WO2013091154A1

WO2013091154A1 - A novel aqueous suspoemulsion

Info

Publication number: WO2013091154A1
Application number: PCT/CN2011/084191
Authority: WO
Inventors: James Timothy Bristow
Original assignee: Rotam Agrochem International Co., Ltd
Priority date: 2011-12-19
Filing date: 2011-12-19
Publication date: 2013-06-27
Also published as: FR2984079A1; CN103997889A; TWI543709B; PH12014501191B1; TW201325451A; PH12014501191A1; CN103997889B; FR2984079B1

Abstract

This present invention now provides a novel aqueous suspoemulsion(SE) product comprising as suspended solid component a Lufenuron, and as emulsified component a Lambda-cyhalothrin.

Description

A NOVEL AQUEOUS SUSPQEMULSIQN

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Lambda-cyhalothrin is the ISO approved common name of the insecticidal active ingredient consisting of the enantiomeric pair of isomers S- alpha- cy ano- 3 -phenoxybenzyl lR,cis-3-(Z-2-chloro-3,3,3-trifluroprop-l-en-l-yl)-2,2-dimehtylcycloprop ane carboxylate and

R- alpha- cy ano- 3 -phenoxybenzyl 1 S , cis- 3 - (Z-2- chloro- 3 , 3 , 3 -trifluoroprop- l-en-l-yl)-2,2-dimethylcyclopropane carboxylate in racemic proportions. The insecticidal product Lambda-cyhalothrin has previously been formulated emusifiable concentrates. Products comprising Lambda-cyhalothrin intended for use in agriculture or horticulture are usually sold under the Registered Trade Mark KARATE.

Lufenuron is the ISO approved common name of the insecticidal active ingredient , chemical name is

N- [ [ [2, 5 - dichloro-4- ( 1,1,2,3,3,3 -hexafluoropropoxy )pheny 1] amino] carbon yl]-2,6-difluorobenzamide. Lufenruon is generally commercialized in emulsificable concentrate (EC) formulation. Because of Lufenuron special properties, the emusificable concentrate with more than 5% Lufenuron tends to crystallization after diluted with water. In recent years there has been a desire to increase the efficacy, broaden the spectrum, and delay the resistance to insecticide by combining the application of two or more products. CNl 176589 describes the premix of benzoyl urea pesticide and pyrethroid. The combination has the high effect and low toxicity of benzoyl urea pesticide maintained and has no resistance like that of pyrethroid. The combination of benzoyl urea and pyrethroid has high application effect, wide application range and long persistent period, and is especially suitable for preventing and killing pests with serious resistance. This patent mentioned the premix could be formulated into emulsion concentrate, oil suspension, microemulsion, water dispersible granule and microencapsulation. But the patents do not provide or teach a method of preparing these formulations of this premix. And this patent also did not give the ambient storage stability data. Commercial products based on the combination of Lufenuron and Lambda- cyhalothrin are not readily available in an emulsion concentrate, oil suspension and microemulsion, water dispersible granule and microencapsulation.

Generally, the combination of Lufenuron or Lambda-cyhalothrin can be formulated into Emulsion Concentrate. But according to the author's experience the content of Lufenuron in the composition should be less than 5% to avoid the crystallization of Lufenuron in dilution. So the premix with high content Lufenuron (more than 5%) in the composition is not suitable to be formulated to emulsion concentrate. On the other hand emulsion concentrate requires substantial quantities of organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, etc. for effective formulation of the active ingredient. However, such organic solvents are known for their toxicological and ecotoxicological properties, creating toxicological and ecoxicological problems. For this traditional formulation, ICAMA (Ministry of Agriculture of China) has canceled the registration of Emulsion Concentrate. Other countries like EU and Brazil has increased the criterion of registration of Emulsion concentrate. According to the author's experience Lufenuron is not stable in emulsion. The emulsion formulation of Lufenuron and Lambda- cyhalothrin tends to crystallization at ambient storage condition.

