeldt, "Grenzfl

chenaktive

thylenoxidaddukte [Surface-active ethylene oxide adducts] ", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-K

chler, "Chemische Technologie [Chemical technology]", Volume 7, C. Hauser Verlag Munich, 4th Ed. It is disclosed in 1986.

In use, the water soluble herbicidal composition according to the invention can be diluted using conventional methods, for example water. To the resulting spray mixtures additional agrochemical active ingredients (e.g., ingredients for tank mixes in the form of suitable formulations) and / or conventional auxiliaries and additives and / or fertilizers commonly used for application It may be beneficial to add. Dilution of the water-soluble herbicidal compositions according to the invention with aqueous fertilizer solutions such as, for example, ammonium nitrate and ammonium sulfate has proved to be beneficial.

The present invention therefore also relates to a water-soluble herbicidal composition comprising the aforementioned pesticide active ingredient, auxiliaries and additives and / or fertilizers.

Water-soluble herbicidal compositions according to the present invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. They have a major impact on controlling perennial problem weeds that occur from rhizomes, root stocks, or other perennial organs. In this regard, the composition according to the invention is generally applied until post-emergence in germination.

Aqueous herbicidal compositions according to the present invention have significant onset and sustained herbicidal activity. The combination of the herbicidal active ingredient and the surfactant according to the invention makes it possible to substantially reduce the required application rate of the active ingredient.

The aforementioned properties and advantages are useful for substantially controlling harmful plants in order to free the crops from undesirable plant competition, thus ensuring and / or increasing productivity in terms of quantity and quality. With regard to the properties described above, this new competition is certainly superior to the prior art.

Although the water-soluble herbicidal composition according to the present invention has excellent herbicidal activity against monocotyledonous and dicotyledonous harmful plants, agricultural plants of economically important crops, such as soybean, cotton, oilseed rape, , Dicotyledonous crops such as sugar beet or crests such as wheat, barley, rye, oats, sorghum and millet, sugarcane, coffee, tea, cacao, coconut, banana or corn ( Graminaceous crops suffer only little or no damage. This is why the water-soluble herbicidal compositions according to the invention are very suitable for selectively controlling plants which are undesirable for the cultivation or decorative cultivation of agriculturally useful crops.

Because of their herbicidal properties, the water soluble herbicidal compositions according to the invention can also be applied to control harmful plants in crops of genetically engineered plants, known or in the future. As a result, transgenic plants have certain beneficial properties, for example beneficial properties such as resistance to certain insecticides, in particular certain herbicides, or resistance to certain insects or pathogens such as fungi, bacteria or viruses that cause plant diseases or plant diseases. Excellent at Other specific properties relate to farming associated with, for example, quantity, quality, storage, composition and certain ingredients. Thus, it is known that transgenic plants or crops with increased starch concentration or controlled starch quality have different fatty acid compositions.

The use of water soluble herbicidal compositions according to the invention is for example rice, crops such as wheat, barley, rye, oats, sugar cane (sorghum) and millet, rice and corn or other sugar beets, cotton, soybeans. It is preferred for the transformation culture of economically important useful plants and decorations, such as the cultivation of oilseed grapefruit, potatoes, tomatoes, peas and other plants. The water-soluble herbicidal compositions according to the invention can be applied as herbicides to crops of useful plants, which are preferably resistant to the phytotoxic effects of the herbicidal active ingredient or made to be resistant by genetic manipulation.

When the water-soluble herbicidal composition according to the present invention is applied to a transgenic crop, specific effects are frequently observed on the application of the transgenic crop in question, and the specific effect is on the effects that can be observed in other crops against harmful plants. In addition, for example, a specifically broadened weed spectrum that is regulated or can be controlled, a controlled application rate that can be applied for a particular use, preferably a good combination with a herbicide to which the transformed crop is resistant, and The effect on the growth and yield of converted crop plants.

The invention furthermore provides methods for controlling the growth of undesirable plants, preferably cereals (eg wheat, barley, rye, oats, rice, corn, forage plants and millet), sugar beets, sugar cane, oilseeds. For plant crops such as grapefruit, cotton and soybeans, more preferably monocotyledonous crops such as cereals, for example wheat, barley, rye, oats and their hybrid products such as rye wheat, rice, corn, sugar cane and millet For crops of the invention, the invention relates to the application of one or more water soluble herbicidal compositions according to the invention to a harmful plant, plant part, plant seed or region in which the plant grows, for example a culture.

Plant crops may also be genetically controlled or obtained by variant selection and are preferably resistant to acetolactate synthase (ALS) inhibitors.

chler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London 참조.Water-soluble herbicidal compositions according to the invention can be prepared by methods known to those skilled in the art, for example by mixing the individual components; In this regard Winnacker-K

chler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. See London.

The following examples illustrate the invention.

