Description:FIELD OF THE INVENTION:

The present invention relates to sprayable microcapsule formulations of semiochemical/s and the process of preparation thereof, which can be used for insect mass trapping and control either by using mating disruption of insects or Push Pull strategy or attract and kill techniques. More particularly, the invention relates to microcapsule spray formulations of semiochemical/s with high loading efficiency, exhibits rainfastness and release the semiochemical/s over longer period of time.

BACKGROUND AND PRIOR ART DISCUSSION:

Growing insecticide resistance, failing genetically modified organisms and with hardly any environment friendly new chemical pest control molecules in pipeline, there is a need to develop pest control technologies by the way of new mechanism of action. Traditional Pest control methods relies on indiscriminate use of insecticides being sprayed at regular intervals from sowing to harvest have induced insecticide resistance, and have toxic effects on non-target beneficial insects. Semiochemical/s which are species specific, have proven useful tool in pest control and have become essential components of Integrated Pest management. The eco-friendly semiochemical/s based pest control strategies are developed by using sex pheromones for mating disruption and mass trapping. Whereas, host-plant volatiles are used for attract-kill and push-pull techniques that have traditionally replaced conventional insecticides. These semiochemical compounds are so far formulated in polymer based protective matrices and have been deployed inefficiently with plastic and rubber dispensers (e.g. hand-applied ropes, tapes, rubber septa and sachets) which restricted the adoption of the technology.

Active Ingredients (AIs) are intended to create a semiochemical/s plumes or cloud or atmospheric saturation in the crop field to modify insect chemical behaviour to control the target pest, which requires high doses of expensive AIs ranging from 80 grams to 250 grams per hectare. Also, these AIs and dispensers have inconsistent performances, generate plastic waste and are very expensive leading to restriction of adaption. However, these dispensers are highly expensive and do not meet the economics of current conventional insecticides practices.
A lot of economic interest is involved in the targeted insect pests. There are several examples to this fall armyworm can cause significant yield loss in maize and other crops. Baudron et al. (2019, Crop Prot. 120: 141–150) have reported maize infestation between 26.4 and 55.9% impacted a yield decrease of 11.57%. Other authors have reported leaf, silk and tassel damage levels ranging between 25 to 50% and grain yield decrease of 58% (Chimweta et al., 2019, International Journal of Pest Management, 66(2), 142–154.). Infestations during the mid- to late-whorl stage of maize development caused yield losses of 15 to 73% when 55 to100% of the plants were infested with S. frugiperda (Hruska and Gould, 1997, J Econ Entomol. 90: 611–622).

Helicoverpa armigera has been reported causing serious losses in a range of crops. Estimated loss in crop productivity (e.g. maize, soybeans, tomatoes and cotton) in Asia, Europe, Africa and Australasia is greater than 2 Billion USD annually (Tay et al., 2013, PLoS ONE, 8: e80134). In India losses to pigeon pea and chickpea production surpassed 300 Million USD (Reed & Pawar, 1981, Proc. Int. Workshop on Heliothis Management, 9-14). In Brazil, one year after detection, economic impact was estimated at 1 Billion USD and the damage reached up to 100% in non-Bt soybeans (Mastrangelo et al., 2014, Journal of Economic Entomology 107, 970–980).

Among the bollworm complex, pink bollworm (PBW) is one of the major insect pests of cotton with a damaging potential of 20-40% yield loss (Ingole et. al. 2019, Journal of Entomology and Zoology Studies 7(1): 583-586).

Crop losses caused by codling moth, Cydia pomonella on pome fruits around the world are difficult to assess, as the methods used are often inadequate and not strictly comparable. In warmer climates, where two or more generations occur, damage to apples has been reported as being as high as 84% in the Crimea (Tanskii and Bulgak, 1981, Entomological Review, 60(2):1-12), or 65 to 100% in Australia (Geier, 1964, Australian Journal of Zoology, 12: 381-416).

The use of pheromones for pest control promises to be an important component of the ongoing challenge to develop alternatives to solve major environmental and human health problems associated with chemical pesticide use in agriculture.
US6506397B1 discloses the sustained-release microcapsule for long-term pest control. A microcapsule has a capsule core including active pest-control ingredients and diluents. In which diluents are arranged to entrap active ingredients to provide resistance to mass transfer of the active ingredient. Where active ingredient is a biopesticide such as pheromones, pyrethroids, insect growth regulators, insect attractants, and insect repellents.

EP0067533B1 discloses a process of spray microcapsules of active ingredients such as fungicides, herbicides, insecticides and the like, in which the material to be encapsulated and a film-forming polymer are sprayed together into the atmosphere in such a way that the polymer coacervates and encapsulates the above-mentioned material after spraying on the substrate.

EP2663183 B1 (WO2012/095444) discloses microcapsules comprising pheromone, a water immiscible organic solvent, and polymethacrylate based capsule wall wherein pheromone is present in dissolved form in the core.

Pheromone-mediated mating disruption relies on the release of synthetic sex pheromones from dispensers in crops, primarily rely upon “passive” dispensers, used at high densities per hectare (200–3000 units/ha). In addition to the labour required for their application, another disadvantage of “passive” dispensers is the continuous release of pheromones, regardless of the time of day or the pest flight activity.

Usage of pheromone-based aerosols have raised with another disadvantage of phytotoxicity. The usage of high-dose lures that still attract some moths even under mating disruption has proven useful for tracking the flights of some pests (such as codling moth) or as a supplemental risk-assessment tool and other species, such as oriental fruit moth (Cydia molesta), do not exhibit this response.

Pink bollworm (Pectinophora gossypiella) has been the target of an intensive, long-term and successful mating-disruption effort, but variety of strategies have been employed, including applications of hollow fibers, chopped laminate flakes, sprayable microencapsulated pheromone, twist-tie ropes or laminate membrane dispensers, resulted in problems with successful mating disruption in fields with high moth populations were detected and supplemental control tactics were yet to be used for complete resolution of pests.
Thus from the prior art to the best of our knowledge there does not exist any sprayable microcapsular semiochemical/s formulation which has all the following properties – i) cost effective ii) having high loading and higher encapsulation efficiency iii) excellent rain-fastness property iv) release its AI over the longer period of time particular to specific crop season with minimum number of applications v) not phytotoxic and vi) compatible with other insecticide formulations.

The prepared sprayable microcapsular (SM) formulation can be mixed with, if required, any insecticide formulation and sprayed together. Surprisingly we found that addition of wax particles along with microcapsules leads to significant improvement in above mentioned properties.

OBJECTIVES OF THE INVENTION:

Main objective of the present invention is to provide a sprayable microcapsule formulation comprising semiochemical/s for insect population control either by mating disruption or by attract and kill technique.

Another objective of the present invention is to provide a process for the preparation of a sprayable microcapsule formulation comprising semiochemical/s.

Yet another objective of the present invention is to provide an application of the microcapsule dispersion formulation comprising semiochemical/s as compatible with insecticides formulations.

Another objective of the present invention is to provide formulation which exhibits rain-fastness after application in the agriculture field.

