DESC:Field of the Invention: The present invention relates to a stable liquid composition. The present invention more particularly relates to a stable liquid composition of two or more agrochemical ingredients.

Background of the Invention:
Agrochemically active ingredients are often provided in the form of concentrates suitable for dilution with water. Many forms of agrochemically active ingredients are known and these consist of the active ingredient and a carrier, which can include various components. Water-based concentrates are obtained by dissolving, emulsifying and/or suspending agriculturally active materials in water. Such concentrates are available as suspension concentrate (SC), Oil Dispersion (OD), Emulsion in Water (EW), Suspoemulsion (SE), Capsule Suspension (CS) etc.

When agrochemically active ingredient is insoluble or only partly soluble in water, the concentrate comprising the active is conveniently supplied in the form of a suspension concentrate (SC) in which finely divided solid particles of agrochemical are suspended in a liquid formulation. The active ingredient in the form of finely divided solid particles is suspended in a liquid dispersing medium utilizing surface-active compounds, such as wetting agents, dispersants and rheological or suspending aids for stabilising the active ingredient particles in the dispersing medium.

A suspension concentrates to be used in the agricultural industry is typically diluted with water to prepare a dilute sprayable composition which is then applied by spraying to soil and/or plants in a field, for example by means of conventional spraying equipment. At the time of use, therefore, it is desirable that the suspension concentrate is readily emulsified in water, with no more than a minimal and acceptable amount of segregation of components into distinct layers referred to in the industry as “creaming”, and/or no more than a minimal and acceptable amount of sedimentation. In order to accomplish this, one or more surfactants or emulsifiers are therefore also typically included in suspension concentrates to improve dispersibility in water.

Suspension concentrates are inherently unstable in a gravitational field because of difference in density between the solid pesticide and the liquid carrier, which can result in separation of the formulation over time into a pesticide-rich layer and a carrier-rich layer. In extreme cases, phase separation occurs, wherein the solid particulate pesticide, typically the denser phase, settles at the bottom of the liquid phase. As a result of settling during prolonged storage or storage at elevated temperatures, the resistance of settled particles to re-suspension leads to the formation of crystalline material upon storage. Therefore, the formulations are difficult to handle and the bioefficacy may be inconsistent. Moreover, since the particle size of the active ingredient particles is large in Suspension concentrate, it may often result in a lower efficacy. It is important that the solid particles remain suspended in the concentrate formulation without significant separation over an extended period of time under typical storage conditions. It is also important to prevent the dispersed solid particles in the suspension concentrate from forming a hard pack sediment upon storage. It is therefore normally necessary to incorporate suspending agents in to the suspension concentrate.

Tetronic acid is a chemical compound, classified as a ?-lactone, with the molecular formula C4H4O3. Tetronic acids comprise a subclass of 4-hydroxybutenolides which includes spirodiclofen, spiromesifen and also Tetramic acids, for example spirotetramat. In 2002, spirodiclofen (Figure 1), a new acaricide was launched with unique symptomology of poisoning, indicating a totally novel biochemical mode of action (Wachendorff et al., 2002; Nauen, 2005). Soon after, the second ketoenol was introduced, spiromesifen, acaricide and insecticide active against spider mites and whiteflies (Nauen et al., 2002, 2005; Kontsedalov et al., 2009). Recently introduced the third cyclic ketoenol, spirotetramat, is an insecticide proved as effective against whiteflies, aphids and other homopteran pests (Nauen et al., 2008).

3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl-2,2-dimethyl butyrate, having the common name of spirodiclofen, is a member of the ketoenol or tetronic acid class of chemicals. It is the first member of the ketoenol group with unique symptomology of poisoning and novel biochemical mode of action. It is used as non-systemic foliar insecticide and acaricide with a wide spectrum. Its pesticidal mode of action is through the inhibition of lipid synthesis by the inhibition of acetyl-CoA-carboxylase, which is a key enzyme in fatty acid biosynthesis. It controls the pests by interfering with mite development, pests such as Panonychus spp., Phyllocoptruta spp., Brevipalpus spp., Aculus spp. and Tetranychus spp. It controls mites and San Joe scales in citrus fruits, grapes, pome fruit, stone fruit, and tree nut crops.

Fig. 1

Spirodiclofen is known to be formulated in the form of a suspension concentrate (SC). However, problem arises when spirodiclofen is to be co-formulated with low melting active ingredients. It has been observed that the compositions comprising spirodiclofen with low melting active ingredients tend to suffer from long-term stability issues when stored. Upon storage, compositions in the form of suspension concentrate containing low melting active ingredients exhibit stability problems related to rapid crystal formation of the low-melting active ingredients. Gelling, caking and settling due to large crystals being formed in the final suspension concentrate formulation result in instability, difficulty in processing and unreliability in usage. Thus, formulating suspension concentrate compositions of spirodiclofen and low melting active ingredients wherein this gelling, caking and settling are minimized is crucial to the stability of the suspension concentrates.