For the single Lambda-cyhalothrin formulation, some environmental-friendly formulations have been developing. CN101828571 describes Lambda-cyhalothrin suspension concentrate. CN101167471 describes Lambda-cyhalothrin water dispersible granules. CN1600099 describes Lambda-cyhalothrin wettable powder. In these formulations, Lambda-cyhalothrin tends to come out during fine grinding and milling because of active ingredient low melting point. Such compositions obtained do not generally exhibit good dispersibility and shelf life especially since the low melting active undergoes a phase change during the ambient storage temperature(-5 to 50°C) leading to caking and crystal growth.

CN1836513, WO2005096820, WO2002028186, CN1274530 and WO9522902 discloses compositions comprising solid actives such as fipronil or imidacloprid and liquid actives such as Lambda-cyhalothrin or chlorpyrifos wherein the compositions are formulated as an oil emulsion, ultra-low content spray, oil-in-water emulsion, microemulsion, wettable powder, water dispersible granule, dry suspensition, granule, water solution, wettable powder, aerosol suspension concentrates and emulsifiable concentrates. While these patents generally disclose various formulations of a combination of pesticidal actives, including a water dispersible granule, suspension concentrate and wettable powder. The patents do not provide or teach a method of preparing the water dispersible granule composition, suspension concentrate composition and wettable powder composition. Commercial products based on the above combinations are not readily available in a water dispersible granule composition, suspension concentrate composition and wettable powder composition. As pointed out above, standard process for preparing a water dispersible granule, suspensition concentrate and wettable powder for a combination of the pesticidal actives above may not be feasible and would not provide a satisfactory composition, as such compositions do not possess good dispersion, stability, shelf life and other properties that a water dispersible granule, suspension concentrate and wettable powder should have. So the wettable powder, suspension concentrate and water-dispersible granule formulations are not suitable for the premix of Lufenuron and Lambda-cyhalothrin because Lambda-cyhalothrin tends to come out during fine grinding and milling because of the low melting point of the active ingredient.

Microencapsulation formulation can solve the problem of low melting point for Lambda-cyhalothrin, and the premix of lufenuron and lambda-cyhalothrin can be formulated into ZC which is a mixed formulation of lambda-cyhalothirn CS and Lufenuron SC. But this formulation cost so much and the production process thereof is complex. The commercial product is not readily available.

It would be very desirable to provide a Lufenuron and Lambda-cyhalothrin composition that is friendly to the environment. It would be also advantageous to provide such a composition that can comprise more than 5% Lufenuron in the composition, so as to provide a higher efficacy. It would be also very important to provide such a composition that is stable at ambient storage condition (-5 to 50°C) and is also stable when diluted.

SUMMARY OF THE INVENTION

This present invention also provides a suspoemulsion composition which is friendly to the environment. This present invention also provides a novel aqueous suspoemulsion that can comprise a suspoemusion composition which can comprise more than 5% Lufenuron in the composition to provide a higher efficacy.

This present invention also provides a novel aqueous suspoemulsion that exhibits both a high degree of physical and chemical stability and flowability, in particular in a temperature range from -5°C to 54°C, in which no crystallization phenomena and caking are observed after storage.

This present invention also provides a novel aqueous suspoemulsion that exhibits both dispersibility and suspensibility before and after storage in a temperature range from -5°C to 54°C, in which no crystallization phenomena are observed after storage.

Accordingly, in a first aspect, the present invention provides an aqueous suspoemulsion, characterized in that it comprises the components:

(a) a dispersed oil phase comprising:

(i) Lambda- cyhalothrin as the first active ingredient,

(ii) at least one solvent having Lambda-cyhalothrin dissolved therein;

(b) a continuous water phase comprising:

(i) Lufenuron as the second active ingredient,

(ii) water having Lufenuron suspended therein.

The oil phase, component (a), may contain one or more solventsand other additives.

The continuous water phase, component (b), may further comprise (iii) one or more dispersants and other additives. In a further aspect, the present invention provides a process for preparing an aqueous suspoemulsion as hereinbefore described, characterized in that it comprises the steps:

Step 1 : Preparing the Lambda-cyhalothrin EC phase by mixing the active ingredient with an suitable solvent;

Step 2: Preparing a dispersion of particles of the Lufenuron active ingredient in a continuous water phase by mixing the active ingredient, a dispersant and a required amount of water; and

Step 3: Combining the oil phase produced in Step 1 with the water phase produced in Step 2.