SUMMARY OF THE INVENTION:

The present invention describes sprayable microcapsule formulation comprising semiochemical/s and the process for the preparation thereof. The microcapsules are prepared by encapsulation of semiochemical or mixture of semiochemical/s along with oil as a release modifier. Other excipients such as wax microparticles as adhesion promoting agents and antioxidants are used to enhance active ingredient stability. In this invention, the microcapsule based sprayable formulation is called as sprayable microcapsule SM throughout the document.

Another aspect of this present invention is to prepare microcapsules reservoir of semiochemical/s comprising core material and shell of synthetic or biopolymer, whereas core material is composed of active /semiochemical/s, release modifier oil and antioxidants.

Another aspect of the present invention is a sprayable microcapsule formulation comprising microcapsules dispersed in phase containing wax particles.

Another aspect of the present invention is the sprayable microcapsule formulation exhibits controlled release profile along with the unique property of rain-fastness.

Another aspect of the present invention is the sprayable microcapsule formulation shows physical and chemical stability at a temperature range from 0°C to 540C when stored for the period of one month and 2 years when stored at room temperature (25 – 30°C)

Still one more aspect of the present invention shows controlled release of pheromone over an extended period of minimum 8 weeks depending on the microcapsule wall thickness and semiochemical/s characteristics.

Further aspect of the invention provides the sprayable microcapsule formulation adheres to the surface of plant foliage. Due to this property, microcapsules from SM formulation, can get retained on the plant foliage, i.e. either stem/leaf or any hydrophobic surface like mulching plastic sheets for longer time thereby achieving and supporting the controlled release of semiochemical/s and enhance bio-efficacy providing season long mating disruption in insects.

Another aspect of the present invention is that the SM formulation is non-phytotoxic.

Yet another aspect of the invention is to provide sprayable microcapsule formulations comprising semiochemical/s for integrated pest management in agriculture.

BRIEF DESCRIPTION OF DRAWINGS:

The invention is further described in the detailed description that follows, by reference to the noted drawings by way of illustrative embodiments of the invention, in which like reference numerals represent similar parts throughout the drawings. The invention is not limited to the precise arrangements and illustrative examples shown in the drawings:

Figure 1 is representing optical microscope image of a) BFSB; b) DBM; and c) RYSB microcapsules;

Figure 2 is representing the release profile of DBM sprayable Microcapsule formulation;

Figure 3 is representing release profile of BFSB sprayable Microcapsule formulation;

Figure 4 is representing release profile of semiochemical/s based sprayable microcapsules formulations with examples of FAW, CL, ME, DBM, LOBESIA, PBW, HELICO and RYSB;

Figure 5 is representing Field Emission scanning electron microscope (FE –SEM) images of neat microcapsules on leaf surface before and after water wash; and

Figure 6 is representing Field Emission scanning electron microscope FE-SEM images of sprayable microcapsular formulation on leaf surface after 25mm, 50 mm and 100mm of water wash.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS:

Detailed embodiments of the present invention are disclosed herein with reference to the drawings. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. Further, the terms and phrases used herein are not intended to be limiting but rather to provide an understandable description of the invention.

ACRONYMS USED TO DESCRIBE THE INVENTION:

AI- Active ingredient
Tween 20: PolyoxyethyleneSorbitan Monolaurate
Tween 80: polyoxyethylenesorbitan monooleate
BHT: butylated hydroxytoluene
Brij:Polyoxyethylene Lauryl Ether
Luwipal® 068: BASF fully-etherified, aminoplast resin

List of pheromones and its abbreviated forms disclosed herein:

Brand Name
Active Blend
PBW (Z, Z)-7, 11- hexadecadien-1-yl acetate
(Z, E)-7, 11- hexadecadien-1-yl acetate
FAW Z9- Tetradecenyl acetate
Z7- Dodecenyl acetate
Z11- Hexadecenyl acetate
BFSB E-11-hexadecen-1-yl acetate
(E)-11-hexadecen-1-ol
TUTA 3E,8Z,11Z-Tetradecatrienyl acetate
3E,8Z-Tetradecadienyl acetate
CLM (Z,Z,E)-7,11,13-Hexadeca trien-1-al
DBM Z-11-Hexadecenal
Z-11-Hexadecenyl-1-acetate
Z-11-Hexadecenol
RYSB Z-11-Hexadecenal
Z-9-Hexadecenal
Helio Z-11-Hexadecenal
Z-9-Hexadecenal
Spodo (Z,E)-9,11-Tetradecadienyl acetate
Z9,E-12-Tetradecadienyl acetate
TMB Cis-3-Hexenyl acetate
2E- Hexen-1-ol
PSB Z-11-Hexadecenyl-1-acetate
(Z)-11-Hexadecenal
Z-11-Hexadecenol
SSB (Z)-11-Hexadecenal
ESB Z-11-Hexadecenol
CAROB (7Z,9E)-Dodeca-7,9,11-trien-1-yl formate
NOW 11Z,13Z-Hexadeca dienal
CYDIA (E,E) -8,10-Dodecadien-1-ol
OFM (Z)-8-Dodecen-1-yl acetate
(E)-8-Dodecen-1-yl-acetate
(Z)-8-Dodecen-1-ol
VERB (1R)-cis-4,6,6-Trimethylbicyclo [3.1.1]hept-3-en-2-one
ISB Z-13-Octadecynyl acetate
Z-13-Octadecenol
MARUCA (E,E)-10,12-hexadecadienal
(E,E)-10,12-hexadecadienol
E-10-hexadecenal
SE Z,E-9,12-Tetradecadien-1-yl-Acetate
Z-9 Tetradecenol
FCM (Z)-8-Dodecen-1-yl acetate
(E)-8-Dodecen-1-yl-acetate
Lobesia 7E, 9Z Dodecadienyl acetate
RLR Z13-18Ac
(Z)-11-Hexadecen-1-yl acetate
Earias insulana E10E12-16Ald
Z11-16:Ald
Earias vitella E10E12-16Ald
Z11-16:Ald
Z11-18:Ald
E10E12-16OH
Carposina Z7-20-11Kt

Z7-19-11Kt

GLF Z11Z13-16Ald
Y11-16Ald
Z11-16Ald
Mythimna Z11–16:Ald
Z11-16:Ac
Chilo supressalis Z11-16Ald

Z13-18Ald

Zeuzera pyrina E2Z13-18Ac
E3Z13-18Ac
Spodoptera exigua (Z)-11-Hexadecen-1-yl acetate
(Z,E)-9,12-Tetradecadienyl acetate
Anarsia lineatella (E)-5-Decen-1-yl acetate
(E)-5-Decen-1-ol
Eupoecilia ambiguella (Z)-9-Dodecen-1-ol
PPM -Thaumetopoea pityocampa (Z)-Hexadec-13-en-11-yn-1-yl acetate
RPW 4 methyl 5 nonanol
4 methyl 5 nonanone
Rhino Ethyl-4-Methyl octanoate
ME Methyl Eugenol
CL Cuelure
WFT Methyl Isonicotinate
Stink Bug Methyl-2,6,10-trimethyl dodecanoate

The major embodiment of the invention provides a sprayable microcapsule formulation comprising a semiochemical/s i.e., a pheromone entrapped in microcapsules, dispersing agent, rain fastening agent and the preparation thereof, wherein the formulation can be used for mating disruption of insects or Push Pull strategy; attract and kill or mass trapping.

