FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See Section 10; rule 13)
"An Improved Agrochemical Formulation"
We, UNITED PHOSPHORUS LIMITED,
a company incorporated under the Companies Act,
1956 and having its corporate office Uniphos House,
11th Road, C, D Marg, Khar (West),
Mumbai-400 052,
State of Maharashtra
INDIA
&
INSTITUTE OF PESTICIDE FORMULATION TECHNOLOGY,
Sector-20, Udyog Vihar, NH-8, Opposite Ambiance Mall,
Gurgaon-122016
Haryana
INDIA
The following specification particularly describes the nature of this invention and the manner in which it is to be performed:-

An improved agrochemical formulation
Field of the Invention
The present invention relates to an improved agrochemical formulation comprising a synthetic pyrethroid. More particularly, the present invention relates to a biodegradable and storage stable pesticide formulation comprising a synthetic pyrethroid.
Background and prior art
Liquid emulsion concentrate formulations based on one or more organic solvents are known in the art of formulating agrochemical active ingredients. However, some of the common organic solvents that are known in the art are known to be non-biodegradable and highly inflammable. An agrochemical formulation devoid of an organic solvent or that includes organic solvents in minimum required quantities is certainly desirable in the art. The present invention provides such a biodegradable and storage stable agrochemical formulation.
It has been known in the art to prepare liquid emulsifiable concentrate formulations of solid or liquid low melting pesticides by dissolving the pesticide in comparatively large quantities of an organic solvent and thereafter adding surfactants and/or emulsifiers to afford a stable emulsion on being diluted with water. The stabilized emulsion thus obtained is ready to be sprayed onto the field. The use of large quantities of the organic solvents renders the formulations toxic to mammals and poses hazards during the manufacture, transport and application of the formulation. The organic solvents conventionally employed in the art, apart from being non-biodegradable and inflammable, are also highly volatile, which is responsible for irritating the eyes of the human personnel working in the field.
Moreover, the regulatory agencies around the world are now considering the public disclosure of all pesticide inert ingredients including solvents. These regulatory bodies are increasingly making it mandatory to identify all the inert ingredients including

solvents etc. on the product label. Thus, a formulation which substantially reduces or totally eliminates the requirement of an organic solvent and further reduces the presence of a surfactant or a co-surfactant and is thus completely biodegradable would be a highly desirable formulation from a regulatory and customer acceptance viewpoint.
Accordingly, there is a need in the art for an agrochemical formulation that is devoid of an organic solvent or that includes organic solvents in minimum required quantities. The present invention provides such an agrochemical formulation comprising a synthetic pyrethroid.
It is generally desirable to prepare formulations of toxic pesticides such as insecticides etc. having minimum volatility to reduce the incidence of off-site injury in order to avoid the unintended insecticidal activity. The volatility of formulations is known to cause various off site unintended injuries. Thus, it is another challenge in the art to prepare storage stable formulations of insecticides having a Substantially reduced volatility without compromising the other desirable properties of the formulation.
The stability of an emulsion can be indirectly measured by testing the turbidity of the formed emulsion with the passage of time. The turbidity of an emulsion is usually measured using a nephelometer, which has a detector set up to a side of the light beam. It has been seen that if there are lot of small particles present in the emulsion which are responsible for scattering the light beam, more light reaches the light detector included within the nephelometer. In an unstable emulsion, the particles tend to coalesce and settle at the bottom of the container and therefore contribute less to the turbidity reading. Thus, an emulsion in which the suspended particles settle quickly and do not contribute to the turbidity reading denotes an unstable emulsion and is undesirable. Accordingly, the stability of an emulsion can be measured using a calibrated nephelometer, which measures the turbidity of a formulation in terms of the nephelometric turbidity units or NTU. It is therefore another challenge in the art to prepare an agrochemical formulation which is storage stable i.e. wherein the particles do not coalesce and settle upon storage thus producing minimal variation in the NTU readings measured with a calibrated nephelometer with the passage of time.

