FORM -2
THE PATENT ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
NOVEL INSECTICIDAL COMPOSITION
We, UNITED PHOSPHOURUS LIMITED, a Company incorporated under the Companies Act, 1956 and having its registered office at 3-11 GIDC , Vapi-396 195, State of Gujarat, India and having its office at Uniphos House, 11th Road, C. D. Marg, Khar (West), Mumbai - 400 052 , State of Maharashtra, India.


The following specification particularly describes and ascertains the nature of this invention and the
manner in which it is to be performed :
ORIGINAL
59/MUM/2003
GRANTED
23-2-2006

[ntroduction
This invention relates to a novel insecticidal composition chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate. The composition containing chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate are useful as insecticides. The composition of the present invention is in the form of solids without containing water or any solvent
Acephate is one of the important commercial insecticides within Phosphoroanmdothoates class of compounds, which is a systemic insecticide of moderate persistence with residual activity lasting about 10 - 15 days. It is effective against a wide range of aphids, leaf miners, lepidopterous larvae, saw flies and thrips. It is non-phytotoxic on many crop plants.
Phosphoroamidothioate (Acephate) has the formula I given below:

wherein R and R 1 individually are an alkyl, alkenyl or alkynyl group containing upto 6 carbon atoms, R 2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms, R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and X is oxygen or sulfur.
Back Ground of the invention.
In recent years, agricultural chemicals are most preferably formulated in the form of dusts, wettable powders, soluble powders, emulsifiable concentrates, soluble liquid/concentrates, granules, coated granules, water dispersible granules, suspension concentrates, solutions.

Occasionally when dust produced by absorbing active ingredient into or mixed with a finely divided inert carrier material, for example China Clay or the likes, at the time of application poses drift problem. With wettable powders and soluble powders the problems faced at the time of dilution is drift and final disposal of container as it has dust particles sticking to its sides, residues of these formulations poses great problem to environment, to operators and user.
Dusts are undesirable because of airborne contamination and handling difficulties, while liquid spray formulations involve solvent and packaging expenses, and container disposal requirements that detract from commercial desirability.
However, Water Dispersible Granules produced by fluidized bed spray dryer overcomes all the problem of Wettable Powders and Soluble Powders but high cost of processing, high value capital investment as well as highly skilled staff requirements imposes a significantly prohibitive factor in widening the market acceptance.
Prior Art
In the US patent No. 5,075,058 (issued on Dec. 24, 1991) pellets comprising of insecticidal N-Hydrocarboyl Phosphoroamidothioates and/or Phosphoroamidodithioates have been described These pellets are prepared by extrusion of a solid composition. The concentration of the active ingredient in the pellets prepared is in the range of about 2 to 80% a.i. with the most likely concentration of 70% ax. The process comprises (i) forming an extrudablc mixture comprising active ingredients; (ii) forming said pellets by extrusion of the said mixture and cutting the extrudate.
Similar pellets have also been prepared by another method described in the said patent. Accordingly such pellets are prepared by (i) forming a suspension or solution containing said active ingredient and a dipersant, wetting agent and/or surfactant (ii) evaporating the solvent from said solution or dispersion (iii) dividing the remaining solids into particles; and (iv) forming the resultant mixture into pellets.
The limitation and difficulties of the pellets by the process described in the above said patent are:
1. The amount of active ingredient is in the range of about 2 to 80%, preferable being 70% so the process does not provide the pellets of a concentration of active ingredient above 80%.
2. The product envisages two active ingredients namely n-hydrocaboyl phosphoroamidothioates and phosphoroamidodithioates in a single product, which complicates the decision to decide the