In an embodiment of the present invention, the sprayable microcapsule dispersion formulation comprises of:
at least one component is semiochemical or mixture of semiochemical/s encapsulated in the polymer shell and/or
at least one component of adjuvant that is homogeneously dispersed in the system,
Wherein, the dispersion medium of the sprayable microcapsule formulation exhibits rain-fastness property.

In yet another embodiment, a sprayable microcapsule formulation comprising semiochemical/s reservoir microcapsules with core and shell, which is characterized as the following:
Core comprises an active agent is a semiochemical or mixture of semiochemical/s in an amount of 0.1 to 20% by weight of formulation;
a release modifier oil the ratio of 10:1 to 1:10 by weight of active agent;
antioxidant in an amount of 0.01 to 3 % by weight of active agent;
Polymer shell of microcapsules in an amount of 5 to 90% by weight of neat microcapsule;
wax particles in an amount of 1 to 30% by weight of formulation;
an emulsifier in an amount of 0.2 to 10% by weight of formulation; and
viscosity modifier in the amount of 0.01 to 0.5 % by weight of formulation,
Wherein the formulation having one or more UV absorbers optionally used with other additive components that is/are homogeneously dispersed in the active/core phase.

Yet another embodiment of the present invention provides a method of preparing a sprayable microcapsule formulation, wherein the method comprises the steps of:
Preparation of microcapsules-
preparing solution A: solution A was prepared by stirring a mixture of emulsifier and aminoplast resin at 300-500RPM for a period of 10 min. at a temperature in the range of 25-30°C; followed by adjusting the pH to 4-4.5 with 10% HCl solution and then further stirring at 300-500RPM for a period of 15-20 minutes at a temperature in the range of 25-30°C;
preparing core solution B: A predetermined quantity of Semiochemical/s, modifier oil and antioxidant were mixed under stirring to make core solution B;
solution B as obtained at step b) added into the solution A as obtained at step a) and homogenizing at 3000-3200 RPM with Remi homogenizer D-127 at a temperature in the range of 25-30°C for a period of 4-5 minutes;
stirring the emulsion obtained at step c) at 1000 RPM at a temperature in the range of 25-30°C for a period of 15-20 minutes;
To continuation in the step d) adding water followed by heating to the temperature of 55°C and maintaining at 1000 RPM for a period of 2 hours, and 700 RPM at 60°C for 1 hour, 80°C for 2 hours;
cooling the obtained microcapsule dispersion at step e) to 27°C and adjusting the pH to 6-6.5 with triethanolamine;

Preparation of wax particles -
Wax was melted in a vessel A at the melting temperature and stirred at 500 rpm for 15-20 min. In a separate vessel B, aqueous phase was prepared by dispersing emulsifiers in water phase maintained at the wax melting temperature. Solution from vessel B was added to vessel A and stirred at 2500 -3000 rpm for 30 min. To this resulting emulsion, cold water is added under stirring at 1000 rpm, the molten wax turned into solid wax particles. The pH of this wax particle dispersion adjusted to 6 to 6.5.

Wax particle dispersion obtained in step 2) were added to the microcapsules dispersion obtained in step1) under stirring at 1000RPM for 1hour followed by addition of viscosity modifier solution.

The capsule wall formed with polymer shell and release modifier added in the core to control the release of pheromone from this sprayable microcapsular formulation.

It has been observed that the microcapsules along with wax particles help the adhesion of microcapsules to the substrate, which is plant leaf or stem or plastic. Even under water washing the microcapsules remain adhered to the substrate showing good rain-fastness property.

Accordingly, the invention provides the sprayable microcapsule formulation is an aqueous dispersion of microcapsule having the pH value of about 6.0 to 6.5.

Accordingly, the invention provides spherical microcapsules having the size in the range of 1 to 200 microns preferably 2- 100 microns and more preferably in the range of 5-50 microns.
In yet another embodiment the sprayable microcapsule formulation dispersion shows physico-chemical stability at 0°C to 540C temperature and microcapsules remain uniformly dispersed in the aqueous dispersion for two years at 27 to 30°C.

In another embodiment the sprayable microcapsule formulation shows controlled release of semiochemical/s over extended period of at least eight weeks (Figures 2, 3 and 4).

In yet another embodiment the sprayable microcapsule formulation can be sprayed in combination with compatible commercially available insecticides which are used for conventional insect control application.

The sprayable microcapsule formulation comprises of semiochemical/s, wherein the semiochemical/s is at least one of a pheromone/s, an allomone/s, a kairomone/s, or a synomone or mixtures thereof, preferably pheromone/s.

The sprayable microcapsule formulation includes semiochemical/s that can be used in the formulations according to the present invention are selected from the group consisting of the active blend of (Z, Z)-7, 11- hexadecadien-1-yl acetate and (Z, E)-7, 11- hexadecadien-1-yl acetate; the active blend of Z 9- Tetradecenyl acetate, Z7- Dodecenyl acetate and Z11- Hexadecenyl acetate; the active blend of E-11-hexadecen-1-yl acetate and (E)-11-hexadecen-1-ol; the active blend of 3E,8Z,11Z-Tetradecatrienyl acetate and 3E,8Z-Tetradecadienyl acetate; the active, (Z,Z,E)-7,11,13-Hexadeca trien-1-al; the active blend of Z-11-Hexadecenal, Z-11-Hexadecenyl-1-acetate and Z-11-Hexadecenol; the active blend of Z-11-Hexadecenal and Z-9- Hexadecenal; the active blend of Z-11-Hexadecenal and Z-9-Hexadecenal; the active blend of (Z,E)-9,11-Tetradecadienyl acetate and Z9,E-12-Tetradecadienyl acetate; the active blend of Cis-3-Hexenyl acetate and 2E- Hexen-1-ol; the active blend of Z-11-Hexadecenyl-1-acetate and Z-11-Hexadecenol; the active of Z-11-Hexadecenol; the active of (7Z,9E)-Dodeca-7,9,11-trien-1-yl formate; 11Z,13Z-Hexadeca dienal; the active blend of 4 methyl 5 nonanol and 4 methyl 5 nonanone; the active of Ethyl-4-Methyl octanoate; the active of Methyl eugenol; the active blend of Methyl eugenol and Cuelure; the active of (E,E) -8,10-Dodecadien-1-ol; the active blend of (Z)-8-Dodecen-1-yl acetate, (E)-8-Dodecen-1-yl-acetate and (Z)-8-Dodecen-1-ol; the active, (1R)-cis-4,6,6-Trimethylbicyclo [3.1.1]hept-3-en-2-one; the active trans-3,7-Dimethyl-2,6-octadien-1-ol&cis-3,7-Dimethyl-2,6-octadien-1-ol; the blend of Z-13-Octadecynyl acetate and Z-13-Octadecenol; the blend of (E,E)-10,12-hexadecadienal, (E,E)-10,12-hexadecadienol and E-10-hexadecenal; the blend of Z,E-9,12-Tetradecadien-1-yl-Acetate and Z-9 Tetradecenol; the blend of (Z)-8-Dodecen-1-yl acetate and (E)-8-Dodecen-1-yl-acetate; the active, (7E,9Z) dodeca- 7,9-dien-1-yl acetate, and the active 4-vinyl Anisole; Methyl Isonicotinate; Mono terpenes&Terpene alcohols; that areoptionally used as blends or individually.