Objectives of the Invention

An objective of the present invention is to develop stable liquid composition of tetronic acid derivatives and low melting active ingredient.

Another objective of the invention is to develop stable liquid composition of spirodiclofen and low melting active ingredient.

Yet another objective of the present invention is to develop stable liquid composition of spirodiclofen and low melting active ingredient in the form of a suspension concentrate.

Still another objective of the present invention is to develop stable liquid composition with wider spectrum of activity.

Summary of the invention:

In accordance with the above objectives, the present invention provides a composition comprising:
a) at least one tetronic acid derivative;
b) at least one low melting active ingredient; and
c) a structuring agent.

In accordance with the above objectives, the present invention provides a stable liquid composition comprising:
a) at least one tetronic acid derivative;
b) at least one low melting active ingredient; and
c) a structuring agent.

In accordance with the above objectives, the present invention provides a stable liquid composition comprising:
a) a tetronic acid derivative;
b) a low melting active ingredient; and
c) a structuring agent selected from inorganic porous compounds.

In accordance with the above objectives, the present invention provides a process of preparing stable liquid composition, said process comprising :
1) preparing a slurry by adding tetronic acid derivative, low melting active and a structuring agent in water;
2) milling the slurry to achieve desired particle size;
3) separately, preparing a gel by adding thickening agent; and
4) adding gel of step 3 to the slurry of step 2 to obtain said liquid composition.

In accordance with the above objectives, the present invention further provides a method of controlling insect pests, said method comprising applying an agrochemically effective amount of stable liquid composition comprising a) a tetronic acid derivative; b) a low melting active ingredient; and c) a structuring agent; to the insect pests or to their locus.

In accordance with the above objectives, the present invention provides use of stable composition according to the present invention as an insecticide.

Additional features and advantages of the present invention will be apparent from the detailed description that follows, which illustrates by way of example, the most preferred features of the present invention which are not to be construed as limiting the scope of the invention described herein.

Detailed Description of the Invention

Without wishing to be bound by theory, the present inventors have surprisingly found that the stable liquid compositions of tetronic acid derivatives with low melting active ingredient can be prepared by using inorganic porous compounds as a structuring agent. Presence of inorganic porous compounds in the liquid composition prevents curdling of dispersed phase in the liquid composition. The liquid composition according to the present invention demonstrate good stability profile as compared to the existing prior art.

Thus, an embodiment of the present invention provides a composition comprising:
a) at least one tetronic acid derivative;
b) at least one low melting active ingredient; and
c) a structuring agent.

According to an embodiment of the present invention, the stable liquid composition comprising:
a) at least one tetronic acid derivative;
b) at least one low melting active ingredient; and
c) a structuring agent.

According to an embodiment of the present invention, the stable liquid composition may be formulated as suspension concentrate (SC), as an emulsion concentrate (EW), as an oil-based suspension concentrate (OD), and/or suspoemulsions (SE).

According to a preferred embodiment of the present invention, the stable liquid composition is formulated as suspension concentrate (SC).

In an embodiment of the present invention, a tetronic acid derivative is selected from the group consisting of spirodiclofen, spiromesifen, their salts, esters and mixtures thereof.

In an embodiment of the present invention, the stable liquid composition comprises from about 0.1% to about 70% w/w and preferably from about 1% to about 50% w/w tetronic acid derivative of the total weight of the stable liquid composition.

In a preferred embodiment of the present invention, the stable liquid composition comprises from about 10% to about 40% w/w tetronic acid derivative of the total weight of the stable liquid composition.

In an embodiment of the present invention, the low melting active ingredient is selected from the group comprising of pyrethroids, triazole, organophosphate, thiadiazole, dioxolane, aminopyrimidine, strobilurins, spinosyn and cyclopropanecarboxylic acid class of active ingredients.

In an embodiment the low melting active ingredient of the present invention is selected from the group comprising of cypermethrin, fenvalerate, permethrin, alphacypermethrin, betacypermethrin, zetacypermethrin, deltamethrin, cyfluthrin, bifenthrin, lambda-cyhalothrin, and/or bioresmethrin, nitrothal-isopropyl, myclobutanil, piproctanyl bromide, isofenphos, Imazalil, lambda-cyhalothrin, triflumizole, vamidothion, xylylcarb, tolclofos-methyl, prothoate, pyriproxyfen, propamocarb hydrochloride, tefluthrin, resmethrin, chlorpropham, cloethocarb, demeton-S, cyfluthrin, cypermethrin, azinphos-ethyl, azinphos-methyl, benalaxyl, benazolin-ethyl, butocarboxim, benzoximate, bioresmethrin, bromopropylate, borax, biphenyl, fluoroglycofen-ethyl, fenbucarb, fenthiocarb, fensulfothion, fosmethilan, furalaxyl, dikegulac, trinexapac-ethyl, ethiofencarb, etridiazole, fenamiphos, fenazaquin, EPN, dodemorph, mecarphon, etaconazole, fluorbenside, furmecyclox, fenfluthrin, fluenetil, acequinocyl, schradan, transfluthrin, cyprodinil, phosfolan, crufomate, chlorphoxim, chloropropylate, di-allate, chlorofenprop, chlorpyrifos, monocrotophos, camphechlor, chlorbenside, chlordimeform, phosphonic acid, trifloxystrobin, picoxystrobin, gamma-cyhalothrin, codlemone, spinetoram, cyflumetofen or mixture thereof.

