JP5797853B2 - Stable aqueous suspension herbicidal composition containing glyphosate - Google Patents

Description

The present invention relates to an aqueous suspension herbicidal composition that is physicochemically stable even in highly concentrated electrolyte solutions such as glyphosate, and more particularly, as a herbicide active ingredient, glyphosate salt and saflufenacil are mixed with an effect enhancer. The herbicidal composition for agricultural use in the form of a physicochemically stable aqueous suspension produced as described above.

Among the herbicidal active ingredients for agriculture, glyphosate salt and saflufenacil are known to have a herbicidal effect over a wide variety of broadleaf and Sasamoto family grasses. In particular, glyphosate salt has a relatively low price and is a herbicide used in a wide range. On the other hand, the herbicidal effect is very gradually developed, and there is a problem in using it as an effective hay control agent. In order to solve such problems, there is an effort to efficiently control weeds by combining the herbicide active ingredient saflufenacyl with glyphosate salt (see, for example, Patent Document 1).

However, the known techniques are mainly for the purpose of increasing the rainfastness of glyphosate, producing glyphosate salt and saflufenacil in a single package formulation form, or separating glyphosate and saflufenacil formulations separately. Refers to a tank mix method which is manufactured and mixed with water at a certain ratio immediately before application. By the way, the specific example with respect to the method of formulating a single package in the single package formulation of the said glyphosate salt and saflufenacyl is not disclosed.

In formulating glyphosate salt and saflufenacil into a herbicidal composition in a single package formulation, it is known that there are problems in physicochemical instability and biological efficacy. That is, glyphosate salt as a herbicide active ingredient consists of a very high aqueous electrolyte solution. Therefore, saflufenacil, a suspended herbicide active ingredient coexisting in an aqueous phase containing glyphosate salt, is very physicochemically unstable, so mutual layer separation between active ingredients and Since particle growth occurs continuously, it makes it very difficult to produce a herbicidal composition in the form of a stable single package formulation containing all glyphosate salt and saflufenacyl. Further, in terms of biological medicinal effects, the herbicidal effect (particularly rapid effect) of such herbicidal compositions is not sufficient, and commercial access is difficult.

Here, as a result of studying an example of a stable single-package preparation in the form of an aqueous suspension in which glyphosate salt and saflufenacyl coexist as an herbicidal active ingredient as the herbicide active ingredient, the effect of using a specific surfactant in combination When formulated with an enhancer, the herbicidal work is surprisingly very physicochemically stable and has an excellent herbicidal effect. The present invention has been completed by discovering that it is possible to produce a herbicidal composition that is useful in the future.

WO2009 / 156322

An object of the present invention is a herbicidal composition containing glyphosate salt and saflufenacyl as active ingredients, which is physicochemically stable and has an excellent herbicidal effect, and rapidly exhibits a medicinal effect. It is providing the formulation and its manufacturing method.

Another object of the present invention is to complete a pre-mixed one pack formulation in which glyphosate salt and saflufenacyl active ingredient are mixed at the same time to increase the efficiency of herbicidal work for farmers.

A stable aqueous suspension herbicidal composition containing glyphosate according to the present invention comprises glyphosate salt and saflufenacil as active ingredients, and (a) polyoxyalkylene alkyl ether, (b) polyoxy as effect enhancers. It contains one or more surfactants selected from the group consisting of ethylene sorbitan fatty acid esters and (c) organic or inorganic salts of polyoxyalkylene alkyl amines, alkyl polyglucosides, and tetraalkyl ammoniums.

According to another aspect of the present invention, the herbicidal composition of the present invention comprises a wetting agent, a dispersant, an antifoaming agent, a thickener, in addition to the herbicide active ingredient and the effect enhancer. Contains preservatives, antifreeze, and water.

According to another aspect of the present invention, the herbicidal composition of the present invention comprises glyphosate salt 20 to 45% by weight, saflufenacil 0.4 to 3% by weight, effect enhancer 1 to 30% by weight, wetting agent 0 0.01 to 5% by weight, dispersant 0.01 to 10% by weight, antifoaming agent 0.01 to 1% by weight, thickener 0.01 to 7% by weight, preservative 0.01 to 1% by weight, It is composed of 1 to 10% by weight of freezing agent and 10 to 60% by weight of water.