The semiochemical/s according to preferred embodiments are selected from the group consisting of (Z, Z)-7, 11- hexadecadien-1-yl acetate and (Z, E)-7, 11- hexadecadien-1-yl acetate for Pink Bollworm; Z 9- Tetradecenyl acetate, Z7- Dodecenyl acetate and Z11- Hexadecenyl acetate for Fall armyworm; Methyl eugenol; Methyl eugenol and Culure for fruit fly; (E,E) -8,10-Dodecadien-1-ol for Codling Moth, Z-11-Hexadecenal and Z-9-Hexadecenal for Helico, for stink bug and Yellow stem borer, that are optionally used as blends or individually.

Other pheromones that may be used as semiochemical/s in the present disclosure include followings -
(Z,Z,E)-3,6,8-Dodecatrien-1-ol (E, E)-10, 14-Hexadecadienal
(Z,Z)-9, 2-Tetradecadien- 1 –ol (Z,Z)-9, 12-Tetradecadienyl acetate
(Z,Z)-9, 11-Tetradecadienyl acetate (Z,Z)-8, 0-Tetradecadienai l
(Z,Z)-8, 0-Dodecadienyi acetate (Z,Z)-11 , 13-Hexadecadienyl acetate
(Z,Z)-8, 10-Dodecadien- -ol ; (Z,Z)-11 ,13-Hexadecadien-1-ol
(Z,Z)-7,9-Dodecadienyl acetate ; (Z,Z)-10, 12-Hexadecadienal
(Z,Z)-7,9-Dodecadien-1-ol (Z,E)- 10,12-Hexadecadienai
(Z,Z)-7, 11-Tridecadienyl acetate (Z)-11-Heptadecenyl acetate
(Z,Z)-5,9-Tridecadieny acetate (Z)-11-Heptadecen-1-ol
(Z,Z)-5,8-Tetradecadienyl acetate (Z,Z)-5,8-Tetradecadien-1-ol
(Z,Z,Z)-9, 12, 15-Octadecatrienal (Z,Z)-5,8~Tetradecadienal
(Z,Z)-5,7-Dodecadienal (E, E)~ 10, 12-Hexadecadien-1 -ol
(Z,Z)-4,7-Tridecadienyl acetate (Z)-8-Heptadecen-1-ol
(Z,Z)-4,7-Tridecadien-1-ol (E)-8-Heptadecenyl acetate
(Z,Z)-4,7-Decadienyl acetate (Z,Z)-9,1 1-Pentadecadienal
(Z,Z)-4,7~Decadien~1-ol (E,Z)-9, 1 1-Pentadecadienal
(Z,Z)-3,8-Dodecadien-1-ol (Z,E)-7,1 1 -Hexadecadienal
(Z,Z)-2,4-Decadienal (E,Z)-8,10-Pentadecadienyl acetate
(Z,Z)~9, -Tetradecadienal (Z,Z)~9, 11-Tetradeeadien-1-ol
(Z,Z)~5,7~Dodecadienyl acetate (Z,Z)-9,1 1-Hexadecadienal
(Z,E,E)-3,6,8-Dodecatrien-1-ol (Z,Z)-11 ,13-Hexadecadienal
(Z,E)-9,1 1-Teiradecadienyl acetate (Z,E)-8, 10-Dodecadienyl acetate
(Z,E)-11 ,13-Hexadecadienyl acetate (Z,E)-7,9-Dodecadienyl acetate
(Z, E)-10, 12-Hexadecadienyl acetate (Z,E)-7,9-Dodecadien-1-ol
(E,Z)-10, 2-Hexadecadienal (Z,E)-5,7-Dodecadienyl acetate
(E,Z)-9, 1 1-Hexadecadienal (Z,E)-5,7-Dodecadienal
(Z,E)-9,1 –Hexadecadienal (Z,E)-3,5-Tetradecadienyl acetate
(Z,Z)-9, 12-Octadecadienal (Z,E)-3,5-Dodecadienyi acetate
(Z,E)-7,1 1 -Hexadecadienyl acetate (Z,E)-3,5-Decadienyl acetate
(Z,Z)-8, 10-Pentadecadienyl acetate (Z,E)~5,9-Tridecadienyl acetate
(E)-10-Heptadecenyl acetate (Z, E)-9, 12-Tetradecadienyl acetate
(Z, E)-9, 12-Tetradecadienal (Z, E)-9, 12-Tetradecadien- 1 -ol
(Z, E)-9, 11 –Tetradecadienal (Z, E)-9, 11 -Tetradecadien-1 -ol
(Z, E)-8, 10-Tetradecadienyl acetate (Z, E)-8, 10-Dodecadienal
(Z, E)- 1 , 13-Hexadecadienal (Z, E)-8, 10-Dodecadien-1-ol
(Z,E)-11 ,13-Hexadecadien-1-ol (Z, E)-5,7-Dodecadien-1 -ol
(E,Z)-9, 1 -Hexadecadienyl acetate (Z, E)~8, 10-Tetradecadien-1 -ol
(Z)-S-Tetradecenyi acetate (Z)-13-Octadecen-1-ol
(Z)-10-Tridecenyl acetate (E, E,Z,Z)-4,6, 1 1 , 13-Hexadecatetraenal
(Z)-10-Tetradecenyl acetate (Z,Z)-2, 13-Octadecadien-1-ol
(Z)-10-Dodecenyi acetate (Z,Z)-7, 0-Hexadecadienyl acetate
(Z)-9-Undecenyl acetate (E)-6-Hexadecenyl acetate
(Z)-9-Tridecenyl acetate (E,E,Z)-10, 12,14-Hexadecatrienal
(Z)-9-Tetradecenyl acetate (E,Z)-2, 13-Octadecadienyi acetate
(Z)-9-Tetradecenal (E,Z)-2, 13-Qctadecadienai
(Z)-9-Tetradecen-1-ol (E,Z)-2, 13-Octadecadien-1-ol
(Z)-9-Dodecenyl acetate (E,Z)-4,6-Hexadecadien-1-ol
(Z)-9-Dodecenal (E,Z)-4,6-Hexadecadienyl acetate
(Z)-9-Dodecen-1-ol (E,E)-1 ,3-Hexadecadien-1-ol
(Z)-8-Undecenyl acetate (Z)-5-Hexadecenyl acetate
(Z)-8-Trideceny! acetate (E,E,E)-10,12, 14-Hexadecatrienai
(Z)-8-Tetradecenal (Z)- 3-Octadecenyl acetate
(Z)-8-Tetradecen-1-ol (E)-13-Octadecenai
(Z)-8-Dodecenyl acetate (Z)-9-Hexadecenyl acetate
(Z)-8-Dodecenyl acetate (Z)-12-Hexadecenyl acetate
(Z)-8-Dodecen-1-ol (Z)-1 1-Hexadecenal
(Z)-7-Tridecenyl acetate (Z,Z, E)-7, 11 , 13-Hexadecatrienal
(Z)-7-Tetradecenyl acetate (Z)-11-Octadecenyl acetate
(Z)-7-Tetradecenai (Z)-1 1-Octadecenal
(Z)-7-Tetradecen-1-ol (Z)- 1 -Octadecen- -ol
(Z)-7-Dodecenyl acetate (E)-1 1-Hexadecen-1-ol
(Z)-7-Dodecenal (E)-1 1-Hexadecenyl acetate
(Z)-7-Dodecen-1-ol (Z)-10-Hexadecenal
(Z)-7-Decenyl acetate (Z,Z)-6,9-Pentadecadienyi acetate
(Z)-6-Tetradecenyl acetate (Z)-9-Octadecenal
(Z)-5-Undecenyl acetate (E)-5-Hexadecenyl acetate
(Z)-5-Tetradecenyl acetate (E)-9-Octadecenal
(Z)-5-Tetradecenal (Z)-9-Octadecen-1-ol
(Z)-5-Tetradecen-1-ol (E)-9-Octadecenyl acetate
(Z)-5-Dodecenyl acetate (E)-9-Hexadecenyl acetate
(Z)-5-Dodecenal (E)-9~Hexadecenal
(Z)-5-Dodecen-1-ol (E)-9-Hexadeceno1-ol
(Z)-5-Decenyl acetate (E)-12-Pentadecenyl acetate
(Z)-5-Decen-1-ol (Z)-10-Pentadecenal
(Z)-4-Tridecenyl acetate (E,Z,Z)-4,6, 10-Hexadecatrienyl acetate
(Z)-4-Tridecenal (E, E,Z)-4,6, 1 -Hexadecatrienyl acetate
(Z)-4-Decenyl acetate (Z)-8-Pentadecenyl acetate
(Z)-4-Decenal (Z)-9-Pentadecenyl acetate
(Z)-3-Tetradecenyl acetate (E)-2-0ctadecenal
(Z)-3-Tetradecen-1-ol (E)-2-0ctadecenyl acetate
(Z)-3-Dodecenyl acetate (Z)-7-Hexadecen-1-ol
(Z)-3-Dodecen-1-ol (E)-7-Hexadecenyl acetate