combination of ingredients. If the selection is not perfect, the product may deteriorate in few days to few months. 3. The product is formed by making a suspension or solution of the active ingredient and a dispersant, wetting agent and/or surfactant, evaporating the solvent etc. which are complicated making the process cumbersome and uneconomical.
In another US Patent No. 5,100,667 (issued on Mar 31, 1992) pellets of insecticidal N-Hydrocarboyl Phosphoroamidothioates and Phosphoroamidodithioates has been disclosed in which the concentration of the insecticidal ingredient in the pellets formed is in the range of about 50 to 95% preferably about 90%. The pellets are prepared mixing technical grade insecticide in a dry form with one or a mixture of surfactants (10% by weight of total dry composition) preferably containing an inert diluents ammonium sulfate (<40% of total pellet composition preferably 2% or less); solid additive (upto about 40% anhydrous Magnesium (Sulphate) and small amounts of deodorants and antifoam agents. The dry ingredients are ground to powdered form Currently available pelletized ORTHENE requires the use of the anticaking agent (such as fumed silica).
Limitations and difficulties of the pellets prepared by US Patent No 5.100.667 are:
1. The amount of insecticidal ingredient present in these pellets is in the range of about 50 to 95 %, preferably about only 90%
2. The final product may also contain inert diluent ammonium sulfate (<40% of total pellet composition preferably 2% or less) by weight of the total pellet composition. The presence of these agents are not desirable in the final product as it adds the cost and gives hardness when the Active ingredient in the granules are in low concentration.
3. The product may also be included up to about 40% anhydrous Magnesium sulphate preferably 2% or less by weight of the total pellet composition as dehydrating agent to absorb trace amounts of the water present in the pellets to prevent hydrolysis of the insecticide. The presence of these agents are not desirable in the final product as it adds insoluble matter in granules which cause problem in the application of the product by way of blocking the nozzle.
4. The final product may also contain small amounts of deodorants which is also not desirable as it may devoid the caution for keeping the material in the closed container which can cause the degradation of the product.

US patent no. 5.464,623 (issued on Nov. 7, 1995 )discloses palletized insecticidal N-Hydrocarboyl phosphoroamidothioates and pbosphoroamidodithioates . These pellets are prepared by a process involving extrusion of a damp sandy loam of a dry mixture of the active ingredient and a solvent.
Limitations and difficulties of the pellets are :
1. The pellets are formed by mixing of active ingredient in a solvent to form a consistency of damp sandy loam and then pellets are formed by extrusion. Hence the pellets formed may contain water which is not preferred
2. The pellets are formed by passing the mixture of active ingredient and the solvent in molten form through an orifice to form molten pellet-sized drops of said active ingredient and solidifying the said drops. The pellets formed may contain solvent which is not preferred
Accordingly, the present invention is directed towards providing a novel insecticidal composition in solid form without using water or solvent, and providing chemically stable, dry flow, low compact, dust free, insecticidally active soulblenules of Phosphoroamidothioate. For convenience, Phosphoroamidothioates is the term referred for certain phosphoroamidothioates and phosphoroamidodithioates ( Acephate) is one of the important commercial insecticide within Phosphoromidothioates class of compounds which is systa insecticide of moderate persistence with residual acting testing about 10-15 days are known to have excellent insecticidal activity against a variety of insects and in a variety of environments.
The applicants have conducted considerable experimentation in the area of producing high-strength Acephate granules, and have confirmed the manufacturing difficulties which earlier applicants apparently experienced. Furthermore, the pellets and methods proposed for making them as discussed in the above said three prior art patents leave considerable room for improvement.
The formulation of Acephate , presently in use, is Acephate 75% Soluble Powder have Acephate active ingredient 75% (w/w), surfactant 1 to 2% (w/w), inert filler (precipitated silica) to make 100% (w/w). It poses the problems like dust, low pourability, high transportation cost, high capital manufacturing investment, not easily measurable, difficulties in packing material disposal, handling problems, high risk of caking and others.

Therefore there is a need for the development of a novel insecticidal composition in solid form produced without using water or solvent finally providing granules of Acephate which is chemically stable, dry flow, low compact, dust free and soluble granules. Such a composition will be much safer and effective. The resultant insecticidal composition will be useful from a practical stand point, as well as for a low cost, practical manufacturing technique which can be practiced on a commercial scale without requiring expensive additives or solvents.
Accordingly the main objective of the present invention is to remove majority of limitations of the present day available insecticides. The insecticidal product provided by this invention will be relatively more advantageous and exhibits certain very desirable characteristics noted herein after.
In the recent years, attention has turned to granular form of application for Acephate and its related insecticidal composition containing it having the following qualities :

> Dust free
> Good pourability
> High active ingredient
> Low transportation cost
> Low capital investment
> Good stability of product
> Freely flowable
> Easy to measure
> Best utilisation of energy sources
> Less wastage during processing
> Better bioefficacy
> Easy disposal of packing material
> Easy to handle
> Limited risk of caking
> Good dispersibility
> Good resistance to attrition
> Semi skilled operators required
> Less space requirements for production
> With good market potential
> Easily reproducible during processing