It is further advantageous to provide an agrochemical formulation that is storage stable i.e. does not separate or sediment on prolonged storage or has reduced flammability.
These and other advantages may be realized by reference to the remaining portions of the specification, claims and abstract.
Objects of the invention ;
It is an object of the present invention to provide an agrochemical formulation comprising a synthetic pyrethroid such that the formulation is devoid of an organic
solvent.
Another object of the present invention is to provide an agrochemical emusifiable concentrate formulation of a synthetic pyrethroid wherein the amount of organic solvent required is less than the amount present in conventional emulsifiable concentrate formulations.
Another object of the present invention is to provide an agrochemical formulation of a synthetic pyrethroid wherein the formulation is devoid of or contains significantly reduced amount of a surfactant.
Another object of the present invention is to provide an agricultural formulation of a synthetic pyrethroid wherein the formulation is biodegradable and is environmentally clean.
Yet another object of the;present invention is to provide an agricultural formulation of a
synthetic pyrethroid wherein the formulation displays substantially reduced volatility
over conventional formulations thereby reducing the incidences of unintended off site
injuries. I
Another object of the present invention is to provide an agricultural emulsion or an emulsifiable concentrate formulation of a synthetic pyrethroid wherein the particles do

not coalesce or settle thus producing minimal variation in the NTU readings measured with a calibrated nephelometer with the passage of time.
Another object of the present invention is to provide a storage stable agricultural formulation that does not suffer from layer separation or sedimentation even after a prolonged storage.
Yet another object of the present invention is to provide a storage stable agricultural formulation of synthetic pyrethroid that possesses a higher flash point than the conventionally known formulations and is consequently less susceptible to fire hazards.
The various aspects and embodiments of the present invention may, but do not necessarily, achieve one or more of the aforesaid objectives.
Summary of the Invention
An agrochemical formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid; and
(b) biodiesel waste solvent.
An agrochemical formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid;
(b) biodiesel waste solvent; and
(c) at least another organic solvent.
An agrochemical emulsifiable concentrate formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid pesticide; and
(b) biodiesel waste solvent.
An agrochemical emulsifiable concentrate formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid;
(b) biodiesel waste solvent; and
(c) at least another organic solvent.

Detailed description of the Invention
Thus, in one aspect, the present invention provides an agrochemical formulation comprising (a) an insecticidally effective amount of at least one synthetic pyrethroid; and (b) biodiesel waste solvent.
The present invention is thus based on the surprising finding that the biodiesel waste solvent generated as the by-product from the transesterification of vegetable oils to biodiesel provides improved storage stability to agrochemical formulations of a synthetic pyrethroid. It has further been surprisingly found that the biodiesel waste solvent provides unexpected improvement in the emulsion stability to the agrochemical emulsifiable concentrate formulations of a synthetic pyrethroid.
It has further been found that emulsifiable concentrate formulations of a synthetic pyrethroid, wherein the formulation comprises the biodiesel waste solvent optionally in combination with a reduced amount of at least another organic solvent possess superior storage stability, are biodegradable and environmentally clean and totally eliminate or significantly reduce the amount of a surfactant required. The presence of at least another organic solvent is not mandatory. Thus, in one embodiment, the agrochemical compositions according to the present invention are substantially free of a conventionally used organic solvent. In another embodiment, the agrochemical compositions according to the present invention comprise a reduced amount of at least another organic solvent.
The term "substantially free of shall be understood to mean that the at least another organic solvent cannot be detected in the formulations using conventional techniques or is present in trace quantities only. It shall be understood to mean that the maximum presence of an organic solvent, if traceable, shall be less than 3%, preferably less than 1% and more preferably less than 0.1% in the formulations according to the present invention.
Thus, in this embodiment, the present invention provides an agrochemical formulation comprising (a) an insecticidally effective amount of at least one synthetic pyrethroid; (b) biodiesel waste solvent; and (c) at least another organic solvent.

The agrochemical compositions according to the invention can be formulated in various ways, depending on the prevailing biological and/or chemical-physical parameters. The following are examples of suitable formulation possibilities: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), seed-dressing materials, granules for spreading and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
In a preferred embodiment, the preferred formulation is an emulsifiable concentrate formulation. In an embodiment, the preferred emulsifiable concentrate formulation may be substantially free of another organic solvent. It has thus been surprisingly found that the presence of the biodiesel waste solvent has now made it possible to prepare emulsifiable concentrate formulations without an organic solvent. Hitherto, it was considered infeasible to prepare an emulsifiable concentrate formulation without using an organic solvent.
Thus, in this embodiment, the present invention provides an emulsifiable concentrate formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid pesticide; and
(b) biodiesel waste solvent.
In another embodiment, the agrochemical emulsifiable concentrate formulations according to the present invention include a reduced amount of an organic solvent. Thus, in this embodiment, the present invention provides an agrochemical emulsifiable concentrate formulation comprising:
(a) an insecticidally effective amount of at least one synthetic pyrethroid pesticide;
(b) biodiesel waste solvent; and