(Z)-2-Tridecenyl acetate (E, E,Z)-4,6, 0-Hexadecatrien-ol
(Z)-12-Tetradecenyl acetate (E,E)-5,9-Octadecadien-1-ol
(Z)-11-Tridecenyl acetate (Z)-2-Heptadecenal
(Z)-11-Tetradecenyl acetate (Z, E)-3, 13-Octadecadienyl acetate
(Z)-11-Tetradecenai (Z,Z)-3, 13-Octadecadienyl acetate
(Z)-10-Dodecen-1-ol (Z,Z)-7, 0-Hexadecadien-1-ol
(Z)~7~Undecenyl acetate (Z)-5-Hexadecen-1-ol
(Z)~5-Decenal (Z)-12-Pentadecenyl acetate
(Z)- 11 -Tetradecen-1 -ol (E,Z)-3, 13-Octadecadienal l
(E,Z,Z)-4,7, 10-Tridecatrienyl acetate (E, E)-4,8-Heptadecadienyi acetate
(E,Z)-9,1 1-Tetradecadienyl acetate (E,Z)-8, 10-Tetradecadienyl acetate
(E,Z)-8, 10-Tetradecadienal (E,Z)-8, 10-Dodecadienyl acetate
(E,Z)-1 1 , 13-Hexadecadienyl acetate (E,Z)-8, 10-Dodecadienal
(E,Z)-11 , 3-Hexadecadienal (E,Z)-8, 10-Dodecadien-1-ol
(E,Z)-11 , 3-Hexadecadien-l-ol (E,Z)-7,9-Dodecadienyl acetate
(E,Z)-10, 12-Hexadecadien-1-ol (E,Z)-7,9-Dodecadienal
(E,Z)-10, 12-Hexadecadienyl acetate (E,Z)-5,9-Tridecadienyl acetate
(Z)-9-Heptadecenal (E,Z)-5,7-Dodecadienyl acetate
(E,Z)-8, 1 1-Hexadecadienal (E,Z)-5,7-Dodecadienal
(E, E)-9, 11-Hexadecadienal (E,Z)-4,9-Tetradecadienyi acetate
(Z,Z)-13, 15-Octadecadienal (E,Z)-4,9-Tetradecadienal
(Z,Z,Z)-3,6,9-Octadecatrienyl acetate (E,Z)-4,7-Tridecadienyl acetate
(E)-8-Heptadecen-1-ol (E,Z)-4, 10-Tetradecadienyl acetate
(E, E, E)-9, 2, 5-Octadecatrien-1 –ol (E,Z)-3,8-Tetradecadienyl acetate
(E, E)-11 , 14-Octadecadienal (E,Z)-3,5-Tetradecadienyl acetate
(Z,Z)-9, 12-Octadecadienyl acetate (E,Z)-3,5-Dodecadienyi acetate
(Z,E)-7, 1 1-Hexadecadien-1-ol (E,Z)-2,4-Decadienal
(E,Z)-8, 10-Pentadecadien-1-ol (E,Z)~7,9-Dodecadien-1-ol
(E, E)-10, 12-Hexadecadienai l (E,Z)~5,7-Dodecadien-1-ol
(Z, Z)-8 , 10- H exadecad ieny I acetate (E,Z)~3,7-Tetradecadienyl acetate
(Z,Z)-1 1 , 13-Octadecadienal (E,E,E)-10,12, 14-Hexadecatrienyl
(E,E)-9,11-Tetradecadienyl acetate (E,E)-8, 10-Dodecadienyl acetate
(E,E)-1 ,13~Hexadecadienyl acetate (E,E)-7,9-Dodecadienyl acetate
(E, E)-10, 12-Hexadecadienyl acetate (E,E)-5,8-Tetradecadienal
(Z,Z,Z)-9, 12, 15-Octadecatrienyi acetate (E,E)-5,7-Dodecadienyl acetate
(Z,Z)-7,1 1-Hexadecadienal (E,E)-5,7-Dodecadien-1-ol
(Z,Z)-7, 1 -Hexadecadienyl acetate (E,E)-4, 10-Dodecadienyi acetate
(Z,Z)-7, 1-Hexadecadien-1-ol (E,E)-3,5-Tetradecadienyl acetate
(E,E)-9,12-Octadecadien-1-ol (E,E)-3,5-Decadienyl acetate
(Z,E)-8,10-Pentadecadienyl acetate (E, E,Z)- 10, 12, 14-Hexadecatrienyl
(E, E)-9, 2-Tetradecadienyl acetate (E, E)-8, 10-Tetradecadienyi acetate
(E, E)-8, 10-Tetradecadienal (E, E)-8, 1 Q-Dodeeadien-1 -ol
(E,E)-11 ,13-Hexadecadien-1-ol (E, E)-8, 0-Dodecadienal
(E,E)-1 1 ,13-Hexadecadienal (E, E)-2,4-Tetradecadienal
(E,E)-5,9-Octadecadienyl acetate (E, E)-2,4-Decadienal
(E, E)-8, 10-Pentadecadienyl acetate (E)-S-Tridecenyl acetate
(E.E.Z)-4,6. 10-Hexadecatrienyl acetate (E)-S-Tetradecenal
(E)-9-Octadecen-1-ol l (E)-S-Tetradecen- 1 -ol
(Z)-2-0ctadecenyl acetate (E)-S-Dodecenyl acetate
(E)-S-Hexadecenyl acetate (E)-S-Decenyl acetate
(Z)-10-Pentadecenyl acetate (E)-I O-Tetradecenyl acetate
(Z, E)-2, 13-Octadecadienyl acetate (E)-I O-Dodecenyl acetate
(E,Z)-6, 11 -Hexadecadienyl acetate (E)-I O-Dodecenal
(E,Z)-6, 1 1 –Hexadecadienal (E)-9-Tridecenyl acetate acetate
(E)-9-Tetradecen- 1 -ol (Z)-13-Octadecenal
(E)-9-Dodecenai (Z)-14-Hexadecenyl acetate
(E)-9-Dodecen~1-ol (Z)-12-Hexadecenal
(E)-9-Tetradecenyl acetate (E)-14-Octadecenal
(E)-9~Dodecenyl acetate (E)-14-Hexadecenal l
(E)-8-Tridecenyl acetate acetate (E)-8-Tetradecenyl acetate
(E)-13-Octadecenyl acetate (E)-8-Dodecenyl acetate
(Z)-1 1-Hexadecen-1-ol (E)-8-Dodecenal
(Z)-1 1-Hexadecenyl acetate (E)-8-Dodecen-1-ol
(E)-1 1-Hexadecenal (E)-8-Decen-1-ol
(Z,Z)-6,9-Pentadecadienal (E)-7-Tetradecenyl acetate
(E)-11-Octadecenal (E)-7-Tetradecen- 1 -ol
(E)-1 1-Octadecen-1-ol (E)-7-Dodecenyl acetate
(E)-10-Hexadecenal (E)-7-Dodecenal
(Z)-10-Hexadecenyl acetate (E)-7-Dodecen-1-ol
(E)-10-Hexadecen-1-ol (E)-7~Decenyl acetate
(Z,Z)-8,9-Pentadecadien-1-ol (E)-6-Tridecenyi acetate
(E, E,Z)~4,8, 1 –Hexadecatrienal (E)-6-Tetradecenyl acetate
(Z)-9-Octadecenyl Acetate (E)-6-Dodecenal
(Z)-9-Hexadecenal (E)-6-Dodecen-1-ol
(Z)-9-Hexadecen-1-ol (E)-5-Dodecen-1-ol
(Z)-7-Hexadecenal (E)-5-Decen-1-ol
(E)-9-Pentadecenyl acetate (E)-5~Tetradecenyl acetate
(Z)-2-0ctadecenal (E)-4-Tridecenyl acetate
(E,Z,Z)-4,6, 10-Hexadecatrien-1 –ol (E)-4-Dodecenyl acetate
(Z)-7-Hexadecenyi acetate (E)-4-Decenyl acetate
(Z)-8-Pentadecen-1-ol (E)-3-Tetradecenyl acetate
(Z,Z)-8, 11 -Heptadecadienyi acetate (E)-3-Tetradecen-1-ol
(Z,Z)-8, 0-Heptadecadien-1-ol (E)-3-Dodecenyl acetate
(E)-7-Hexadecenal (E)-2-Undecenyi acetate
(Z)-3-Hexadecenyi acetate (E)-2-Undecenal
(E)-5-Hexadecen-1-ol (E)-2-Tridecenyl acetate
(Z, E)- 1 ,14-Hexadecadienyl acetate (E)-2~Dodecenal
(E)-7-Hexadecen-1~ol l (E)-12-Tetradecenyl acetate
(Z,Z)-3, 13-Octadecadienai (E)-11-Tetradecenyl acetate
(E, E)-3, 13-Octadecadienyl acetate (E)-10-Dodecen-1-ol
(E,Z)-4,6-Hexadecadienal (E)-1 -Tetradecen-1-ol
(Z,Z)-2, 13-Octadecadienyl acetate (E)-1 1-Tridecenyl acetate
(E)-2-Heptadecenal (E)-1 1-Tetradecenal
(E,Z)-3, 13-Octadecadienyl acetate (E , E)-8, 10-Tetradecadien- 1-ol