Summary of the Invention.
This invention relates to novel solid insecticidal composition in solid form without water or solvent finally providing chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate which are insecticidally active, along with specified adjuvants and other inert ingredients which are all solids. The concentration of the active ingredient present in the formulation of the present invention, namely, chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate varies from 50 - 97% of Phosphoroamidothioates (Acephate) active ingredient.
The process comprises (i) preparing a dry premix by mixing 95% to 99% of the Phosphoroamidothioate of the formula I, dispersing agent 0.1% to 5.0%, wetting agent 0.1% to 3.0%, binding agent 0.1% to 0.3%, antifoaming agent 0.01% to 0.08%, disintegrating agent 0.01% to 10.0%, Stabilizers) 0.01% to 1.0% and filler(s) to make 100% (w/w), all in the form of solids without water or solvent, in a premixer ; (ii) grinding the resulting mixture in microniser to obtain 5 microns to 10 microns particle size; (iii) mixing the ground mixture in a post mixer ; (iv) charging it, through a rotary feeder, into a feeding hopper of granulator for granulation ; (v) passing the granules through hot air chamber to condition the surface finish of granules ; (vi) passing the resultant granules through an oscillating cutter and thereafter sieved to obtain granules of desired length ; (vii) fines collected are recycled to obtain the conversion yield of 99.0% minimum wherein according to step (iv) in the granulator the dry powder mix on attaining its softening point, during rubbing off process between the perforated bottom plate and the flattened edge of the rotating worm which guides the mix through the perforated plate to exit from the other side of the plate, in the form of chemically stable, low compact, dry flow, soluble granules of Phosphoroamidothioate.
By using this process for preparation of a novel solid insecticidial composition containing chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate the use of water or any solvent in any step of the process is avoided. Further the compaction or extrusion of the dry mix for making the resulting granules are also avoided. By avoiding the use of water or any solvent, the resulting product is completely free flowing. The avoidance of compaction and / or extrusion makes the resulting granules low compact and readily soluble in water at the time of application and use.

Whereas in the granulation process employed using the processes described by using the apparatus, the dry powder mix of Acephate on attaining its softening point during rubbing off process are converted into granules. Such a novel composition containing chemically stable, low compact, dust free, soluble granules of Phosphoroamidothioate compound of the formula I defined above is not known prior to this invention.
For preparing the novel solid insecticidal composition containing chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate the required quantity of technical is premixed with specified adjuvants and other inert ingredients which are all solids. It is to be noted that no water or solvent is used in preparing this pre mix. The resultant pre-mix is then ground in a microniser and then the pre-mix is granulated through a low compact granulator. The product is further passed through hot air chamber to condition for good surface finish. The dried product is sized and then sieved for removal of fines, which are later recycled, to have a chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate (Acephate)
Accordingly, the present invention provides a novel insecticidal composition prepared by without using water or any solvent, comprises
(i) 50% to 97% of Phosphoroamidothioate of the formula I:


R2.

(I)
wherein R and R 1 individually are an alkyl, alkenyl or alkynyl group containing upto 6 carbon atoms, R 2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms, R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and X is oxygen or sulfur,

(ii) 0.1% to 5.0% of dispersing agent,
(iii) 0.1% to 3.0% of wetting agent,
(iv) 0.1% to 0.3% of binding agent,
(v) 0.01% to 0.08% of antifoaming agent,
(vi) 0.01% to 10.0% of disintegrating agent,
(vii) 0.01% to 1.0% of Stabilizers) and
(viii) filler(s) make 100%(w/w)
In the composition of the present invention the chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate (Acephate) may be preferably of 1.5 to 3.0 mm long and 0.5 to 1.50 mm in diameter. These granules of Phosphoroamidothioate are characterized by aging stability of minimum two years and with following specific compositions.
Composition used for the preparation of the dry mix, may be
Ingredients Quantity (% w/w)
Acephate content Min. 50,0 to 97 Max. (on 100% basis)
Dispersing agents Min. 0.1 to 5,0 Max.
Wetting agent Min. 0.1 to 3.0 Max.
Binding agent Min. 0.1 to 0.3 Max.
Antifoaming agent Min. 0.01 to 0.08 Max
Disintegrating agents Min. 0.01 to 10.0 Max.
Stabilizers) Min. 0.01 to 1.00 Max
Fillers) Q.S.
Total 100.00 % w/w