In an embodiment of the present invention, the low melting pyrethroid is selected from the group comprising of bifenthrin, cypermethrin, fenvalerate, permethrin, alphacypermethrin, betacypermethrin, zetacypermethrin, deltamethrin, cyfluthrin, bifenthrin, lambda-cyhalothrin, and/or bioresmethrin or mixtures thereof.

In a preferred embodiment of the present invention, the low melting pyrethroid is bifenthrin.

In an embodiment of the present invention, stable liquid composition comprises from about 0.1% to about 50% w/w and preferably from about 0.5% to about 40% w/w low melting active ingredient, of the total weight of the stable liquid composition.

In a preferred embodiment of the present invention, the stable liquid composition comprises from about 1% to about 30% w/w low melting active ingredient of the total weight of the stable liquid composition.

According to an embodiment of the present invention, the composition comprises of a structuring agent.

According to an embodiment of the present invention, the stable liquid composition comprising:
a) a tetronic acid derivative;
b) a low melting active ingredient; and
c) a structuring agent selected from inorganic porous compounds.

In an embodiment of the present invention, the structuring agent is an inorganic porous compound selected from the group comprising of precipitated silica, fumed silica, glass and diatomaceous earth, clay, zeolite, kaolinite, montmorillonite, attapulgite, smectite, illite, bentonite, halloysite, vermiculite, and sepiolite.

In an embodiment of the present invention, the structuring agent of the stable liquid composition is selected from precipitated silica or fumed silica.

In a preferred embodiment of the present invention, the structuring agent of the stable liquid composition is precipitated silica.

In an embodiment, the stable liquid composition comprises of a structuring agent in an amount less than about 15% by weight of the stable liquid composition.

In an embodiment, the stable liquid composition comprises of a structuring agent in an amount which is about 10% by weight of the stable liquid composition.

In an embodiment, the stable liquid composition comprises of a structuring agent in an amount which is about 8.5% by weight of the stable liquid composition.

In an embodiment, the stable liquid composition comprises of a structuring agent in an amount which is about 5% by weight of the stable liquid composition.

In an embodiment, the composition comprises of a structuring agent in an amount which is about 1% by weight of the composition.

In an embodiment, the present invention provides a stable liquid composition comprising:
a) Spirodiclofen;
b) Bifenthrin; and
c) a structuring agent selected from inorganic porous compounds.

In an embodiment, the present invention provides a stable liquid composition comprising:
a) Spirodiclofen;
b) Bifenthrin; and
c) Precipitated silica.

In an embodiment, the present invention provides a stable liquid composition comprising:
a) Spirodiclofen;
b) Chlorpyrifos; and
c) a structuring agent selected from inorganic porous compounds.

In an embodiment, the present invention provides a stable liquid composition comprising:
a) Spiromesifen;
b) Bifenthrin; and
c) a structuring agent selected from inorganic porous compounds.

In an embodiment, the present invention provides stable liquid composition comprising:
a) a tetronic acid derivative;
b) a low melting active ingredient;
c) a structuring agent selected from inorganic porous compounds in an amount from about 0.1% to about 12% by weight of the composition; and
d) optionally, other auxiliary ingredients.

In an embodiment, the present invention provides stable liquid composition comprising:
a) a tetronic acid derivative;
b) a low melting active ingredient;
c) a structuring agent selected from inorganic porous compounds in an amount from about 0.1% to about 10% by weight of the composition; and
d) optionally, other auxiliary ingredients.

In an embodiment, the present invention provides stable liquid composition comprising:
e) a tetronic acid derivative;
f) a low melting active ingredient;
g) a structuring agent selected from inorganic porous compounds in an amount from about 0.1% to about 5% by weight of the composition; and
h) optionally, other auxiliary ingredients.

In an embodiment of the present invention, the auxiliary ingredients of the stable liquid composition are selected from one or more dispersing agents, wetting agents, fillers, surfactants, anticaking agents, pH-regulating agents, preservatives, biocides, antifoaming agents, colorants and other formulation aids.

Dispersing agents are selected from the group comprising salts of polystyrene sulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid/formaldehyde condensates, salts of condensates of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid, polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone and copolymers of (meth)acrylic acid and (meth)acrylic esters, alkyl ethoxylates, methacrylic acid-methyl methacrylate-polyethylene glycol copolymer, Tersperse 2500, Morwet D-425 , polyalkylene oxide block copolymers of a simple primary alcohol (e.g. ethylene oxide-propylene oxide block copolymers of butanol) such as Atlas™ G-5000, Termul™ 5429 or Tergitol™ XJ, XD or XH; polyisobutene succinic anhydride-polyethylene glycol such as Atlox™ 4914; polyhydroxystearate polyethers such as Atlox™ 4912, or polyalkylene oxide triblock copolymers of the type EO/PO/EO (where EO is ethylene oxide and PO is propylene oxide) such as Synperonic™ PE/F 127 and Poloxomer™ 338 and the like.