Alternatively, it comprises the steps:

Step 2: Lambda-cyhalothrin EC phase in step 1 was added into water with high shear, resulting in the lambda-cyhalothrin EW phase;

Step 3: Preparing a dispersion of particles of the Lufenuron active ingredient in a continuous water phase by mixing the active ingredient, a dispersant and a required amount of water; and

Step 4: Combining the oil in water emulsion phase produced in Step 2 with the water phase produced in Step 3.

Use of the suspoemulsion described above and a method of treating pests at a locus comprising applying the suspoemulsion are also provided by the present invention.

DETAILED DESCRIPTION OF THE INVENTION A suspoemulsion (SE) is a combination of an emulsion concentrate (EC) of one component with a suspension concentrate (SC) of another component. An EC phase is one in which the first active ingredient is dissolved in oil. An SC is a suspension of another active ingredient in water. When the two are mixed, water used as the continuous phase in the emulsion, carrying oil droplets used as the dispersed phase containing one active ingredient, is intermingled with suspended particles of another active ingredient. Generally, the SC, and hence the resulting SE, additionally contains other components such as a dispersant to aid the stability of the suspension and hence of the whole system.

In a first aspect, the present invention provides an aqueous suspoemulsion, characterized in that it comprises the components:

(a) a dispersed oil phase comprising:

(i) Lambda- cyhalothrin as the first active ingredient,

(ii) at least one solvent having Lambda-cyhalothrin dissolved therein;

(b) a continuous water phase comprising:

(i) Lufenuron as the second active ingredient,

(ii) water having Lufenuron suspended therein.

In a further aspect, the present invention provides a process for preparing an aqueous suspoemulsion as hereinbefore described, characterized in that it comprises the steps:

Alternatively, it comprises the steps:

Step 2: Lambda-cyhalothrin EC phase in step 1 was added into water with high shear, and got the lambda-cyhalothrin EW phase

Step 4: Combining the oil phase produced in Step 2 with the water phase produced in Step 3.

The suspoemulsion of the invention may be produced in a known manner using techniques known to the one skilled in the art.

The suspoemulsion of the present invention may comprise one or more solvents in component (a). Suitable solvents are aromatic hydrocarbon, methyl oleate, N-methyl pyrrolidone, propylene carbonate, N-octyl pyrrolidone, cyclohexyl-1 -pyrrolidone; a mixture of paraffinic, isoparaffinic, cycloparaffinic. Suitable solvents are commercially available.

The suspoemulsion of the present invention may comprise one or more emulsifiers in component (a). Suitable emulsifiers for inclusion in the compositions of the present invention are also known in the art and commercially available. Suitable emulsifiers include both ionic and non-ionic emulsifiers, such as fatty acid esters, fatty alcohol esters, ethers, alkyl sulphonates and aryl sulphonates. Other suitable surface active emulsifiers will also be known to the person skilled in the art.

The suspoemulsion of the present invention may comprise one or more suitable dispersants in component (b). The suspoemulsion according to the invention preferably comprise a mixture of two different dispersants. Preferred dispersants are the substances as mentioned below:

Methacrylic acid-methyl methacrylate-polyehyleneglycol graft copolymer, for example those commercially available under the name Atlox® 4913 (from Uniqema) and Tersperse 2500 (Huntsman Surfactant);

Tristyrylphenolethoxylates have an average of 16 to 60, preferably 16 to 50, oxyethylene units; moreover sulfated or phosphated tristylphenolethoxylates having an average of 6 to 20, preferably 7 to 16, oxyethylene units, and also salts of these substances; wherein specific mention may be made of commercial products known under the names Soprophor FLK (from Rhodia), Soprophor 3 D33 (from Rhodia), and Soprophor S/40-P (from Rhodia); and

Propylene oxide/ethylene oxide block copolymers have at least 40 mol% polyoxyethylene units, a central polyoxypropylene portion preferably having a molecular mass of from 1500 to 2000. The products commercially available under the names Pluronic PE10100 (from BASF), Pluronic PE10500 (from BASF) and Pluronic 6800 (From BASF) may be mentioned by way of example. The surfactants mentioned above are believed to impart the stability to the system.