Detailed description of the present invention
The process is described by referring to the Flow Chart given on the next page -10.
The Acephate Technical, dispersing agent, wetting agent, binding agent, antifoaming agent, disintegrating agent, stabilizer(s) and fillers), which are solids, charged in the required quantities in a premixer and mixed without using water or solvent to get a homogeneous


mixture. Then, the homogeneous mixture is ground in a microniser to get a product with particle size of 5 microns to 10 microns. The ground product is taken for post mixing in a post mixer. Thereafter, the mixture is fed through a hopper into the granulator to obtain granules.
The temperature of the granulator is maintained at 32-35°C at the inlet and at 40-45°C at the outlet The granules are passed through hot air chamber to condition the surface finish, then passed through an oscillating cutter, and thereafter sieved to obtain granules. The granules are then collected to obtain the composition containing chemically stable, dry flowable, low compact, dust free, soluble granules of the Phosphoroamidothioate. The fines collected after sieving are recycled
When the apparatus is used for preparing the composition of the present invention the dry powder mix on attaining its softening point, during rubbing off process between the perforated bottom plate and the flattened edge of the rotating worm which guides the mix through the perforated plate to, exit from the other side of the plate in the form of granules.
The resulting composition is tested for required quality specifications and packed in desired packing. This granulation technique gives atleast 99% of conversion yield. The granules with incorporation of solid adjuvants, by proper choice, enjoys all the formulation advantages as mentioned earlier. All the advantages makes the composition of the present invention beneficial from economic aspect, handling aspect and shows a very good performance during the application.
In a preferred embodiment of the present invention the wetting agents used is selected from calcium or sodium salt of alkyl aryl sulphonate; the dispersing agents used is selected from the derivative of sulfonated fatty alcohol; the binding agent used is selected from sucrose and starch derivatives or a blend thereof; the disintegrating agents used is selected from swelling type clays like bentonite, zeolite ; the antifoaming agents used may be selected from silicon oil derivative; the stabilizers used selected from salts of higher fatty acids; and the filler(s) used selected from precipitated silica, kaoline, bentonite, dolomite and the like.
The following examples are presented to illustrate the invention only and therefore should not be construed to restrict the scope of the present invention. Parts and percentage are by weight unless otherwise specified.

Example -1

Composition providing granules of Acephate 97.0%.
Composition
Ingredients Quantity (% w/w)
Acephate technical 98.5% purity 98.48
Dispersing agents (Dispersol -PS) 0.50
Wetting agent (Lisapol -D) 0.10
Binding agent (Lactose impregnated with
sucrose octacetate) 0.10
Antifoaming agent (Agnique Soap-L) 0.03
Disintegrating agents (Bentonite ) 0.50
Stabilizers (Salts of higher fatty acids) 0.05
Fillers) (Kaoline) 0.24
TOTAL 100.00%w/w
Example - 2
Composition providing granules of Acephate 90.0%

Ingredient Quantity(%w/w)
Acephate technical 98.5% purity 91.38
Dispersing agents (Dispersol -PS) 0.75
Wetting agent (Lisapol -D) 0.10
Binding agent (Lactose impregnated with sucrose
octacetate) 0.20
Antifoaming agent (Agnique Soap-L) 0.03
Disintegrating agents (Bentonite) 1.00
Stabilizers (Salts of higher fatty acids) 0.05
Fillers (Kaoline) 6.49
TOTAL 100 .00 % w/w

Example - 3
Composition providing granules of Acephate 85% Ingredient
Acephate technical 98.5% purity 86.30
Dispersing agents (Dispersol -PS) 1.50
Wetting agent (Lisapol -D) 0.50
Binding agent (Lactose impregnated with sucrose
octacetate) 1.00
Antifoaming agent (Agnique Soap-L) 0.05
Disintegrating agents (Bentonite) 2.00
Stabilizers (Salts of higher fatty acids) 0.60
Fillers (Kaoline) 8.05

TOTAL

100.00%w/w

Example -A
Composition providing granules of Acephate 75%.
Ingredient Quantity (% w/w)
Acephate technical 98.5% purity 76.15
Dispersing agents (Dispersol -PS) 2.00
Wetting agent (Lisapol -D) 1.50
Binding agent (Lactose impregnated with
sucrose octacetate) 1.50
Antifoaming agent (Agnique Soap-L) 0.06
Disintegrating agents (Zeolex) 5.00
Stabilizers (Salts of higher fatty acids) 0.75
Fillers (Precipitated Silica) 13.04
TOT AL 100 .00% w/w