The effect enhancer comprises (a) 25 to 35% by weight of polyoxyalkylene alkyl ether, (b) 5 to 15% by weight of polyoxyethylene sorbitan fatty acid ester, It is composed of 50 to 60% by weight of one or more surfactants selected from the group consisting of organic or inorganic salts of oxyalkylene alkyl amines, alkyl polyglucosides, and tetraalkyl ammoniums.

The thickener is one or more organic polymer thickeners selected from the group consisting of gum derivatives, cellulose derivatives, starch, and water-soluble starch derivatives, and montmorillonite-based mineral fine powder And one or more solid fine powder thickeners selected from the group consisting of pyrolytic silica and attapulgite.

According to yet another aspect of the present invention, there is provided a method for producing a stable aqueous suspension herbicide composition containing glyphosate, wherein saffenacil as a herbicide active ingredient is added to a wetting agent, a dispersing agent, Step of mixing the antifoaming agent, solid fine powder thickener and water, followed by wet pulverization to an average particle size of 0.1 to 30 μm (Process 1), organic polymer thickener, preservative, and water Are mixed and then stirred to produce an organic thickening liquid (process 2). After mixing the glyphosate salt with the product of the above process 1, (a) polyoxyalkylene alkyl ether, (b) polyoxyethylene Sorbitan fatty acid ester, and (c) one or more selected from the group consisting of organic or inorganic salts of polyoxyalkylene alkylamine, alkylpolyglucoside, and tetraalkylammonium Includes effect enhancer comprising a surface active agent, antifreezing agent, an organic increase mucus of the step 2, and step of water were mixed to produce a herbicidal composition (step 3).

Hereinafter, the configuration of the present invention will be described in more detail.

In the present invention, the herbicide active ingredient means an active ingredient exhibiting an activity capable of removing unwanted weeds, etc., among which “glyphosate salt” is represented by the following <Chemical Formula 1>: Various salts of N- (phosphonomethyl) glycine (CAS RN 1071-83-6) which is “glyphosate”, preferably isopropylammonium salt, potassium salt, ammonium salt, diammonium salt , Dimethylammonium salt and sesquisodium salt, and “saflufenacyl” is N ′-[2-chloro-4-fluoro-5- (3-methyl-2,6-deoxo-] as shown in the following <chemical formula 2>. 4- (trifluoromethyl) -3,6-dehydro-1 (2H) -pyrimidinyl) benzoyl] -N-isopropyl-N-methylsulfamide (N ′-[2-chloro-4-fluoro-5- ( 3-m ethyl-2,6-dioxo-4- (trifluoromethyl) -3,6-dihydro-1 (2H) -pyrimidinyl) benzoyl] -N-isopropyl-N-methylsulfamide: CAS RN 372137-35-4).

In the present invention, the “effect enhancer” means an effect enhancement in biological and physicochemical aspects. Biological effect enhancement can be achieved by adding an effect enhancer when we expect the herbicidal effect using the above herbicidal active ingredient, which is the intended purpose of the present invention. Physicochemical effect enhancement means that the other components present in the same phase as the glyphosate salt, which is a high concentration electrolyte solution, lose electrostatic repulsion, precipitate, layer This means that a stable suspension state is maintained without separation or particle growth.

In the present invention, as an effect enhancer, (a) polyoxyalkylene alkylether, and (b) polyoxyethylene sorbitan fatty acid ester, (c) as a nonionic surfactant Formulated with polyoxyalkylene alkyl amine and alkyl polyglucoside and one or more organic or inorganic salts of tetraalkyl ammonium as a cationic surfactant use. When combined with a surfactant as described above, the herbicide active ingredients glyphosate and saflufenacil are very physicochemically stable and have an excellent herbicidal effect, as well as an effect in which a medicinal effect is rapidly expressed. Can be obtained.

As the polyoxyalkylene alkyl ether of the component (a), polyoxyethylene alkyl ether or polyoxypropylene alkyl ether is preferably used. More specifically, a preferred component is when 2 to 30 moles of ethylene oxide or propylene oxide is added to a saturated or unsaturated alcohol having 8 to 24 carbon atoms in the alkyl chain.