(c) at least another organic solvent.
Unless otherwise indicated, the term "biodiesel waste solvent" as used herein denotes the crude glycerol fraction generated from the transesterification of vegetable oils to biodiesel.
The biodiesel waste solvent of the present invention typically includes one or more of glycerin; methyl esters; alcohols; mono-, di- and tri-glycerides; free fatty acids, triglyceride esters and combinations thereof.
The preferred process for the preparation of biodiesel and the waste solvent produced therewith is otherwise known to a person skilled in the art and does not limit the present invention.
The transesterification reaction herein described affords two phases wherein the first phase comprises predominantly of methyl esters (biodiesel phase) while the remaining phase (by-product phase) comprises predominantly of glycerol, which is the biodiesel waste solvent of the present invention.
Preferably, the biodiesel waste solvent of the present invention is obtained as a by-product during the production of biodiesel by the transesterification of jatropha oil or karanja oil.
In a preferred embodiment, the waste solvent generated as a by-product during the transesterification of vegetable oil, which is found suitable for the present invention comprises glycerol (40-50%), methyl ester (40-45%), alcohol (0.2-1%), mono-, di- and tri- glycerides (1.5-3%), free fatty acid (1-20%), triglyceride ester (0.1-0.2%) and water (0.1-0.3%).
The known methods for separating biodiesel waste solvent of the present invention from the biodiesel fraction includes decanting, centrifuging and hydrocycloning and further refining by a sequence of steps including chemical and physical refining followed by

purification. These steps per se axe known in the art and do not limit the present invention in any manner.
Thus, it has been found that the biodiesel waste solvent eliminates the need for an additional organic solvent in emulsifiable concentrate formulations of synthetic pyrethroids.
The concentration of the biodiesel waste solvent in the compositions according to this embodiment of the present invention is not particularly limiting and depends on the amount of the synthetic pyrethroid active ingredient present in the composition. For example, in one preferred embodiment, a predetermined amount of the synthetic pyrethroid active ingredient sufficient to prepare a known formulation strength of the pyrethroid may be formulated with the remaining percentage of the formulation constituted entirely of the biodiesel waste solvent. In another embodiment, the remaining percentage of the formulation may comprise other adjuvants and additives that are conventionally included in the known agrochemical formulations.
It has further been found that the biodiesel waste solvent may be used in combination with other organic solvents for preparing emulsifiable concentrate formulations comprising synthetic pyrethroids, wherein the amount of the organic solvent is significantly reduced from the amount of the organic solvent employed in conventional formulations.
Unless otherwise indicated, the term "at least another organic solvent" used throughout the specification denotes another organic solvent that is conventionally employed in the art for preparing known agrochemical compositions, preferably emulsifiable concentrate formulations. The choice of the organic solvent is not particularly limiting.
Preferably, the "at least another organic solvent" may be selected from the group comprising acetic acid, acetone, acetonitrile, benzene, 1-butanol, 2-butanone, t-butyl alcohol, carbon tetrachloride, chloroform, cyclohexane, diethylene glycol, diglyme, dimethoxyethane, dimethyl formamide, dimethyl sulfoxide, dioxane, ethanol, diethyl ether, dimethyl ether, ethylene glycol, glycerin, heptane, hexane, methanol, methyl t-