In addition to the aforementioned components, the composition may comprise one or more further additives, as may be required. Additives for inclusion in the formulation are known in the art and commonly employed. Suitable additives which may be comprised in the suspoemulsion according to the invention are all customary formulation adjuvants, such as anti-foams, emulsifiers, antifreeze agents, preservatives, antioxidants, colorants, thickeners and inert fillers. Suitable anti-foams include all substances which can normally be used for this purpose in agrochemical compositions. Particularly preferred antifoam agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as the silicone anti foam agents available from GE or Compton.

Suitable preservatives include all substances which can normally be used for this purpose in agrochemical compositions of this type. Suitable examples which may be mentioned include preventol®( from Bayer AG) and Proxel® (from Bayer AG).

Suitable antioxidants are all substances which can normally be used for this purpose in agrochemical compositions. Preference is given to butylated hydroxy toluene.

Suitable inert fillers include all substances which can normally be used for this purpose in agrochemical compositions and which do not act as thickeners. Preference is given to inorganic particles, such as carbonates, silicates and oxides, and also to organic substances, such as urea/formaldehyde condensates. By way of example, kaolin, rutile, silica, finely divided silica, silica gels, and natural and synthetic silicates, and also talc may be mentioned.

Suitable thickeners include all substances which can normally be used for this purpose in agrochemical compositions. For example xanthan gum, PVOH, cellulose, clay hydrated silicates, magnesium aluminum silicates or a mixture thereof. Again, such thickeners are known in the art and available commercially.

In addition, the suspoemulsion according to the invention also comprises water, present in the aqueous component (b).

The content of the individual components in the suspoemulsion according to the invention can be varied within a relatively wide range. Thus, the concentrations of the components as may be present are typically as follows: of the active compounds from the group (i) of (a) are generally between 1% and 40% by weight, preferably between 5% and 20% by weight; of the active compounds from the group (i) of (b) are generally between 1% and 40% by weight, preferably between 5% and 20% by weight; of the solvent from the group (ii) of (a) are generally between 1% and 30% by weight, preferably between 5% and 20% by weight; of the water content in the suspoemulsion according to the invention from the group (ii) of (b) can be varied within a wide range. Depending on the other components, the water content is generally between 25% and 80% by weight; of the dispersants from the group (iii) of (b) are generally between 1% and 10% by weight, preferably between 1% and 5% by weight;

The suspoemulsions according to the present invention may be prepared using any suitable method. The preferred formulations are preferably prepared by the following procedure:

Step 1 : Preparing the Lambda-cyhalothrin EC phase by mixing the active ingredient with a solvent along with suitable emulsifiers;

Step 2: Preparing a dispersion of particles of the Lufenuron active ingredient in a continuous water phase by mixing the active ingredient, a dispersant and a required amount of water;

The active ingredient Lufenuron along with suitable dispersants and other additives such as antifreezing agent and antifoaming agent, and a required amount of water are initially mixed well and finely milled using a horizontal agitating bead mill maintaining the process parameters like the average particle size d50 not to exceed 3 microns and for almost all the particles d90 not to exceed 6 microns.

Step 3: The EC phase produced in step 1 is added to the water phase produced in step 2 under continuous agitation for an optimum amount of time.

Step 4: The thickeners, like polysaccharides or Xanthan gums, are prepared in advance to enable them to be hydrated and be ready for the addition in the following step as mentioned as Step 5.

Step 5: Suitable quantity of the thickener such as a gum in step 4 is added to the mixture in step 3 and continuously agitated till the mixture is a homogeneous suspension.

The preferred formulations are also preferably prepared by the following procedure:

Step 2: Lambda-cyhalothrin EC phase in step 1 was added into water with high shear, resulting in the lambda-cyhalothrin EW phase

Step 3: Preparing a dispersion of particles of the Lufenuron active ingredient in a continuous water phase by mixing the active ingredient, a dispersant and a required amount of water;

Step 4: The oil in water emulsion produced in step 2 is added to the water phase produced in step 3 under continuous agitation for an optimum amount of time.

Step 5: The thickeners, like polysaccharides or Xanthan gums, are prepared in advance to enable them to be hydrated and be ready for the addition in the following step as mentioned as Step 6.