The polyoxyethylene sorbitan fatty acid ester of component (b) is preferably polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monostearate, or polyoxyethylene sorbitan monolaurate. used.

The polyoxyalkylene alkylamine as the component (c) is preferably polyoxyethylene alkylamine or polyoxypropylene alkylamine. More specifically, preferred components are those in which the alkyl chain has 8 to 24 carbon atoms and 2 to 30 moles of ethylene oxide or propylene oxide is added.

The alkyl polyglucoside (c) is preferably an alkyl polyglucoside having 8 to 18 carbon atoms in the alkyl chain and a polymerization degree of 1.2 to 2.5.

Among the components (c), the organic or inorganic salt of tetraalkyl ammonium which is a cationic surfactant is preferably an alkyl chain consisting of 1 to 20 carbons or hydroxyethyl. (hydroxyethyl), hydroxypropyl (hydroxypropyl), a 2-hydroxy-polyethoxylate (2-hydroxypolyethoxylate) form, salt _{-Cl, -Br, -acetate, -CH 3} OSO 3, such as _-C 2 H 5 OSO ₃ As specific examples, stearyltrimethylammonium chloride, stearyltrimethylammonium methosulfate, and the like can be given.

In the present invention, a herbicide active ingredient, saflufenacil, is included in an aqueous dosage form (water based formulation), and is wetted and dispersed to be milled and suspended in a state of several μm or less. Can be used. Preferred wetting agents include sodium disulfosuccinate and low molecular weight naphthalene formaldehyde condensates. Dispersing agents include phosphated or sulfated forms of polyoxyethylene tristyryl phenyl ether. And a condensate of polymer naphthalene formaldehyde, an acrylic acid polymer, and the like.

Thickeners are organic polymer thickeners such as xanthan gum, gum derivatives such as arabia gum, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc. Cellulose derivatives, starch or water-soluble starch derivatives, montmorillonite-based fine mineral powders such as bentonite as a solid fine powder thickener, hydrophilic or hydrophobic fumed silica (Fumed Examples thereof include pyrogenic silica such as silica and attapulgite. Each of these thickeners can be used alone, but based on the weight of the dosage form, 2% by weight or less of the organic polymer and 5% by weight or less of the solid fine powder thickener are used in combination. If treated, the thickening effect is particularly effective because the polymer performs the role of cross-linking between the fine particles.

Moreover, additives, such as an antifoamer, antiseptic | preservative, and an antifreezing agent required for an aqueous suspension formulation, can further be added to the herbicidal composition of this invention.

As the antifoaming agent, a silicon-based antifoaming agent such as Rhodorsil Antifoam 432 can be used, but is not limited thereto, and an antifoaming agent that is usually used in an agrochemical composition can be used.

As the preservative, substances such as Preventol and Proxel can be used, but the present invention is not limited thereto, and substances used in usual agricultural chemical compositions can be used.

Examples of the antifreeze include glycols such as ethylene glycol, propylene glycol, and dipropylene glycol, glycerol, and urea. However, the antifreeze is not limited thereto, and substances that are normally used in agricultural chemical compositions can be used.

In addition to the above, a colorant may be added as necessary. For the colorant, titanium dioxide, carbon black, zinc oxide, blue pigment, permanent red FGR, and the like can be used, but are not limited thereto. It is not a thing.

The herbicidal composition of the present invention is preferably 20 to 45% by weight of glyphosate salt, 0.4 to 3% by weight of saflufenacil, 1 to 30% by weight of an effect enhancer, 01-5 wt% wetting agent, 0.01-10 wt% dispersant, 0.01-1 wt% antifoaming agent, 0.01-7 wt% thickener, 0.01-1 Contains wt% preservative, 1-10 wt% antifreeze, and 10-60 wt% water.

The effect enhancer preferably contains 10 to 30% by weight, most preferably 15 to 30% by weight, and each component content is (a) polyoxyalkylene alkyl ether with respect to 100% by weight of the effect enhancer as a whole. Selected from the group consisting of 25-35 wt%, (b) polyoxyethylene sorbitan fatty acid esters 5-15 wt%, (c) polyoxyalkylene alkylamines, alkylpolyglucosides, and tetraalkylammonium organic or inorganic salts. When the composition is composed of 50 to 60% by weight of one or more surfactants, the herbicide active ingredients glyphosate salt and saflufenacil are physicochemically stable, and their medicinal effects are rapidly expressed.