The surfactants and adjuvants used below are as follows:

Geronol ^® CF / AS30 = mixture of quaternary ammonium compounds, supplied by Rhodia

Rhodapex ^® ESB 70 / FEA = sodium lauryl ether sulfate (70% strength aqueous solution), supplied by Rhodia

Synergen ^® B01 = fatty alcohol polyglycerol esters (glycerol, coconut fatty acid and phthalic anhydride) from Clariant

Rhodorsil ^® 481 = Silicone-based antifoaming agent from Rhodia

Rhodameen CF / 15H® = ethoxylated fatty amine, manufacturer: Rhone-Poulenc Geronazzo SpA, Div. of Rhone-Poulenc S.A

Formulation Example 1:

  34.30 g Ashlam (in the form of sodium salt),

13.57 g Rhodapex ^® ES B70,

0.03 g Rhodorsil ^® 481 and

  52.1O g water

  Stir to prepare a homogeneous solution.

Formulation Example 2:

  34.30 g Ashlam (in the form of sodium salt),

13.97 g Geronol ^® CF / AS30,

0.03 g Rhodorsil ^® 481 and

  51.7O g water

  Stir to prepare a homogeneous solution.

Formulation Example 3:

  34.30 g Ashlam (in the form of sodium salt),

13.57 g Rhodameen CF / 15H ^® ,

0.03 g Rhodorsil ^® 481 and

  52.1O g water

  Stir to prepare a homogeneous solution.

Formulation Example "V", known in the prior art, was prepared as follows for comparison purposes:

  43.80 g Ashlam (in sodium salt form) and

  56.2O g water

  Stir to prepare a homogeneous solution.

Biological Examples:

1. Herbicide activity until post-emergence in germination of harmful plants

Seeds of monocotyledonous and dicotyledonous harmful plants are placed in cardboard jars containing sandy loam, covered with soil and grown in greenhouses with good growth conditions. Two or three weeks after sowing, the three-leaf stage test plants were treated with water-soluble herbicidal compositions according to the invention and herbicidal compositions according to the prior art for comparison purposes. The herbicidal composition is sprayed onto the surface of the green plant part at various dosages at a water application rate of 600 to 800 I / ha (converted). After the test plants are allowed to grow for 3 to 4 weeks under optimal growth conditions in the greenhouse, the effect of the water soluble herbicidal composition according to the invention is evaluated.

The abbreviation means:

CYNDA Cynodon dactylon DIGSA Digitaria sanguinalis

PANDI Panicum dichotomiflorum PANRA Panicum ramosum

PESGL Pennisetum glaucum SORHA Sorghum halepense

a.i. Active ingredient, in each case asulam

Herbicide Composition [Example Number] Dosing rate [g a.i./ha] Herbicidal activity against harmful plants DIGSA SORHA PANRA PESGL One 1400 73% 63% 63% 93% 2 1400 62% 57% 58% 92% 3 1400 53% 53% 63% 88% V 1400 25% 30% 48% 73%

Herbicide Composition [Example Number] Dosing rate [g a.i./ha] Herbicidal activity against harmful plants PANDI CYNDA One 2800 63% 89% 2 2800 62% 84% 3 2800 60% 83% V 2800 40% 30%

The results in Tables 1 and 2 show that at the same application rate, the water-soluble herbicidal compositions according to the invention have better herbicidal activity against various harmful plants than are known in the art.

In a further experiment, in each case 120 g of ammonium sulfate (AMS) per hectare was applied when treating the water-soluble herbicidal compositions 1 and 2 according to the invention.

Herbicide Composition [Example Number] Dosing rate [g a.i./ha] Herbicidal activity against harmful plants PANDI CYNDA One 2800 63% 89% 1 + 120g AMS 2800 68% 91% 2 2800 62% 84% 2 + 120g AMS 2800 65% 88% 3 2800 60% 83% 3 + 120g AMS 2800 63% 93%

The results in Table 3 show that the water-soluble herbicidal composition according to the present invention exhibits higher herbicidal activity when it comprises ammonium sulfate, a fertilizer.

2. A synergistic herbicidal combination comprising a water-soluble preparation of asulam according to the invention and an additional herbicidal active ingredient

The synergistic effects of herbicides exist when the effects on the weeds of the herbicide combinations are applied individually, exceeding the total effect of each herbicide. The expected effect for a given combination of two active compounds can be calculated according to S. R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 15, (1967), 20-22), as follows:

X is the percent growth inhibition by herbicide A at an application rate of m g / ha,

Y is the percent growth inhibition by herbicide B at an application rate of n g / ha,

If E is the expected growth, which is the percentage of control achieved with herbicide A + B when applying active compounds A and B at application rates of m and n g / ha,

E = 100-(X + Y-XY / 100).