Step 6: Suitable quantity of the thickener such as a gum in step 5 is added to the mixture in step 4 and continuously agitated till the mixture is a homogeneous suspension.

The suspension is tested for the low temperature storage stability at -5°C for 7 days, elevated temperature storage stability at 54°C for 14 days, and the stability when diluted for 24h at 30°C.

The suspoemulsions according to the invention are formulations which, even after storage at elevated temperatures or in the cold, remain stable as no crystal growth is observed. By the dilution with water, they can be converted into homogeneous spray fluids without finding the nozzles blocked as a result of crystallization of the active ingredients in the spray fluids. These spray fluids are suitable to be applied by customary methods, for example, by spraying or pouring.

The application rate of the suspoemulsion according to the invention can be varied within a relatively wide range. Concentration depends on the amounts of the active ingredients in the composition and intended purpose, which can be determined by a skilled person in this field.

In a further aspect, the present invention provides a method for controlling pests at a locus, in particular insects, the method comprising applying to the locus an effective amount of a formulation as hereinbefore described.

Still further, the invention also provides the use of a concentrate formulation as hereinbefore described in the control of pests at a locus. These suspoemulsions of the present invention exhibited improved physical and chemical stability across a wide range of conditions, in particular across a temperature range from -5°C to 54°C, where no crystallization phenomena are observed during storage. The formulations are also environmentally friendly.

The advantage of the formulations of the present invention is that commercially viable concentrations of stable formulations of the pesticide may be used without any substantial or detrimental formation of crystals.

The formulations of the present invention exhibit a low degree of phytotoxicity compared to the commercial E.C.

The suspoemulsion formulations of the present invention have further advantages of being non-flammable and of being of low dermal toxicity and low skin irritancy.

Finally, the suspoemulsion formulations of the present invention can be considered ecotoxicologically safe, since they are prepared from safe and substantially inert ingredients. The result is not only useful formulations, but also formulations which can meet stringent requirements of the EPA in the United States and the standards of European control of volatile organic compounds.

While the invention will now be described in connection with certain preferred embodiments in the following examples, it will be understood that it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of procedures as well as of the principles and conceptual aspects of the invention.

PREPARATION EXAMPLES

Example 1

A suspoemulsion formulation was prepared as follows: a) Emulsion Concentrate Preparation of Lambda- cyhalothrin phase:

The Active ingredient Lambda-cyhalothrin (JiangsuYoushi Chemistry) was mixed with Methyl oleateClariant) at room temperature. It was allowed to stand for 30 minutes before the addition of the emulsifier EL360 (Clariant) and under stirring until a homogeneous solution was achieved.

Component Composition (g) Remark

Lambda-cyhalothrin Tech

5 (as pure) Active ingredient (Jiangsu Youshi)

Methyl oleate (Clariant) 5 solvent

EL360 (Clariant) 3 Emulsifier b) Preparation of Dispersed particles of Lufenuron (Shanghai Stone) active ingredient in a continuous water phase:

Component Composition (g) Remark

5 (as pure) Active ingredient

Lufenuron Tech (Shanghai Stone)

soprophorBSU (Rhodia) 0.5 dispersant

Soprophor FLK (Rhodia) 1.5 dispersant

Propylene glycol (DOW) 4 Antifreezing

Rhodopol 23/W (Rhodia) 0.15 thickener

Silicon oil (Degussa) 0.5 defoamer

water balance to 100 carrier

The active ingredient Lufenuron, along with suitable dispersants Soprophor BSU and Soprophor FLK and other additives such as Antifreezing agent and Antifoaming agent and required amount of water were initially mixed well and finely milled using a horizontal agitating bead mill maintaining the process parameters, such as the average particle size d50 not to exceed 3 microns and for almost all the particles d90 not to exceed 6 microns.

c) Preparation of the Suspoemulsion

The oil phase (a) was added to water phase (b) under a continuous agitation for an optimum amount of time at room temperature. Then suitable quantity of the thickener gum (Rhodopol 23/W) were added to the above mixture and continuously agitated until the mixture was a homogeneous suspension at room temperature. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C. Example 2

A suspoemulsion formulation was prepared as follows: a) Oil in water emulsion preparation of Lambda-cyhalothrin EW phase