In an embodiment, encapsulating polymer is selected from the group consisting of synthetic and/or natural polymer wherein the synthetic polymer is/are selected from the group consisting of, epoxy resins; aminoplast resin and natural polymer is/are selected from the group gelatine-gum, chitosan-gum, pectin-gum, sodium alginate and not limited to these. Amino resins are, urea / melamine formaldehyde resin, resorcinol formaldehyde resin and which are commercially available as Luwipal068, Luwipal063, luracoll SD and cymel 303/323/327, or in-house prepared aminoplast resin and not limited to this.

In particularly this embodiment, Luwipal068 and in-house prepared resin were used as encapsulating materials.
In yet another embodiment wax particles are prepared by methods such as phase separation, spray drying, solvent evaporation etc. with wax selected from natural waxes such as rice bran wax, sunflower wax, carnauba wax, candelilla wax, bee’s wax and synthetic waxes such as microcrystalline wax, fatty acid amide wax, polyolefin wax, paraffin wax.

The sprayable microcapsule formulation comprises of release modifier oil, selected from the group consisting of vegetable oil, and synthetic oil. The oil is selected from the group of plant oil, sunflower oil, peanut oil, soybean oil, rapeseed oil, corn oil, olive oil, grape oil, walnut oil, linseed oil, palm oil, coconut oil, argan oil, avocado oil, almond oil, hazel nut oil, pistachio oil, rice oil, cotton seed oil, wheat germ oil, sesame oil, mineral oil and mixtures thereof. Synthetic origin oils are selected from light and heavy paraffin oil, silicone oil, and mixture thereof preferably heavy paraffin oil.

The emulsifier is selected from the group consisting of hydrophilic polymers such as poly vinyl alcohol, poly vinyl pyrrolidone, poly styrene malic anhydride, polyethylene maleic anhydride or nonionic emulsifiers selected from, Brij50, Brij 52, Brij 30, Brij 35, Brij 90, Brij 92, Span 20, Span 40, Span 60, Span 80, tween 20, tween 40, tween 60 or tween 80, and mixtures thereof.