Wetting agents that can be added to the formulations of the present invention include but are not limited to: polyarylalkoxylated phosphate esters and their potassium salts (e.g., Soprophor® FLK; Stepfac TSP PE- K . Other suitable wetting agents include sodium dioctylsulfosuccinates (e.g., Geropon® SDS; Aerosol® OT; and ethoxylated alcohols (e.g., Trideth-6; Rhodasurf® BC 610; Tersperse® 4894).

Optionally, about 0.1 w/w % to about 5.0 w/w % of antifoaming or defoamers are employed to stop any unwanted foam generated while manufacturing stable liquid composition. The preferred antifoaming agent is selected from the group consisting of silicone-based compounds, alcohols, glycol ethers, mineral spirits, acetylene diols, polysiloxanes, organosiloxanes, siloxane glycols, reaction products of silicon dioxide and organosiloxane polymer, polydimethylsiloxanes or polyalkylene glycols alone or in combination. Defoamers that are suitable include SAG-10; SAG-1000AP; SAG-1529; SAG-1538; SAG-1571; SAG-1572; SAG-1575; SAG-2001; SAG-220; SAG-290; SAG-30; SAG-30E; SAG-330; SAG-47; SAG-5440; SAG-7133 and SAG-770.

Examples of thickening agents based on anionic heteropolysaccharides from the xanthan gum group e.g. Rhodopol® . Previously known commercial products from this group are Rhodopol 23®, Rhodopol G®, Rhodopol 50 MD®, Rhodicare T®, Kelzan®, Kelzan S® and Satiaxane CX91®, which are also preferred.

Preservatives used may be benzisothiazolinone (Proxel GXL) or phenols.

Suitable colorants (for example in red, blue and green) are, preferably, pigments, which are sparingly soluble in water, and dyes, which are water-soluble. Examples are inorganic coloring agents (for example iron oxide, titanium oxide, and iron hexacyanoferrate) and organic coloring agents (for example alizarin, azo and phthalocyanin coloring agents).

In an embodiment, the present invention provides stable liquid composition comprising from about 0.1% to about 70% w/w tetronic acid derivative, from about 0.1% to about 50% w/w low melting active ingredient and from about 0.1% to about 10% structuring agent of the total weight of the stable liquid composition is provided.

In a preferred embodiment of the present invention, stable liquid composition comprising from about 10% to about 40% w/w tetronic acid derivative, from about 1% to about 30% w/w low melting active ingredient, from about 0.5% to about 5% structuring agent of the total weight of the stable liquid composition is provided.

In a preferred embodiment of the present invention, stable liquid composition comprising from about 10% to about 40% w/w spirodiclofen, from about 1% to about 30% w/w bifenthrin, from about 0.5% to about 5% precipitated silica of the total weight of the stable liquid composition is provided.

In an embodiment of the present invention, the stable liquid composition comprising from about 10% to about 40% w/w spiromesifen, from about 1% to about 30% w/w bifenthrin, from about 0.5% to about 5% precipitated silica of the total weight of the stable liquid composition is provided.

In an embodiment of the present invention, the stable liquid composition comprising from about 10% to about 40% w/w spirodiclofen, from about 1% to about 30% w/w cypermethrin, from about 0.5% to about 5% precipitated silica of the total weight of the stable liquid composition is provided.

In an embodiment, the present invention provides the stable liquid composition comprising tetramic acid derivative, low melting active ingredient and a structuring agent .

In an embodiment, the present invention provides the stable liquid composition comprising from about 0.1% to about 70% w/w tetramic acid derivative, from about 0.1% to about 50% w/w low melting active ingredient and from about 0.1% to about 10% structuring agent of the total weight of the stable liquid composition.

In an embodiment, the present invention provides stable liquid composition comprising from about 0.1% to about 70% w/w spirotetramat, from about 0.1% to about 50% w/w bifenthrin and from about 0.1% to about 10% structuring agent of the total weight of the stable liquid composition.

In an embodiment of the present invention, a process of preparing stable liquid composition comprises:
1) preparing a slurry by adding a tetronic acid derivative, a low melting active and a structuring agent in water;
2) milling the slurry to achieve desired particle size;
3) separately, preparing a gel by adding thickening agent to a solvent; and
4) adding gel of step 3 to the slurry of step 2 to obtain the stable liquid composition.