The method for producing a stable aqueous suspension herbicidal composition containing glyphosate of the present invention is as follows. First, saflufenacil as a herbicide active ingredient is added to a wetting agent, a dispersing agent, an antifoaming agent and a solid fine powder. After mixing the adhesive and water, the mixture is wet pulverized by passing through a pearl mill, dyno mill, or sand mill containing microspherical beads, and pulverized so that the average particle size of saflufenacil is 0.1 to 30 μm. (Step 1).

Then, after mixing an organic polymer thickener, antiseptic | preservative, and water, it passes through the step which stirs and manufactures an organic thickener (process 2).

The product of step 1 above and the glyphosate salt include (a) polyoxyalkylene alkyl ether, (b) polyoxyethylene sorbitan fatty acid ester, and (c) polyoxyalkylene alkyl amine, alkyl polyglucoside, and tetraalkyl ammonium. After mixing the effect enhancer consisting of one or more surfactants selected from the group consisting of organic or inorganic salts, and then mixing the antifreeze, the organic thickening liquid obtained in the above step 2 and water are mixed. Homogenously mix to produce a herbicidal composition.

The aqueous suspension herbicidal composition according to the present invention has a rapid onset rate and requires a large labor force for agricultural workers, in addition to the effect of improving herbicidal efficiency in a very stable physicochemical manner. In addition, it is possible to increase the efficiency of physically arduous weeding work and improve psychological satisfaction.

Sequence diagram showing a method for producing the herbicidal composition of the present invention

Hereinafter, preferred embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments described herein, and may be embodied in other forms. It is provided so that the content introduced herein will be thorough and complete, and will fully convey the spirit of the invention to those skilled in the art.

Unless otherwise stated in the following embodiments and comparative examples,% is by weight and the glyphosate salt used contained 62% by weight of active ingredient as Glyphosate isopropylamine, and saflufenacil Contained 93% by weight of active ingredient.

(Embodiments 1 to 5 and Comparative Examples 1 to 10)
Production of herbicide composition First, saflufenacil as an herbicide active ingredient and a wetting agent, a dispersing agent, an antifoaming agent, a solid fine powder in the proportions shown in the following <Table 1> and <Table 2> A thickener and water (5 to 15% of the total amount of water used) were mixed and wet pulverized (Dynomill, KDL-A Type) to maintain the average particle size of saflufenacil at 1.5 to 3 μm. As a next step, an organic polymer thickener, an antiseptic, and water (5 to 10% of the total amount of water used) were mixed, and then an organic thickener was produced using a homogenizer (IKA / T-25 basic). . Add the herbicide active ingredient glyphosate salt, effect enhancer, antifoaming agent, antifreeze and organic thickener to the wet milled product and add extra water to make the whole composition 100 After adjusting to a weight percent, a herbicide composition in the form of a pre-mixed one pack formulation in which glyphosate and saflufenacil were mixed at the same time was completed.

Hereinafter, the physicochemical stability and biological effect of the herbicidal composition of the present invention will be described through specific evaluation tests.

<Evaluation test>
300 ml each of the herbicidal compositions of the above embodiment and the comparative example are put in a plastic pesticide container, sealed, stored for 6 weeks in a 54 ° C. incubator, each changed in particle size (particle size), and storage stability (storage stability) ), Suspensibility, and biological activity. It is a fact that anyone recognizes that such an evaluation factor is an important evaluation item in manufacturing an agrochemical composition that exhibits excellent efficacy in the industry.

1. Particle size
The particles of the herbicidal composition mean the particle size of saflufenacil, an agrochemical active ingredient suspended in water. If the particle size at the time of initial production is not maintained, the physical stability of the pesticide is ensured. In addition, it cannot exhibit biologically sustained medicinal effects. The particle size was measured using a laser particle sizer (Mastersizer 2000) that can be measured by a laser diffraction technique, and the results are shown in Table 3.