butyl ether, methylene chloride, pentane, 1-propanol, 2-propanol, tetrahydrofuran, toluene, xylene and ethyl acetate, though known organic solvents are not excluded.
In another embodiment, the organic solvent that is particularly preferred may be selected from the group consisting of Aromax, C-9, SoIvesso-100, Solvesso-150, Solvesso- 200, xylene, bonemax, naphtha and R-9.
The amount of the organic solvent in this aspect of the present invention is not particularly limiting and may be determined accordingly by a person skilled in the art. Preferably, the organic solvent is present in an amount of about 0%% to about 70% by total weight of the formulations according to the present invention.
Unless otherwise indicated, the term "synthetic pyrethroid" used throughout the specification denotes an agrochemical compound selected from the group consisting of cypermetnrin, permethrin, fenvalerate, deltamethrin, bifenthrin, cyhalothrin and lambda cyhalothrin.
The term "insecticidally effective amount" of a synthetic pyrethroid shall denote an amount of the synthetic pyrethroid, which when administered at a locus, causes one or more selected insects present at the locus to be killed or controlled. Preferred insecticidally effective amounts are those that are sufficient to kill one or more insects.
Preferably, the compositions and more preferably, the emulsifiable concentrate formulations according to this aspect of the present invention comprise from about 2% to about 25% of the synthetic pyrethroid by total weight of the formulation.
The amount of the "at least another organic solvent" and the biodiesel waste solvent in the compositions according to the instant embodiment is not limiting. Preferably, the biodiesel waste solvent is present in an amount of about 4% to about 50% of the agrochemical emulsifiable concentrate formulation according to the present aspect of the invention.

In a preferred embodiment of the above aspects of the present invention, the compositions according to the present invention may further include a surfactant in an amount of about 4% to about 20% by total weight of the composition. In another embodiment, the agrochemical compositions, preferably the emulsifiable concentrate formulations according to the present invention comprise from 0% to upto 10%, preferably upto 5% of a co-surfactant.
In a preferred embodiment, the surfactant and/or co-surfactant may be any industrial surfactant or co-surfactant known in the art without limitation. In an embodiment, the surfactant and/or co-surfactant may be selected from the group comprising nonyl phenol ethoxylate, ethoxylated castor oil, calcium salt of an alkyl benzene sulfonate and n-butyl alcohol. More preferably, the co-surfactant is n-butyl alcohol.
However, the presence and amount of the surfactant is not particularly limiting and may be determined by a skilled artisan without departing from the spirit and scope of the present invention.
EXAMPLES
The following examples illustrate embodiments of the proposed invention that are presently best known. However, other embodiments can be practiced that are also within the scope of the present invention. All of the agrochemical formulations exemplified below had acceptable to excellent emulsion stability and each exhibited at least acceptable storage stability properties.
EXAMPLE 1
Cypermethrin 25%EC
The 254 gm. of molten Cypermethrin technical was added to 576 gm. of organic solvent(s) i.e. Xylene, Naphtha, Bonemax, CIX, and 80 gm. Of biodiesel waste solvent was mixed, thereafter added 90 gm. of blend of surfactants/emulsifiers i.e. alkyl benzyl sulfonates and alkyl phenyl ethoxylates. The mixture was then mixed until it become homogenous and clear one phase liquid. Finally EC formulation was formed. Emulsions

of any desired concentration can be obtained from such concentrates by dilution with
water.
This formulation has the following characteristics:
1. It is stable at 54°C for 14 days.
2. It shows no phase separation / sedimentation with time.
3. Gives stable emulsion when diluted with water.
EXAMPLE 2 Permethrin 25 % EC
The 264 gm. of molten Permethrin technical was added to 546 gm. of organic solvent(s) and added 90 gm.of green solvent i.e., biodiesel waste and mixed well; thereafter added l00gm. of blend of surfactants/ernulsifiers i.e. alkyl benzyl sulfonates and alkyl phenyl ethoxylates. The mixture was then mixed until it become homogenous and clear one phase liquid. Finally EC formulation was formed. This formulation had the following characteristics:
1. It is stable at 54°C for 14 days.
2. It shows no phase separation / sedimentation with time.
3. Gives stable emulsion when diluted with water.
EXAMPLE 3 Cypermethrin 10 % EC
The 109 gm. of molten Cypermethrin technical was added to 686 gm. mixture of organic solvent(s) i.e.Xylene, Bonemax, CIX, Naphtha and added 80 gm of green solvent i.e.,biodiesel waste and 35 gm. of n-butyl alcohol and mixed well to have a homogenous liquid, thereafter added 90 gm.. of combination of alkyl benzyl sulfonates and alkyl phenyl ethoxylates in a ratio of 3:2. The mixture was then mixed until it become homogenous and clear one phase liquid. Finally EC formulation was formed. This formulation had the following characteristics:
1. It is stable at 54°C for 14 days.
2. It shows no phase separation / sedimentation with time.