The Active ingredient Lambda-cyhalothrin was mixed with SolvessolOO and at room temperature. It was allowed to stand for 30 minutes before the addition of the emulsifier EL360 and under stirring until a homogeneous solution was achieved. Then adding the lambda-cyhalothrin EC phase into water with high shear and got the lambda-cyhalothrin EW phase. b) Preparation of Dispersed particles of Lufenuron in a continuous water phase:

Component Composition (g) Remark

Lufenuron Tech 8 (as pure) Active ingredient

Tersperse 2500 (Huntsman) 0.4 dispersant

Pluronic 6800 (Basf) 1.2 dispersant Propylene glycol 4 Antifreezing

Rhodopol 23/W (Rhodia) 0.15 thickener

Silicon oil (Degussa) 0.5 defoamer

water balance to 100 carrier

The preparation of the suspension concentrate of Lufenuron was carried out using the same general method as set out in b) of Example 1.

c) Suspoemulsion

The oil in water phase (a) was added to water phase (b) under a continuous agitation for an optimum amount of time. Then suitable quantity of the thickener gum were added to the above mixture and continuously agitated until the mixture was a homogeneous suspension. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C.

Example 3

A suspoemulsion formulation was prepared as follows: a) Emulsion Concentrate Preparation of Lambda-cyhalothrin phase

Component Composition (g) Remark Lambda-cyhalothrin Tech 10(as pure) Active ingredient

Methyl oleate (Clariant) 10 solvent

Alkamuls OR/36 (Rhodia) 3 Emulsifier

The emulsion concentrate of Lambda-cyhalothrin was prepared in the same general manner as set out in a) of Example 1.

b) Preparation of Dispersed particles of Lufenuron in a continuous water phase

Component Composition (g) Remark

Lufenuron Tech 10 (as pure) Active ingredient

Soprophor 3 D33 (Rhodia) 2.3 dispersant

Pluronic 10100 (Basf) 2.3 dispersant

Propylene glycol

4 Antifreezing (DOW)

Rhodopol 23/W

0.15 thickener

(Rhodia)

Silicon oil 0.5 defoamer water balance to 100 carrier The preparation of the suspension concentrate of Lufenuron was carried out using the same general method as set out in b) of Example 1.

c) Suspoemulsion

The suspoemulsion was prepared using the same general procedure set out in c) of Example 1. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C.

Example 4

A suspoemulsion formulation was prepared as follows: a) Emulsion Concentrate Preparation of Lambda-cyhalothrin EC phase

b) Preparation of Dispersed particles of the Lufenuron in a continuous water phase :

c) Suspoemulsion

Example 5 A suspoemulsion formulation was prepared as follows: a) Oil in water emulsion Preparation of Lambda-cyhalothrin EW phase

The oil in water emulsion of Lambda-cyhalothrin EW phase prepared in the same general manner as set out in a) of Example 2.

b) Preparation of Dispersed particles of the Lufenuron continuous water phase :

Component Composition (g) Remark

Lufenuron Tech 20 (as pure) Active ingredient

Atlox 4913 (Croda) 2.3 dispersant

Pluronic 6800 (BASF) 0.8 dispersant

Propylene glycol 4 Antifreezing

Rhodopol 23/W (Rhodia) 0.15 thickener Silicon oil 0.5 defoamer water balance to 100 carrier

The preparation of the suspension concentrate of Lufenuron was carried out using the same general method as set out in b) of Example 2.

c) Suspoemulsion

The suspoemulsion was prepared using the same general procedure set out in c) of Example 2. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C.

Example 6

Component Composition (g) Remark

Lambda-cyhalothrin Tech 5 (as pure) Active ingredient

Methyl oleate ( Clariant) 5 solvent

Alkamuls OR/36 2 Emulsifier The oil in water emulsion of Lambda- cyhalothrin EW phase prepared in the same general manner as set out in a) of Example 2.

b) Preparation of Dispersed particles of the Lufenuron continuous water phase :

c) Suspoemulsion

The suspoemulsion was prepared using the same general procedure set out in c) of Example 2. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C. Example 7

The emulsion concentrate of Lambda-cyhalothrin was prepared in the same general manner as set out in a) of Example 1

b) Preparation of Dispersed particles of Lufenuron in a continuous water phase:

Component Composition (g) Remark

Lufenuron Tech 40(as pure) Active ingredient

Tersperse 2500 (Huntsman) 0.4 dispersant Pluronic 6800 (Basf) 1.2 dispersant

Propylene glycol 4 Antifreezing

Rhodopol 23/W (Rhodia) 0.15 thickener

Silicon oil (Degussa) 0.5 defoamer

water balance to 100 carrier

c) Suspoemulsion

Example 8

Component Composition (g) Remark Lambda-cyhalothrin Tech 30(as pure) Active ingredient

Corn oil 30 solvent

Alkamuls OR/36 3 Emulsifier

The oil in water emulsion of Lambda-cyhalothrin EW phase was prepared in the same general manner as set out in a) of Example 2.

b) Preparation of Dispersed particles of Lufenuron in a continuous water phase

The preparation of the suspension concentrate of Lufenuron was out using the same general method as set out in b) of Example 2. c) Suspoemulsion

Example 9

The emulsion concentrate of Lambda-cyhalothrin was prepared in the same general manner as set out in a) of Example 1. b) Preparation of Dispersed particles of the Lufenuron in a continuous water phase : Component Composition (g) Remark

Lufenuron Tech 1 (as pure) Active ingredient

Tersperse 2500 (Huntsman) 2.5 dispersant

Soprophor FLK (Rhodia) 1 dispersant

Propylene glycol 4 Antifreezing

Rhodopol 23/W 0.15 thickener

Silicon oil 0.5 defoamer

water balance to 100 carrier

The preparation of the suspension concentrate of Lufenuron was carried out using the same general method as set out in b) of Example 1. c) Suspoemulsion

Example 10

A suspoemulsion formulation was prepared as follows: a) Oil in water emulsion Preparation of Lambda-cyhalothrin EW phase Component Composition (g) Remark

Lambda-cyhalothrin Tech 15 (as pure) Active ingredient

Propylene carbontate 15 solvent

Alkamuls OR/36 3 Emulsifier

The oil in water emulsion of Lambda-cyhalothrin EW phase was prepared in the same general manner as set out in a) of Example 2. b) Preparation of Dispersed particles of the Lufenuron continuous water phase :

The preparation of the suspension concentrate of Lufenuron was out using the same general method as set out in b) of Example 2. c) Suspoemulsion The suspoemulsion was prepared using the same general procedure set out in c) of Example 2. The suspension was tested for low temperature storage stability (-5°C), elevated temperature storage stability (54°C) and the stability when diluted at 30°C.

Stability Test results

The samples were tested for low temperature stability and heat storage stability. Low temperature stability was tested in a low temperature apparatus at -5°C for 7 days. Heat storage stability was tested in an oven at 54°C for 14 days. After finishing the test, the formulation was filtered through a 342 mesh sieve, and the flowability of the formulation and the formation of crystals were observed.

In addition, the elevated storage phenomena was observed after the samples were taken out from 54°C and kept at ambient for one to two days.

The performance of the formulation upon suspensibility and dispersibility were also determined for the sample before and after low temperature storage at -5°C and heat storage at 54°C. In one 250 ml cylinder with CIPAC D water, lg sample was added. If the sample dropped to the down of cylinder quickly, it means the sample has a bad dispersibility. If the sample can disperse in water simultaneously, it means the sample has a good dispersibility. Then the cap was covered and the cylinder was shaken 10 times up and down then kept the cylinder stand for lmin. If the settled solids were much then the sample has a bad suspensibility. If the settled solids were trace, then the sample has a good suspensibility.