In an embodiment of the present invention, the process of preparing -stable liquid composition comprises:
1) preparing a slurry by adding a tetronic acid derivative, a low melting active ingredient, a structuring agent and other auxiliary ingredients in water;
2) milling the slurry to achieve desired particle size;
3) separately, preparing a gel by adding thickening agent and optionally biocide to water; and
4) adding gel of step 3 to the slurry of step 2 to obtain the stable liquid composition.

In an embodiment of the present invention, the process of preparing a composition comprises:
1) preparing a slurry by adding spirodiclofen, bifenthrin, precipitated silica and other auxiliary ingredients in water;
2) milling the slurry to achieve desired particle size;
3) separately, preparing gel by adding xanthan gum and optionally a biocide; and
4) adding the gel of step 3 to the slurry of step 2 to obtain the stable liquid composition.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D10 of less than about 3.5 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D10 of less than about 0.05 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D50 of less than about 7.0 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D50 of less than about 2.0 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D50 of less than about 5 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D90 of less than or equal to about 30 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D90 of less than or equal to about 15 microns.

In an embodiment, the stable liquid composition of the invention has a particle size distribution D90 of less than or equal to about 5 microns.

According to an embodiment of the present invention, the slurry prepared in above steps is subjected to particle size reduction by applying shear to the mixture of active ingredients, structuring agent and other auxiliary agents. Suitable devices for applying shear include any high shear devices, e.g. high shear mixers, such as Ultra-Turrax apparatus, and dissolvers, static mixers, e.g. systems having mixing nozzles, bead mills, vibratory mills, agitator bead mills, colloid mills, cone mills, circulating mills (agitator ball mills with pin grinding system), disk mills, annular chamber mills, double cone mills, sprocket dispersers or homogenizers and other homogenizers.

According to an embodiment of the present invention, due to presence of low melting active ingredients, the milling operation may be performed in cryogenic or refrigerated cooling.

According to an embodiment of the present invention, the relative amount of tetronic acid derivative and low melting active from 50:1 to 1:50 and in particular from 20:1 to 1:20 (weight ratio) in the stable liquid composition.

In an embodiment of the present invention, the stable liquid composition comprising from about 10% to about 40% w/w spirodiclofen, from about 1% to about 30% w/w bifenthrin, from about 0.5% to about 5% precipitated silica of the total weight of the composition is provided wherein said composition is formulated as suspension concentrate.

According to an embodiment of the present invention, the stable liquid composition is intended to be diluted with water (or a water-based liquid) to form the corresponding end-use agrochemical formulations, typically spray formulations.

According to an embodiment of the present invention, the stable liquid composition has a pH ranging from 5-7.

According to an embodiment of the present invention, the stable liquid composition has a variation in pH of no more than 20% when at 54°C between 24 hours and 28 days. Preferably, no more than 10%. Most preferably, no more than 5%.

According to an embodiment of the present invention, the stable liquid composition provides a formulation which allows the active compounds to be taken up by the plant/the target organisms.

According to an embodiment of the present invention, the stable liquid composition is used as the source of active agrochemical ingredients and will typically be diluted to form end-use formulations, typically spray formulations. The dilution may be with water at from 1 to 10,000, particularly 10 to 1,000, times the total weight of the composition to form the spray formulation. Said composition may be diluted for use having an agrochemical active concentration of about 0.5 wt.% to about 1 wt.%. In said diluted composition the agrochemical active concentration may be in the range from about 0.001 wt.% to about 1 wt.% of the total formulation as sprayed.

Spray formulations include all the components which it is desired to apply to the plants or their environment. Spray formulations can be made up by simple dilution of the composition containing agrochemically active ingredients, or by mixing of the individual agrochemically active ingredients, or a combination of diluting the composition and adding further individual agrochemically active ingredients or mixtures of agrochemically active ingredients. Typically such end use mixing is carried out in the tank from which the formulation is sprayed, or alternatively in a holding tank for filling the spray tank. Such mixing and mixtures are typically termed tank mixing and tank mixtures.

In an embodiment of the present invention, there is provided a method of controlling insect pests wherein said method comprises applying an effective amount of stable liquid composition comprising a tetronic acid derivative; a low melting active ingredient; and a structuring agent, to the insect pests or to their locus.

In an embodiment of the present invention, there is provided a method of controlling insect pests, said method comprising applying an agrochemically effective amount of stable liquid composition comprising a) spirodiclofen, b) bifenthrin, c) a structuring agent and d) optionally, other auxiliary ingredients according to the present invention, to the insect pests or to their locus.

In an embodiment of the present invention, there is provided a method of controlling insect pests said method comprising applying an agrochemically effective amount of the stable liquid composition comprising a) spirodiclofen, b) bifenthrin, c) silica and d) optionally, other auxiliary ingredients according to the present invention, to the insect pests or to their locus.

In an embodiment of the present invention, the stable liquid composition is used as an insecticide.

In an embodiment of the present invention, the stable liquid composition comprising a tetronic acid derivative; a low melting active ingredient; and a structuring agent is used as an insecticide.

In an embodiment of the present invention, the stable liquid composition comprising a tetronic acid derivative, bifenthrin, silica is used as an insecticide.