Example - 5
Composition providing granules of Acephate 50%.
Ingredients Quantity (% w/w)
Acephate Technical 98.5% purity 50.77
Dispersing agent (Dispersol -PS) 3.00
Wetting agent(LisapolD) 2.00
Binding agent(Lactose impregnated with
sucrose octacctate) 3.00
Antifoaming agent (Agnique Soap-L) 0.08
Disintegrating agent (Zeolex) 10.00
Stabilizer(Salts of higher fatty acids) 1.00
Filler (Precipitated Silica) 30.15
Total 100.00 %w/w
TESTS
The physical properties of the composition of the present invention were determined before and after aging at 45°C for 500 hrs and for flowability, wetting time, attrition test, disintegration rate, tap density, suspensibiliry, sedimentation and persistent foam. No noticeable difference in all the above properties observed.
The dynamic wetting time and solubility test is measured as per MT-167 of CIPAC.
> The flowability is measured as per MT-172 of CIPAC.
> The dry sieve analysis is measured as per MT-170 of CIPAC.
> The sedimentation is measured as per MT-15.1 of CIPAC.
> Dustiness of granules is measured as per MT-171 of CIPAC.
> The tap density is measured as per MT-58.4 and MT-33 of CIPAC.
The Acephate technical content can be determined by GLC method published in AOAC.

Advantages of the invention
> The insecticidal composition s contains granules of Acephate in an amount from 50 to 97% active ingredient.
> The Composition is chemically stable .
> The composition does not include water or solvent which makes the composition very safe for processing and prevents any handling hazards.
> The composition is free flowing as the ingredients used are all solids, which facilitates the pouring of the granules from product pack to measuring device. In addition these ingredients are easily available and cheaper, making the composition and process economical.
> The composition does not include any deodorants as the granules produced have less odourless as
compared to that of the currently available formulation of Acephate in the market.
> The composition is produced by granulation and not extrusion thereby having the advantage of low compacted product granules that dispose easiliy when added to water.
> The composition is dry which has the advantage of being non-caking or non lumping and is free flowing in nature.
> The composition is produced at the temperature in the softening point of the dry mix. Thereby having the advantage of being free from water or any other solvent.

We Claim:
1) A novel insecticidal composition containing chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate in solid form without using water or any solvent which comprises:

wherein R and R 1 individually are an alkyl, alkenyl or alkynyl group containing upto 6 carbon atoms, R 2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, an alkenyl group containing 2 to 18 carbon atoms or an alkynyl group containing 3 to 18 carbon atoms, R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and X is oxygen or sulfur,
(ii) 0.1% to 5.0% of dispersing agent,
(iii) 0.1% to 3.0% of wetting agent,
(iv) 0.1% to 0.3% of binding agent,
(v) 0.01 % to 0.08% of antifoaming agent,
(vi) 0.01% to 10.0% of disintegrating agent,
(vii) 0.01% to 1.0% ofStabilizer(s), and
(viii) filler(s) to make 100% (w/w).

2) A composition as claimed in claim 1, wherein the size of chemically stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothioate (Acephate) employed is of 1.0 to 50 mm, preferably of 1.5 to 3.0 mm long; and preferably 0.5 to 1.50 mm in diameter.
3) A composition as claimed in claims 1 & 2, wherein the binding agents used are selected from sucrose and starch derivatives or a blend thereof.
4) A composition as claimed in claims 1 to 3, wherein the wetting agents used are selected from calcium or sodium salt of alkyl aryl sulphonate.
5) A composition as claimed in claims 1 to 4, wherein the dispersing agents used are selected from the derivative of sulfonated fatty alcohol.
6) A composition as claimed in claims 1 to 5, wherein the disintegrating agents used are selected from swelling type clays like bentonite, zeolite.
7) A composition as claimed in claims 1 to 6, wherein the antifoaming agents used are selected from silicon oil derivative.
8) A composition as claimed in claims 1 to 7, wherein the stabilizers used are selected from salts of higher fatty acids.
9) A composition as claimed in claims 1 to 8, wherein the filler(s) used are preferably selected from precipitated silica, kaoline, bentonite and dolomite.
10) A novel insecticidal composition containing chemically, stable, dry flow, low compact, dust free, soluble granules of Phosphoroamidothiate useful as insecticides prepared without using water or any solvent, substantially as herein described and exemplified.
Dated this 16th day of January, 2003.
MR. M B TRIVEDI (COMPANY SECRETARY) FOR UNITED PHOSPHORUS LIMITED UNIPHOSHOUSE, C. D MARG 11™ ROAD, KHAR (W) MUMBAI-400 052 MAHARASHTRA, INDIA