2. Storage stability
<Physical stability>
The herbicidal composition is a form in which glyphosate salt and saflufenacyl, which are high-concentration electrolyte solutions, coexist in water, and the solid-state saflufenacyl particles lose their electrostatic repulsion and remain in the bottom of the agricultural chemical container during storage. Of course, commercial use is possible only if it is caked or if phase separation does not occur severely. The storage stability was measured after the herbicidal composition was stored in a 54 ° C. incubator for 6 weeks (considered to be 3 years at room temperature in the agricultural chemical management method), and the results are shown in Table 3.

<Chemical stability>
Under severe conditions (stored in a 54 ° C. incubator for 6 weeks), the change in the content of the pesticidal active ingredient contained in the herbicidal composition was measured. This is because the herbicidal active ingredient content hardly changes or must be generated minutely in order to exert its medicinal effects stably over time. The initial content was measured using an analytical instrument (glyphosate salt: spectrophotometric method, saflufenacyl: HPLC method) in which samples of each embodiment and comparative example were presented by the pesticide process analysis method, and the sample was placed in a 54 ° C incubator. After weekly storage, the content of the pesticidal active ingredient present in the composition was measured using the same analytical instrument. Such test results are shown in Table 3 below.

3. Suspensibility
The herbicidal composition is used by diluting 500 to 1000 ml of the herbicidal composition per 10 a area to be controlled in 40 to 100 liters of water and spraying it while taking a certain time. Therefore, it is natural that the herbicidal composition diluted in water for a certain period of time does not settle to the bottom of the dilution vessel and must be distributed uniformly throughout the water. It is called suspension. In particular, it is possible to expect the intended medicinal effect by evenly spraying the agrochemical composition having excellent suspension properties over the entire area to be controlled. The suspension properties of the herbicidal compositions of the embodiment and the comparative example were measured, and the results are shown in <Table 3>.

1) Particle size: Means average particle size 2) Precipitation (%) = (weight of precipitate / weight of the entire herbicidal composition) × 100
3) Layer separation (%) = (liquid height separated transparently / height of the entire herbicidal composition) × 100
4) Chemical stability (%) = (analyzed value at the time of initial production−analyzed value after storage at 54 ° C. for 6 weeks) / initial analyzed value × 100
5) Suspension test method = Sample active ingredient (A) g was flattened in a beaker, 50 ml of 20 ° C. water was added, and the mixture was sufficiently stirred and dispersed evenly. Add water (20 ° C.) to 250 ml. In this way, the mixture is allowed to stand for 15 minutes, and then it is gently inverted 30 times per minute, mixed well, and then allowed to stand for 5 minutes. After that, gradually put it into the liquid with a 25ml volumetric pipet so that the end is at the center of the liquid, and gently inhale 25ml of the test liquid to measure the content of the active ingredient. Or (B) If the analysis of g or active ingredient is impossible, the dry matter is weighed and the suspension rate is calculated by the following formula.
(It means that the herbicidal composition diluted in water so that the suspension property is close to 100 does not settle to the bottom of the dilution container, and is distributed uniformly throughout the water)
Suspension (%) = BX 10 / AX 100

As confirmed in <Table 3> above, the herbicidal compositions of Embodiments 1 to 5 containing all of the components (a), (b), and (c) as effect enhancers are glyphosate salts. Even a high-concentration electrolyte solution can be produced with an agrochemical composition that is very physicochemically stable and can maintain a good state over a long period (three years or more).

4). Biological Activity Test To carry out the biological medicinal effect investigation test of the herbicidal composition according to the present invention, the mosquitoes that are abundantly produced in orchards and non-agricultural lands, such as flies, barnyard grass, and broadleaf weeds A test field predominateed by Canamgra, king caterpillar and bovine chickweed was sectioned and treated with drugs as shown in Table 4. In the case of Enomoto Kasushi, the drug efficacy is investigated 3 days, 5 days, 10 days, and 40 days after drug treatment, and in the case of broadleaf camellia, 4 hours, 1 day, 3 days, and 40 days, respectively. The results are shown in Table 5 and Table 6 as the control was judged from 0 (no drug effect) to 100 (the drug effect was expressed and the above-ground weeds were completely dead).