According to an embodiment of the present invention, the various components of the composition can be used individually or already partially or completely mixed with one another to prepare the stable liquid composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.

In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare the stable liquid composition. E. g., kits may include active ingredients and/or structuring agent. One or more of the components may already be combined together or pre-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister.

In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for the composition.

In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination of stable liquid composition according to the invention for preparing the composition according to the invention.

In a preferred embodiment of the present invention, there is provided a stable liquid composition comprising a) a tetronic acid derivative, b) a low melting active ingredient, c) a structuring agent and d) optionally, other auxiliary ingredients, in the form of a kit with single pack or multi pack.

The stable liquid composition described above is insecticidally efficacious and is stable. It has been found that the structuring agent of said composition of the present invention, when used in quantity that is less than 15%, or less than 10%, or less than 5% by weight of the composition, provides excellent stability over time and at various temperatures, and even when the composition undergoes shear forces for example on mixing. Also, the composition obtained by the process have superior suspensibility, better dispersibility, very low or no sedimentation and little particle degradation.

All the features described herein may be combined with any of the above aspects, in any combination.

In order that the present invention may be more readily understood, reference will now be made, by way of example, to the following description. It will be understood that all tests and physical properties listed have been determined at atmospheric pressure and room temperature (i.e. 25°C), unless otherwise stated herein, or unless otherwise stated in the referenced test methods and procedures.

In any aspect or embodiment described hereinbelow, the phrase comprising may be replaced by the phrases “consisting of” or “consisting essentially of” or “consisting substantially of”. In these aspects or embodiment, the combination or composition described includes or comprises or consists of or consists essentially of or consists substantially of the specific components recited therein, to the exclusion of other fungicides or insecticide or herbicides or plant growth promoting agents or adjuvants or excipients not specifically recited therein.

Example 1: Spirodiclofen 24% and Bifenthrin 16% SC

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Propylene glycol 5.0

4 Precipitated silica
1.0
5 Alkyl EO/PO copolymer
2.5
6 Alkyl naphthalene sulfonate
1.5
7 Silicone antifoam
1.00
8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

5.0g Propylene glycol was added to water in a slurry preparation vessel. 2.5g Alkyl EO/PO copolymer and 1.5g Alkyl naphthalene sulfonate were added to the same vessel and stirred well to obtain homogeneous solution. To the homogeneous solution, 1.0g Silicone antifoam, 0.05g 1,2-benzisothiazolin-3-one and 1.0g precipitated silica was added under continuous stirring condition. Further, to the same vessel 22.45gm spirodiclofen and 15.03g bifenthrin was added with vigorous stirring to obtain the mixture. The mixture was further subjected to bead milling to achieve desired particle size. The uniform mixture thus obtained in bead milling was then transferred to gellification vessel containing pre-formulated 2% gel obtained by mixing 0.2g xanthan gum in 10 ml water to obtain suspension concentrate. The suspension concentrate was allowed to stand for 4 hours before use.

Example 2: Spirodiclofen 24% and Bifenthrin 16% SC

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Precipitated silica
5.0
4 Sodium dioctylsulfosuccinate
2.05
5 Alkyl naphthalene sulfonate
6.50
6 Silicone antifoam
1.00
7 1,2-benzisothiazolin-3-one
0.05
8 Xanthan gum
0.2
9 D M Water
QS
100.003

Spirodiclofen, bifenthrin, precipitated silica, Sodium dioctylsulfosuccinate, Alkyl naphthalene sulfonate, Silicone antifoam, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 3: Spirodiclofen 24% and Bifenthrin 16% SC (comparative example)

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Alkyl EO/PO copolymer
8.0
4 Sodium dioctylsulfosuccinate
3.5
5 Silicone antifoam
1.00
6 Propylene glycol 5.00

7 1,2-benzisothiazolin-3-one
0.05
8 Xanthan gum
0.2
9 D M Water
QS
100.00

Spirodiclofen, bifenthrin, alkyl EO/PO copolymer, Sodium dioctylsulfosuccinate, silicone antifoam, propylene glycol, 1,2-benzisothiazolin-3-one and Xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 4: Spirodiclofen 28% and Bifenthrin 14% SC

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
26.24
2 Bifenthrin Technical @98%
11.24
3 Fumed silica
1.00
4 Alkyl naphthalene sulfonate
2.00
5 Alkyl EO/PO copolymer
2.00
6 Silicone antifoam
1.00
7 Propylene glycol 5.00

8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

Spirodiclofen, bifenthrin, fumed silica, Alkyl naphthalene sulfonate, alkyl EO/PO copolymer, silicone antifoam, propylene glycol, and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 5: Spirodiclofen 20% and Chlorpyrifos 20% SC

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
18.74
2 Chlorpyrifos Technical
18.74
3 Fumed silica
1.00
4 Alkyl naphthalene sulfonate
2.00
5 Alkyl EO/PO copolymer
2.00
6 Silicone antifoam
1.00
7 Propylene glycol 5.00