An antioxidant is selected from the group consisting of BHT (butylhydroxytoluene), BHA (butylhydroxyanisole), ethyl protocatechuate, isoamyl gallate, propyl gallate, NDGA (nor dihydroguauaretic acid) and guaicum gum.

The pH modifier used are selected from the group consisting of sodium hydroxide solution, triethanolamine, hydrochloric acid, Acetic acid, preferably triethanolamine and hydrochloric acid solution.

Yet the embodiment includes viscosity modifiers or stabilizers selected from the group of xanthan gum, acacia gum, polyvinyl pyrrolidone, polyvinyl alcohol, guar gum, acrylic acid copolymers, and corn starch, preferably xanthan gum.

In one more embodiment, the sprayable microcapsule formulation dispersion comprises of an active agent up to 150 grams per acre upon spray, with the release rate of semiochemical/s from microcapsules is of about 0.1 to 5 milligram per day per gram of formulation.

In an embodiment, the sprayable microcapsule formulation, wherein the microcapsules exhibits controlled release pattern along with the unique property of rain fastness by withstanding on the surface under certain extreme weather conditions.

Yet an embodiment includes the sprayable dispersion comprising a semiochemical/s entrapped microcapsules does not have phytotoxicity upon spraying with 1:5 dilution in water medium.

In one more embodiment, the sprayable microcapsule formulation, wherein the dispersion is used alone or in combination with insecticides or agricultural adjuvants for its application as a tank mix along with or without water and wherein the dispersion is used with or without dilution as aerosol spray system, or non-aerosol spray system, or liquid spray, or hand applied dispensers optionally in combination with insecticides.

Sprayable microcapsular formulation resulting from this invention was successfully field tested against the fall armyworm, Spodoptera frugiperda in a large scale for its mating disruption efficiency in Andhra Pradesh (India) in Maize crop. Phytotoxicity studies were carried out for the formulations in crops such as Maize, Paddy, Soy bean, Red and Black grams. These studies demonstrated that the formulation is non-phytotoxic.

Sprayable microcapsules from this present invention shows compatibility with a wide range of agrochemicals.

The present invention, being a sprayable micro encapsulated formulation will help to utilize this in a range of integrated insect pest management concepts such as mating disruption, attract-kill and push-pull strategies targeting a wide range of pest species.

While applying the formulation for area wide mating disruption program, it will be an expensive approach by using hand-applied pheromone dispensers. To overcome such problems of manual applied dispensers, the current sprayable microencapsulated (SM) formulations can be sprayed by equipment through aerial mode using drones or airplanes.

The current invention stands alone as the most advantageous aspect for pest management in row crops and others like maize, sorghum, rice, soybean, grape yards, sugarcane, cotton, red gram, black gram etc., that are cultivated in thousands of hectares at a stretch where adoption of area wide pest management is possible through aerial applications.

The present invented formulation can be used to a) disrupt the mating of important injurious insect pests like Spodoptera frugiperda, Sesamia inferens and Chilo partellus in maize, Scirpophaga incertulas, Cnaphalocrocis medinalis & Chilo suppressalis in rice, Mythimna separata in rice and Maize, Helicoverpa armigera & Helicoverpa zea in maize, sorghum, soybean, red gram, black gram etc., Chilo infuscatellus, Chilo sacchariphagus indicus and Scirpophaga excerptalis in sugarcane, Tuta absoluta in tomato, Plutella xylostella in cabbage, cauliflower and broccoli, Leucinodes orbonalis in brinjal, Pectinophora gossypiella, Earias insulana & Earias vittella in cotton, Maruca vitrata in leguminous crops, Phyllocnistis citrella in citrus crops, Amyelois transitella in almond and pistachios, Lobesia botrana & Desmia funeralis in grapes, Grapholita molesta & Cydia pomonella in apple, Spodoptera litura, S.exigua, S.littoralis & Thaumatotibia leucotreta in wide range of plants, Ectomyelois ceratoniae, Carposina sasakii & Zeuzera pyrina in apple, pear, pomegranate, almond, citrus etc., Anarsia lineatella in peach etc; and also b) can be used as attract-kill formulation along with appropriate insecticides for mass trapping and control of Bactrocera dorasalis in fruit crops, Bactrocera cucurbitae in cucurbitaceae plants.

As per all the embodiments of the invention, the sprayable microcapsule formulation of semiochemical/s will control the pest either through mating disruption or mass trapping and control by using mechanical devices or can be used to attract and kill strategies in combination with insecticides.

EXAMPLES:

The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention. It is being understood that the particulars shown are by the way of example and for purpose of illustrative discussion of preferred embodiments of the invention.

Example 1 - Preparation of Amino-plast resin:

32 g of 37 % formaldehyde aqueous solution was taken and adjusted to pH 7 to 8 with sodium hydroxide and placed in a reactor equipped with overhead mechanical stirrer. 12.6 g of melamine were added to the formaldehyde solution under stirring. The resulting mixture was continuously stirred at 70 -80°C for 20 to 30 minutes and then the temperature was reduced to 60°C. Further 80 grams of 3.8% urea solution and 10 ml of methanol was added and the resulting solution was allowed to cool to get clear resin solution. Solid content was adjusted to 40 to 50 % by rotatory evaporation of methanolic resin solution.

Example 2 - Preparation of wax particles:

52 g of crude rice bran wax (RBW) was melted at the melting temperature 80-85 C in a reactor A and stirred at 500 rpm for 15-20 min. In a second reactor B, 78 g of water containing 6 g of SPAN-40 and 20 g of Tween 60 were mixed under stirring and maintained at 80-85 °C for 30 min. Solution from reactor B was added to solution of reactor A and stirred at 2500 -3000 rpm for 30 min. To this resulting emulsion 90g of cold water (5 to 10 °C) is added under stirring at 1000 rpm. The resulting molten wax turned into solid wax particles. The pH of this wax particle dispersion was adjusted to 6 to 6.5 with triethanol amine.

Example 3: Preparation of SM formulation with commercially available MF resin:

Solution A was prepared by stirring 66 g solution of 1% aqueous solution of Polyethylene maleic anhydride (ZeMac 400) and 3.85 g of aminoplast resin (Luwipal 068) with an overhead stirrer at 300 to 500 RPM for 10 min at room temperature/ 27°C and further the pH of solution was adjusted to 4 to 4.5 with 10% Hydrochloric acid solution., The solution was further stirred with overhead stirrer at 300 to 500 RPM for 15-20 min at Room Temperature 27°C.

Solution B - Core solution was prepared by mixing 15 g of DBM pheromone, 15 g of paraffin oil and 1 g of BHT under stirring.