3. Gives stable emulsion when diluted with water as per BIS / CIPAC standard.
EXAMPLE 4 Fenvalerate 10 % EC
The 110 gm. of molten Fenvalerate technical was added to 650 gm. mixture of organic solvent(s) i.e. Xylene, OX, Naphtha, 100 gm. of combination of alkyl benzyl sulfonates (60%) and alkyl phenyl ethoxylates (40%) , 100 gm. of green solvent i.e. biodiesel waste and 40 gm. of n-butyl alcohol. The mixture was then mixed until it become homogenous and clear one phase liquid. Finally EC formulation was formed. This Formulation had the following characteristics:
1. It is stable at 54°C for 14 days.
2. It shows no phase separation / sedimentation with time.
3. Gives stable emulsion when diluted with water as per BIS / CIPAC standard.
EXAMPLE 5
Fenvalerate 0.4% Dust
To 990 gm of solid carrier (soap stone clay) was added a mixture of 4.35 g of Fenvalerate technical and 5.65 gm of green solvent. The product was mixed to have a homogenous distribution of the active content. The product obtained was in the form of fine dustable powder which can be used in agriculture or public health purpose.
Example-6
Permethrin 10% Granules CG
To the 830 gm of solid carrier (bentonite blank granules) was added a mixture of 106 g of Permethrin technical, 24 gm of green solvent and 20 gm of stabilizer. The addition of mixture was done by using the required quality of spraying equipment, which provides a uniform homogenous distribution of the active content. The product obtained was then coated with 20 gm of Stearic acid solution. The product obtained was in the form of coated granules (CG) which can be used in agriculture or public health purpose with or without dilution.

The active ingredient (or active ingredient mixture) is dissolved in green solvent and stabilizer and applied to the carrier by spraying, and the coating solution is then applied on these granules.
Example-7
Lambda cyhalothrin 10% DF
The Lambda cyhalothrin is mixed with the green solvent and ground with the other inert ingredients, and the mixture is moistened with required quantity of water. The mixture is extruded and then dried in a stream of air to have the extruded granules.
Example 8
An artificial biodiesel waste solvent sample was prepared by adding all the constituents that are normally present in the biodiesel waste solvent. Thereafter, an agrochemical formulation was prepared comprising the artificial waste solvent and another formulation was prepared with the naturally prepared waste solvent. The two formulations were then compared with each other. It was observed that the formulation comprising the artificial waste solvent sample was not as homogenous as the formulation comprising the naturally produced biodiesel waste solvent. It was further found that oil droplets settled at the bottom of the formulation sample comprising the artificial biodiesel waste solvent sample. The volatility of the formulation comprising the artificial biodiesel waste solvent sample was found approximately 10% greater than the volatility of the formulation comprising the biodiesel waste solvent.
It was further found that the agrochemical formulations comprising the biodiesel waste solvent demonstrated superior emulsion stability, reduced volatility and higher flash points.
Following the procedure laid down in the above examples for the preparation of emulsifiable concentrate formulations, the following emulsifiable concentrates were also prepared.

Example 9 Cypermethrin 25 EC

Example 10 Cypermethvrin 10 EC

Example 11

Emulsion Stability

A series of experiments were devised to compare the emulsion stability for emulsifiable concentrate formulations of cypermethrih (25EC) with and without the biodiesel waste solvent. A formulation A was prepared comprising about 25 g of cypermethrin in the presence of an organic solvent (one or more of C-9, xylene, bonemax, naphtha in an amount of about 60-70%), surfactant (in an amount of about 10-20%) and co-surfactant in an amount of about 3-5% (one or more of nonyl phenol ethoxylate, ethoxylated castor oil, calcium salt of alkyl benzene sulfonate and n-butyl alcohol). A formulation B was prepared comprising about 25 g of cypermethrin in the presence of biodiesel waste solvent (about 50g), surfactant and co-surfactant (one or more of nonyl phenol ethoxylate, ethoxylated castor oil, calcium salt of alkyl benzene sulfonate and n-butyl alcohol). The emulsion stability of formulation A was tested and compared vis-a-vis the emulsion stability of formulation B using the digital turbidity meter 211 R, with the following results:

It was surprisingly found that NTU measurement of the formulation without the biodiesel waste solvent fell rapidly after two hours from a comparable initial reading. It was concluded that the particles in the formulation A without the biodiesel waste solvent rapidly coalesced and settled at the bottom of the container after about 2 hours while sample B containing biodiesel waste solvent maintained uniform NTU readings, which are indicative of no coalescence or settling. The formulation B particles did not coalesce and settled producing minimal drop (about 0.7% drop) in the NTU readings measured with a calibrated nephelometer even two hours after storage in contrast to the formulation A, which dropped by about 16.5%. It was concluded that formulation B was about 24 times more emulsion stable than the formulation A while the two formulations differed only in the presence or absence of the biodiesel waste solvent. Importantly, the

formulation B did not show any layer separation or sedimentation after 14 days at room temperature as well as at 54 C.
Reduced Volatility
The volatility of the emulsifiable concentrate formulations with and without biodiesel waste solvent i.e. formulations B and A respectively was compared. 20 ml of the respective samples were taken in 50 ml of beaker and volatility of these formulations was checked for 72 hrs under same condition. It was found that the % loss was more in formulation A as compared to the formulation B containing biodiesel waste as a solvent. The % loss in the formulation A was 30% as compared to the formulation B containing biodiesel waste solvent, in which the percentage loss was only about 12.0%.

Thus, the present inventors believe that the volatility of the formulations containing biodiesel waste solvent being substantially less by a factor of about 2.5 times than the volatility of formulation A, the formulation B containing biodiesel waste solvent could be expected to substantially reduce the incidence of off-site injury and thus substantially reduce the occurrence of unintended insecticidal activity.
Flash Point
The flash point of an emulsifiable concentrate formulation containing biodiesel waste solvent i.e. formulation B was found to be about 38°C as compared to formulation A, which measured a flah point of about 32°C. Thus, formulation B comprising biodiesel waste solvent could be expected to possess a reduced susceptibility to fire hazards.
Efficacy
The formulations according to the present invention comprising biodiesel waste solvent and exemplarily cypermethrin were tested for their activity against a variety of insect pests and were found to possess surprisingly enhanced efficacy against the tested pests.

A series of experiments were conducted to measure the contact insect-toxicity using an emulsifiable concentrate formulation of cypermethrin (25EC) with biodiesel waste solvent, without biodiesel waste solvent and with biodiesel waste solvent in the presence of a reduced amount of another organic solvent. It was surprisingly found that biodiesel waste solvent showed good synergism with cypermethrin. It was further found that the active content of cypermethrin in the tested pests surprisingly increased in the treatments with added biodiesel waste solvent than the treatments in which no biodiesel waste solvent was added. Without wishing to be bound by theory, it is believed that this resulted due to the enhanced penetration of cypermethrin active ingredient within the target species upon administration of the formulation comprising biodiesel waste solvent in comparison to the conventional formulation without biodiesel waste solvent. It is believed, without wishing to be bound by theory, that this surprising enhancement in the penetration of the active ingredient in the presence of biodiesel waste solvent could be attributed to the presence of certain biodegradable surfactants in biodiesel waste solvent, which synergistically enhance the penetration of the active ingredient within the target species, thereby resulting in a surprising enhancement in efficacy of the active ingredient. The field trials conducted demonstrated that the addition of biodiesel waste solvent substantially and surprisingly reduced the pest population in the formulations containing cypermethrin as the pesticidal active ingredient.
Moreover, it was surprisingly found that the formulation of cypermethrin in the presence of the biodiesel waste solvent demonstrated unexpected, surprising and rapid knockdown activity. It was found to be effective in control against a wide range of chewing and sucking insects such as Lepidoptera, Coleoptera and Hemiptera in fruits including citrus fruits, vegetables, vines, cereals, maize, beet, oilseed rape, potatoes, cotton, rice, soybeans, forestry and other crops. It was also found effective to control cockroaches, mosquitoes, flies and other insect pests. It was surprisingly found effective in controlling mammalian health as an ectoparasiticide.

While the invention has been described by reference to specific examples, this was for purposes of illustration only. Numerous alternative embodiments will be apparent to those skilled in the art and are considered to be within the scope of the invention.