Efficacy is calculated as percent control: 0% is the potency corresponding to the results of the untreated control and 100% potency means no growth at all.

If the actual activity on the weeds of the herbicide combination exceeds the calculated value, it means that the activity of the combination is better than additive, ie there is a synergistic effect. In this case, the actually observed efficacy should be greater than the value of the expected efficacy (E) calculated from the above mentioned formula.

Furtherance Herbicidal efficacy against harmful plants (weeds) applied before germination in germination Redroot pigweed Boradleaf signalgrass Crabgrass Fall panicum Prickly Sida A + NIS 25 93 85 94 60 B + NIS 95 59 68 79 20 TM 100 99 99 99 78 TM-E1 3.75 1.87 3.8 0.26 10

The abbreviations are as follows: efficacy is expressed in percent of control; A + NIS = Asulam plus nonionic surfactant (NIS), where NIS is 4 pints / acre application well known to those of ordinary skill as used in Formulation Example 2; B + NIS = Envoke ™ formulation plus triple-locksulfuron plus a nonionic surfactant (NIS), NIS is well known to those of ordinary skill in the application of 0.3 oz / acre; TM = tank mix (A + NIS + B) of the Envoke ™ formulation, which is the Ashula formulation Example 2 plus triple-locksulfuron equivalent to the above dose; E1 = (B potency + A potency-((B potency x A potency) / 100), where E1 is the potency expected if the tank mix compositions are additive; TM-E1 = the expected additive effect and the actual tank mix Difference in the effect (values greater than zero indicate synergy).

The results in Table 4 show that using a tank mix (TM = A + B + NIS) produced a good synergistic effect that was not expected in each of all tested weeds. In a further experiment, the formulations according to the invention shown in Example 1 were applied together with triplelocksulfuron until ripening in germination against various harmful plants. As a result, an unexpected synergistic effect was obtained.

Although the present invention has been described with reference to preferred examples and embodiments thereof, the scope of the present invention is not limited to such described embodiments. As will be apparent to those skilled in the art, modifications and variations of the present invention described above can be carried out without departing from the spirit and scope of the present invention, the scope of the present invention is set forth in the following patents It is defined by the claims.

Claims (13)

a) herbicide active ingredient asulam or a salt thereof, preferably a sodium salt, b) with a mixture of quaternary ammonium compounds (B1), sodium lauryl ether sulfate (B2), fatty alcohol polyglycerol esters (B3) and ethoxylated fatty amines (B4) At least one surfactant selected from group B) Aqueous herbicidal composition comprising a. The water-soluble herbicidal composition of claim 1, wherein the surfactant selected from group B) is selected from Geronol ^® CF / AS30, Rhodapex ^® ESB 70 / FEA, Rhodameen CF / 15H® and Synergen ^® BOl. The water-soluble herbicidal composition according to claim 1, further comprising c) an antifoaming agent. The water-soluble herbicidal composition of claim 1, further comprising: d) adjuvant and adjuvant selected from anticoagulant, colorant, fragrance and preservative. 2. The water soluble herbicidal composition of claim 1, further comprising e) an additional herbicidal active ingredient. The method of claim 1, wherein the composition a) 10 to 50% asulam or salts thereof, preferably sodium salts, b) 1 to 30% of a surfactant selected from group B), c) 0-1% antifoam, d) 0-10% adjuvant and adjuvant, e) 0-5% additional herbicidal active ingredient, and f) 25 to 75% water Water-soluble herbicidal composition comprising a. The method of claim 1, wherein the composition a) 20 to 50% asulam or salts thereof, preferably sodium salts, b) 5 to 25% of a surfactant selected from group B), c) 0-1% antifoam, d) 0-10% adjuvant and adjuvant, e) 0-5% additional herbicidal active ingredient, and f) 25 to 75% water Water-soluble herbicidal composition comprising a. The method of claim 1, wherein the composition a) 25 to 40% asulam or salts thereof, preferably sodium salts, b) from 10 to 20% of a surfactant selected from group B), c) 0-1% antifoam, d) 0-5% adjuvant and adjuvant, e) 0 to 3% additional herbicidal active ingredient, and f) 40 to 65% water Water-soluble herbicidal composition comprising a. The water-soluble herbicidal composition according to any one of claims 5 to 8, wherein the additional herbicidal active ingredient is trifloxysulfuron or a salt thereof, preferably a sodium salt. The water-soluble herbicidal composition of claim 1, further comprising a fertilizer. The water-soluble herbicidal composition according to claim 10, wherein the fertilizer is ammonium sulfate or ammonium nitrate. A method of controlling undesirable plants, characterized in that the effective amount of components a) and b) of the water-soluble herbicidal composition of claim 1 is applied to the plant, part of the plant, seeds or the area in which the plant grows. Use of the water soluble herbicidal composition of claim 1 for controlling undesirable plants.