8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

Spirodiclofen, chlorpyrifos, fumed silica, Alkyl naphthalene sulfonate, Alkyl EO/PO copolymer, silicone antifoam, 1,2-benzisothiazolin-3-one, propylene glycol xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 6: Spirodiclofen 24% and Chlorpyrifos 16% SC
# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Chlorpyrifos Technical
15.03
3 Precipitated silica
2.5
4 Sodium dioctylsulfosuccinate
2.0
5 Alkyl EO/PO copolymer
2.0
6 Silicone antifoam
1.00
7 Propylene glycol 5.00

8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

Spirodiclofen, chlorpyrifos, precipitated silica, Sodium dioctylsulfosuccinate, alkyl EO/PO copolymer, silicone antifoam, propylene glycol, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 7: Spirodiclofen 24% and Monocrotophos 16% SC

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Monocrotophos Technical
15.03
3 Precipitated silica
5.00
4 Alkyl naphthalene sulfonate
2.00
5 Alkyl EO/PO copolymer
2.00
5 Silicone antifoam
1.00
6 Propylene glycol 5.00

7 1,2-benzisothiazolin-3-one
0.05
8 Xanthan gum
0.2
9 D M Water
QS
100.00

Spirodiclofen, monocrotofos, precipitated silica, Alkyl naphthalene sulfonate, alkyl EO/PO copolymer, silicone antifoam, propylene glycol, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 8: Spirodiclofen 24% and Bifenthrin 16% SC
# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Propylene glycol 4.0

4 Precipitated silica
8.5
5 Sodium dioctylsulfosuccinate
3.0
6 Alkyl EO/PO copolymer
8.5
7 Silicone antifoam
1.00
8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

Spirodiclofen, bifenthrin, propylene glycol, precipitated silica, Sodium dioctylsulfosuccinate, alkyl EO/PO copolymer, Silicone antifoam, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 9: Spirodiclofen 24% and Bifenthrin 16% SC
# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Fumed silica
10.0
4 Alkyl EO/PO copolymer
2.0
5 Alkyl naphthalene sulfonate
2. 0
6 Silicone antifoam
1.00
7 1,2-benzisothiazolin-3-one
0.05
8 Xanthan gum
0.2
9 D M Water
QS
100.00

Spirodiclofen, bifenthrin, fumed silica, alkyl EO/PO copolymer, Alkyl naphthalene sulfonate, Silicone antifoam, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

Example 10: Spirodiclofen 24% and Bifenthrin 16% SC (comparative example)

# Ingredients
Quantity (%w/w)
1 Spirodiclofen Technical @98%
22.45
2 Bifenthrin Technical @98%
15.03
3 Propylene glycol 5.0

4 Precipitated silica
15.0
5 Alkyl EO/PO copolymer 3.5

6 Alkyl naphthalene sulfonate
5.0
7 Silicone antifoam
1.00
8 1,2-benzisothiazolin-3-one
0.05
9 Xanthan gum
0.2
10 D M Water
QS
100.00

Spirodiclofen, bifenthrin, propylene glycol, precipitated silica, alkyl EO/PO copolymer, Alkyl naphthalene sulfonate, silicone antifoam, 1,2-benzisothiazolin-3-one and xanthan gum were mixed in water in a given ratio shown above and suspension concentrate was prepared as per the process of Example 1.

The following test methods were used to determine performance of the structuring agent in the stable liquid compositions.

Formulation stability studies
Table 1
Structuring
Agent Test Suspensibility
(Gravimetric)
(%) Wet Sieve Analysis
(% Passed from 75µ mesh) Visual Observation

Example 1 1.00 Ambient 98.2 100% v
AH S 14 days 97.8 - v
Example 2 5.00 Ambient 99.1 100% v
AHS 14 days - v
Example 3 0.00 Ambient 97.6 100% v
AHS 14 days 100% X
Example 8 8.5 Ambient 98.7 100% v
AHS 14 days 100% v
Example 9 10.00 Ambient 98.2 100% v
AHS 14 days 100% v
Example 10 15.00 Ambient 97.6 100% v
AHS 14 days - X
v: Off white colored suspension concentrate free from extraneous matter.
X: Sample become solidify after removing from AHS and keeping at room temperature for 2-3 days.

A comparative study was performed to understand the effect of structuring agent in the liquid composition. The liquid compositions (Example 1, 2, 8, 9 and 10) were prepared by varying the amount of structuring agent. Also, composition as Example 3 was prepared without structuring agent. All the compositions were evaluated in ambient as well as in Accelerated Heat Stability (AHS) conditions. Results of the study are presented in Table 1. It was observed that compositions of Example 1, Example 2, Example 8 and Example 9 were found to be stable in ambient conditions as well as in AHS. These compositions remained as an off-white colored suspension concentrate free from extraneous matter. However, Example 3 and Example 10 failed in AHS conducted for 14 days at 54°C. Curding of dispersed phase was observed and became solidified thus failed to comply the standard specifications when tested in AHS. It was concluded that structuring agent in the range from about 0.1% to about 10% impart stability to the liquid compositions prepared according to the present invention. Quantity of structuring agent below and above the specified range failed to provide stable liquid compositions. The compositions prepared according to the present invention were also investigated for suspensibility and wet sieve analysis. All the compositions were found to have acceptable suspensibility and passed wet sieve test as 100% of the sample passed through 75µm mesh.