WE CLAIM :
1. An agrochemical formulation comprising an insecticidally effective amount of at least one synthetic pyrethroid; and biodiesel waste solvent.
2. An agrochemical emulsifiable concentrate (EC) formulation comprising an insecticidally effective amount of at least one synthetic pyrethroid pesticide; and biodiesel waste solvent.
3. The formulation as claimed in claim 1 or claim 2 additionally comprising at least another organic solvent.
4. The formulation as claimed in claim 1 or claim 2, wherein said formulation is substantially free of an organic solvent.
5. The formulation as claimed in claim 1, wherein said formulation is formulated as wettable powder (WP), water-soluble powder (SP), emulsion such as oil-in-water (EW) and water-in-oil emulsion (EO), suspension concentrate (SC), oil based dispersion (OF) or water-based dispersion, oil-miscible solution, capsule suspension (CS), dust, seed-dressing material (DS or WS or SS), granule for spreading and soil application, granule (GR) in the form of microgranule (MG), spray granule, coated granule (CG) and adsorption granule (G), water-dispersible granule (WG), water-soluble granule (SG), ULV formulation, microcapsule and wax.
6. The formulation as claimed in claim 1 or claim 2, wherein said biodiesel waste solvent comprises the crude glycerol fraction generated from the transesterification of vegetable oils to biodiesel.

7. The formulation as claimed in claim 1, claim 2 or claim 16, wherein said biodiesel waste solvent comprises glycerin; methyl esters; alcohols; mono-, di- and tri-glycerides; free fatty acids, triglyceride esters and combinations thereof.
8. The formulation as claimed in claim 6, wherein said vegetable oil is jatropha oil or karanja oil.
9. The formulation as claimed in claims 1, 2, 6 or 7, wherein said biodiesel waste solvent comprises glycerol in an amount of about 40% to about 50%, methyl ester in an amount of about 40% to about 45%, alcohol in an amount of about 0.2% to about 1%, mono-, di- and tri- glycerides in an amount of about 1.5% to about 3%, free fatty acid in an amount of about 1% to about 20%, triglyceride ester in an amount of about 0.1% to about 0.2% and water in an amount of about 0.1% to about 0.3%.
10. The formulation as claimed in any preceding claim additionally comprising one or more agrochemical adjuvants.
11. The formulation as claimed in claim 3, wherein said at least another organic solvent is selected from Aromax, C-9, Solvesso-100, Solvesso-150, Solvesso- 200, xylene, bonemax, naphtha and R-9.

12. The formulation as claimed in claim 3 or claim 11, wherein said at least another organic solvent is present in an amount of about 0% to about 70% by total weight of the formulation.
13. The formulation as claimed in claim 1 or claim 2, wherein said synthetic pyrethroid is selected from cypermethrin, permethrin, fenvalerate, deltamethrin, bifenthrin, cyhalothrin and lambda cyhalothrin.

14. The formulation as claimed in claim 1, claim 2 or claim 13, wherein said insecticidally effective amount of a synthetic pyrethroid comprises from about 2% to about 25% by total weight of the formulation.
15. The formulation as claimed 1 or claim 2, wherein the amount of biodiesel waste solvent is from about 4% to about 50% by total weight of the formulation.
16. The formulation as claimed in any preceding claim additionally comprising a surfactant optionally in combination with a co-surfactant.
17. The formulation as claimed in claim 16, wherein said surfactant is present in an amount of about 4% to about 20% by total weight of the formulation.
18. The formulation as claimed in claim 16, wherein said co-surfactant is present in an amount of from about 0% to about 10% by total weight of the formulation.
19. The formulation as claimed in claim 16 or claim 17, wherein said surfactant is selected from nonyl phenol ethoxylate, ethoxylated castor oil, calcium salt of an alkyl benzene sulfonate and n-butyl alcohol.
20. The formulation as claimed in claim 16 or claim 18, wherein said co-surfactant is n-butyl alcohol.
21. An emulsifiable concentrate formulation comprising about 25% cypermethrin and biodiesel waste solvent.
22. An emulsifiable concentrate formulation comprising about 25% permethrin and biodiesel waste solvent.

23. An emulsifiable concentrate formulation comprising about 10% cypermethrin and biodiesel waste solvent.
24. The formulation substantially as disclosed herein with reference to examples 1-11.
Dated this 11th day of November 2008
Ashwini Sandu GM - IPR United Phosphorus Limited