As shown in <Table 5>, the herbicidal compositions of Embodiments 1 to 5 in the scorpion moths such as barnyard grass and mosquito, the medicinal effects were expressed 3 days after the spraying of the drug, and they were completely dead after 10 days. On the other hand, the herbicidal compositions of Comparative Examples 1 to 10 exhibited a medicinal effect gradually from 5 days after spraying the drug, and were completely killed after 40 days. Further, as shown in <Table 6>, in the broad-leaved weeds such as canamgras, king caterpillar, and bovine chickweed, the herbicidal composition of Embodiments 1 to 5 exhibited a medicinal effect 4 hours after drug application, and 3 days later. While the herbicidal compositions of Comparative Examples 1 to 10 were completely killed, the medicinal effects were gradually developed one day after the spraying of the drugs, and they were completely dead after 40 days. As a result, the herbicidal compositions of Embodiments 1 to 5 in which the effect enhancer containing the components (a), (b), and (c) of the present invention is used have improved herbicidal efficiency, It was confirmed that the efficacy of the herbicidal active ingredient was quickly expressed.

Claims (6)

Contains glyphosate salt and saflufenacyl as herbicide active ingredients,
As an effect enhancer,
(A) polyoxyalkylene alkyl ether,
(B) polyoxyethylene sorbitan fatty acid ester,
(C) A stable aqueous solution containing glyphosate characterized in that it contains one or more surfactants selected from the group consisting of organic or inorganic salts of polyoxyalkylene alkylamines, alkylpolyglucosides, and tetraalkylammonium salts. Suspension herbicide composition. The herbicidal composition is:
The stable aqueous suspension herbicidal composition containing glyphosate according to claim 1, comprising a wetting agent, a dispersing agent, an antifoaming agent, a thickening agent, a preservative, an antifreeze agent, and water. The herbicidal composition is:
20-45% by weight of glyphosate salt,
Saflufenacil 0.4-3 wt%,
1-30% by weight of an effect enhancer,
Wetting agent 0.01 to 5% by weight,
0.01 to 10 wt% dispersant,
Antifoaming agent 0.01 to 1% by weight,
Thickener 0.01-7 wt%,
Preservative 0.01-1% by weight,
1-10% by weight of antifreeze,
A stable aqueous suspension herbicidal composition comprising glyphosate according to claim 2 composed of 10 to 60% by weight of water.
The effect enhancer is 100% by weight of the total effect enhancer,
(A) 25-30% by weight of polyoxyalkylene alkyl ether,
(B) 5 to 15% by weight of polyoxyethylene sorbitan fatty acid ester,
(C) One or more surfactants selected from the group consisting of organic or inorganic salts of polyoxyalkylene alkylamines, alkylpolyglucosides, and tetraalkylammonium salts, comprising 50 to 60% by weight. A stable aqueous suspension herbicide composition comprising the glyphosate according to any one of the above. The thickener is
One or more organic polymer thickeners selected from the group consisting of gum derivatives, cellulose derivatives, starch, and water-soluble starch derivatives;
The glyphosate according to claim 2 or 3, comprising a thickener in the form of one or more solid fine powders selected from the group consisting of montmorillonite-based mineral fine powder, pyrogenic silica, and attapulgite. A stable aqueous suspension herbicidal composition. A process for producing a stable aqueous suspension herbicidal composition containing glyphosate, comprising:
Saflufenacil, a herbicide active ingredient, is mixed with a wetting agent, a dispersant, an antifoaming agent, a solid fine powder thickener, and water, and then wet pulverized to an average particle size of saflufenacil of 0.1 to 30 μm. Crushing step (process 1) so that
After mixing the organic polymer thickener, preservative, and water, stirring to produce an organic thickener (process 2);
After mixing the glyphosate salt with the product of Step 1, (a) polyoxyalkylene alkyl ether, (b) polyoxyethylene sorbitan fatty acid ester, (c) polyoxyalkylene alkylamine, alkyl polyglucoside, and tetraalkyl An herbicide composition obtained by mixing an effect enhancer containing one or more surfactants selected from the group consisting of organic or inorganic salts of ammonium, an antifreeze, the organic thickening solution of Step 2 and water. A process for producing a stable aqueous suspension herbicidal composition containing glyphosate, characterized by comprising:

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