Particle Size determination

Particle size analysis of the stable liquid compositions was performed using Malvern Particle Size Analyzer 3000. 50 ml distilled water was taken in clean & dry 100 ml glass beaker. 5.0 g of sample from the composition according to Example 1 was added and stirred using glass rod to form the diluted suspension for analysis. Parameters in the analyser was set as per the standard (Refractive index-1.56, absorption-0.1, Particle type–Non-spherical, stirring RPM–2000, Dispersant refractive index–1.33). Particle size was determined with sonication in the analyser. Similarly, Example 2, 4, 5 and 6 were analysed on the Malvern analyzer. It was observed that particle size in all the compositions were well below 20µm. Results of particle size analysis is depicted in Table 2.

Table 2
Test Conditions Particle Size
D10 D50 D90

Example 1 Ambient 0.09 2.79 6.85
Example 2 Ambient 0.84 2.28 5.83
Example 4 Ambient 1.92 4.2 9.4
Example 8 Ambient 0.9 2.49 6.2
Example 9 Ambient 1.06 3.52 9.70

CONCLUSION:
The structuring agent of the present invention were used successfully to structure various compositions, with stability monitored over 14 days. The structuring agent provided good rheology performance over time, low or no sedimentation, and little particle size degradation. The Suspension Concentrate composition prepared according to the present invention also passed suspensibility test indicating that the structuring agent do not cause negative effects when the concentrates are diluted with water as they would be prior to normal use. It is to be understood that the invention is not to be limited to the details of the above embodiments, which are described by way of example only.
,CLAIMS:
1. A stable liquid composition comprising:
a. at least one tetronic acid derivative;
b. at least one low melting active ingredient; and
c. a structuring agent.

2. The stable liquid composition as claimed in claim 1 wherein said tetronic acid derivative is selected from the group consisting of spirodiclofen, spiromesifen their salts, esters and mixtures thereof.

3. The stable liquid composition as claimed in claim 1 wherein said tetronic acid derivative is spirodiclofen.

4. The stable liquid composition as claimed in claim 1 wherein said low melting active ingredient is selected from the group comprising of pyrethroids, triazole, organophosphate, thiadiazole, dioxolane, aminopyrimidine, strobilurins, spinosyn and cyclopropanecarboxylic acid.

5. The stable liquid composition as claimed in claim 1 wherein said low melting active ingredient is selected from the group comprising of bifenthrin, cypermethrin, fenvalerate, permethrin, alphacypermethrin, betacypermethrin, zetacypermethrin, deltamethrin, cyfluthrin, bifenthrin, lambda-cyhalothrin and bioresmethrin.

6. The stable liquid composition as claimed in claim 1 wherein said low melting active ingredient is bifenthrin.

7. The stable liquid composition as claimed in claim 1 wherein said structuring agent is selected from inorganic porous compounds.

8. The stable liquid composition as claimed in claim 7 wherein said inorganic porous compound is selected from the group comprising of precipitated silica, fumed silica, glass and diatomaceous earth, clay, zeolite, kaolinite, montmorillonite, attapulgite, smectite, bentonite, halloysite, vermiculite, and sepiolite.

9. The stable liquid composition as claimed in claim 1 wherein said stable liquid composition comprising of spirodiclofen, bifenthrin and a structuring agent selected from inorganic porous compounds.

10. The stable liquid composition as claimed in claim 9 wherein said inorganic porous compound is precipitated silica.

11. The stable liquid composition as claimed in claim 1 wherein said stable liquid composition is formulated as suspension concentrate (SC).

12. A process of preparing stable liquid composition comprising (a) at least one tetronic acid derivative; (b) at least one low melting active ingredient; and (c) a structuring agent, wherein said process comprising steps of:
(1) preparing a slurry by adding tetronic acid derivative, low melting active ingredient and a structuring agent in water;
(2) milling the slurry to achieve desired particle size;
(3) separately, preparing a gel by adding thickening agent; and
(4) adding gel of step 3 to the slurry of step 2 to obtain said stable liquid composition.

13. A method of controlling pests said method comprising applying an agrochemically effective amount of a stable liquid composition comprising a) a tetronic acid derivative; b) a low melting active ingredient; and c) a structuring agent; to the pests or to their locus.

14. The method of controlling pests as claimed in claim 13 wherein said method comprising applying an agrochemically effective amount of the stable liquid composition comprising a) spirodiclofen; b) bifenthrin; and c) a structuring agent; to the pests or to their locus.