The suspoemulsion formulations of the present invention had the following characteristics: Example Low temperature stability Heat storage stability Disperibility and at -5°C for 7days at 54°C for 14days Suspensibility before and after storage

Example 1 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 2 Good flowability,no crystal Good flowability, no good

formation crystal formation

Example 3 Good flowability,no crystal Good flowability, no good

formation crystal formation

Example 4 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 5 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 6 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 7 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 8 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 9 Good flowability, no crystal Good flowability, no good

formation crystal formation

Example 10 Good flowability, no crystal Good flowability, no good

formation crystal formation Phytotoxicity test results

The trials to check relative phytotoxicity were carried out with the following samples according to the present invention and the comparative trial based on a commercial Lufenuron 50 EC ( Match, Syngenta) product and Lambda- cyhalothrin 120EC ( KARATE, Syngeta). In terms of the severity of the symptoms, the test samples are categorized as follows:

Cat 0: no phytotoxicity

Cat 1 : slight phytotoxicity

Cat 2: strong phytotoxicity

The trials to test phytotoxicity of the formulations showed that the formulations of Examples 1-10 all exhibited a phytoxicity of Cat 0 level. The comparative trial with the commercial Lufenuron 50EC product and Lambda- cyhalothrin 120EC showed the product to exhibit Cat 2 level phytotoxicity. In summary, the suspoemulsion formulation of the present invention was significantly less phytotoxic than the commercial EC product.

From the experimental data set out above, it can be seen that the suspoemulsion formulation according to this present invention has good flowability and storage stability at both low temperatures and high temperatures. Further, the suspoemulsion has good dispersibility and suspensibility for the sample before and after low temperature storage at -5°C and heat storage at 54°C. Still further, the phytotoxicity exhibited by the formulation of this invention is significantly less than the commercial EC formulation.

Claims

1. An aqueous suspoemulsion, characterized in that it comprises the components:

(a) a dispersed oil phase comprising:

(i) Lambda-cyhalothrin as the first active ingredient

(ii) at least one solvent having Lambda-cyhalothrin dissolved

(b) a continuous water phase comprising:

(i) Lufenuron as the second active ingredient

(ii) water having Lufenuron suspended therein

2. The suspoemulsion as claim 1, characterized in that it comprises Lambda-cyhalothrin as emulsified component and Lufenuron as suspended component.

3. The suspoemulsion as claim 1, characterized in that component (b) further comprises:

(iii) at least one dispersant.

4. The suspoemulsion as claimed in claim 4, wherein the at least one dispersant in (iii) of component (b) is selected from the group consisting of methacrylic acid-methyl methacrylate-polyethyleneglycol graft copolymers, tristyrylphenolethoxylates and/or propylene oxide/ethylene oxide block copolymer with 10% to 50% EO, preferably with 20% to 50% EO, and more preferably with 30% to 40% EO.

5. A process for preparing the suspoemulsion as claimed in any preceding claim, characterized in that it comprises the steps:

Step 1 : Preparing the Lambda-cyhalothrin EC phase by mixing the active ingredient with an suitable solvent; Step 2: Preparing a dispersion of particles of the Lufenuron active ingredient in a continuous water phase by mixing the active ingredient, a dispersant and a required amount of water; and

6. A process for preparing the suspoemulsion as claimed in any preceding claim, characterized in that it comprises the steps:

Step 4: Combining the oil in water phase produced in Step 2 with the water phase produced in Step 3.

7. A process for preparing the suspoemulsion as claimed in any preceding claim, characterized in that it comprises the steps:

Step 1 : Preparing the Lambda-cyhalothrin EC phase by mixing the active ingredient with a solvent along with suitable emulsifiers

Step 3: The EC phase produced in step 1 is added to the water phase produced in step 2 under continuous agitation for an optimum amount of time. Step 4: The thickeners, like polysaccharides or Xanthan gums, are prepared in advance to enable them to be hydrated and be ready for the addition in the following step as mentioned as Step 5.

8. A process for preparing the suspoemulsion as claimed in any preceding claim, characterized in that it comprises the steps:

Step 1 : Preparing the Lambda-cyhalothrin EC phase by mixing the active ingredient with a solventalong with suitable emulsifiers;

Step 4: The oil in water emulsion in step 2 is added to the water phase in step 3 under continuous agitation for an optimum amount of time.

Step 6: Suitable quantity of the thickener such as a gum in step 5 is added to the mixture in step 4 and continuously agitated until the mixture is a homogeneous suspension.

9. The process in claim 8 wherein in step 2, or in claim 9 wherein in step 3, the components are mixed by being finely milled using a horizontal agitating bead mill maintaining the process parameters like the average particle size d50 not to exceed 3 microns and for almost all the particles d90 not to exceed 6 microns.