Solution B was added to solution A and the mixture was homogenised at 3000 to 3200 RPM with Remi Homogenizer at room temperature for 4 to 5 min. The mixture was then stirred at 1000 Rpm for 30 min at RT for 15 to 20mins and then 65 g of water was added. This resulting mixture heated at 55° C for 2h at 1000 rpm with overhead stirrer, followed by heating at 65° C for 1 h and 80° C for 2h at 700 rpm with overhead stirrer. The obtained microcapsule dispersion was cooled to 27° C and the pH was adjusted to 6 to 6.5 with triethanolamine.

To obtained sprayable microcapsular dispersion, 171.68 g of wax particle dispersion obtained as described in Example 2 and 165.83 g of microcapsule dispersion as described in Example 3 were added under stirring at 1000 rpm followed by addition of 37.30 g of 2 w/w% Xanthan gum solution. Thus, this process resulted in sprayable microcapsular formulation having around 4% AI of pheromone.

Example 4:

The complete process was carried out as described in Example 3 and DBM pheromone was replaced with BFSB pheromone.

Example 5 to 10:

The complete process was carried out as described in Example 3 wherein amino resin Luwipal 068 was replaced by amino resin prepared as described in Example 1 with different pheromones and attractants as follows -
Example No. Pheromone
5 DBM
6 Lobesia
7 RYSB
8 Helico
9 FAW
10 PBW
11 CL
12 ME
13 (+) Verbenone
14 (-) Verbenone

Example 15 - Characterization of SM formulation:

Optical Microscopic observation:

A drop of SM formulation is taken on glass slide and was observed under optical microscope.
The size of the microcapsules was found to be in the range of 10-50 microns and are spherical in shape as observed in optical microphotograph (Fig 1)

Encapsulation efficiency:

Encapsulation efficiency was determined as follows -
Weigh microcapsules dispersion in 30mL glass vial/beaker.
Dilute it with distilled water and disperse capsules with normal handshake.
Filter microcapsules through 0.45micron membrane. Record the weight of dry membrane before filtration.
Remove the membrane in petri plate and kept for drying at 60C for 30min.
Note down the dry weight of membrane with microcapsules.
Keep membrane in dry glass vial and tightly close and take it for GC analysis.
Add 10 ml of internal standard solution in in glass vial and tightly closed with Teflon.
Extract the active present in the solid microcapsules by incubating the sample in the pre heated oven for 2 hours at 80 C.
Filter the sample through 0.25micron syringe filter and run in the gas chromatography.
Quantify the active by calculation against internal standard from GC chromatogram.
All process carried out in triplicate and measurements carried out with 0.1mg scale analytical balance.

Encapsulation efficiency (%)=(percent activeobtainedbyGC in solids)/(percent theoreticalactiveinsolids)*100

The Encapsulation efficiency of DBM (Example 3) and BFSB (Example 4) was calculated using the formula above is tabulated in Table 1.

Table 1
Active Theoretical active in solid (%) Actual active obtained
by GC (%) Encapsulation
Efficiency (%)
DBM 42.24 41.33 97.84
BFSB 42.64 39.22 91.98

Similar process was adopted for other semiochemical/s microcapsules and observed encapsulation efficiency found more than 90%.

Release profile studies:

The SM formulation was diluted such that resulting dispersion has ~ 2 % AI. 150 – 200 mg of this diluted SM formulation was taken on butter paper (2 x 2 inch) and was allowed to dry at room temperature (25- 30C) for 12 hours. This butter paper piece was then hung in open air space with the help of thread. After specific time interval the paper is collected and put in 30 ml glass vial to which 10 ml of ethyl acetate was added and heated for 2 h at 80 C. The amount of active extracted in ethyl acetate was then determined by standardized GC procedure.

The amount of pheromone released was thus determined at different time interval. A typical release data of DBM SM formulation is given in Table 2. Release profiles of DBM and BFSB SM formulations are shown in Fig 2 and 3 respectively.

% release of AI was calculated by following formula
amount of AI retained in microcapsules at time 0 days = X
amount of AI retained in microcapsules at time t days = Y
amount of AI released at time t = X-Y
% Release = [(X-Y) / X ] x 100

Table 2: DBM Microcapsule Spray Release data
Days Weight of AI retained
in microcapsules , mg % Retained % Release
0 3.88 100 0.00
4 3.6 92.78 7.22
7 3.42 88.14 11.86
14 3.34 86.08 13.92
21 3.24 83.51 16.49
30 3.02 77.84 22.16

Table 3: BFSB Microcapsule Spray Release data
Days Weight of AI retained in microcapsules (mg) % Retained % Release
0 3.86 100 0.00
4 3.74 96.89 3.11
7 3.56 92.23 7.77
14 3.32 86.01 13.99
21 3.1 80.31 19.69
30 2.820 73.06 26.94

Valerie D. et al (Environmental Science and Pollution Research, June 2021) reported Lobesia botrana pheromone microcapsules which showed 30% release on first day and 650 mg of AI release per day per hectare over the period of 12 days whereas SM formulation from our invention show 10 % release on the first day and 250-350 mg of AI release per day per hectare over the period more than 30 days.

Rain-fastness studies with Scanning electron microscope (SEM) observation:

Rainfall Simulator set up:

Rain fastness studies were carried out under controlled conditions using a battery-operated knapsack sprayer equipped with a 4 LTS heavy motor that ensured the constant flow of water at a set pressure. A four hole hallow cone nozzle was used specifically for the purpose that exactly simulate the natural rainfall conditions with even distribution of droplets on the complete wetting surface. Before initiating the rain-fastness study, the rainfall measurements were calibrated using a rain gauge at specified pressure. The nozzle was positioned at 1 meter height from the ground surface and rain gauge was placed at the ground surface. At specified pressure (5.6 psi), water collected in the rain gauge per minute was measured multiple times and accordingly the exposure timing for 25 mm, 50 mm and 100 mm were calculated and fixed. The rainfall was calibrated at the rate of 1.25 mm per minute.

Test Procedure

The tomato saplings were collected from the nursery and transplanted onto the pots and acclimatized for a week before treatment. The treatment solution was prepared by adding 100 ml of SM formulation with 500 ml of water at 1:5 ratio (formulation: water) in a 1 litre glass beaker.

Saplings were randomly selected and the test solution was sprayed using a 1 Litre capacity hand held pressurized atomizer and allowed to dry for 24 hours. Then treated tomato plants were exposed to 25 mm, 50 mm and 100 mm simulated rainfall conditions separately for a period of 20 minutes, 40 minutes and 80 minutes respectively. The plants were again allowed to dry for 24 hours before SEM analysis.

Treated leaves under the test were collected from the sprayed foliage and observed under FE-SEM. Samples were sputter coated with gold before SEM imaging to avoid charging. It can be seen that neat microcapsules sprayed are washed away after 25mm rain simulation study (Fig.6). Whereas, SM formulation containing microcapsules withstanding upto 100mm (Fig.6) simulated rainfall conditions intact microcapsules are seen on the leaf indicating the good adherence to the substrate and rain-fastness property.

Phytotoxicity Studies

The phytotoxicity studies were undertaken at different dilutions of SM formulations with water such as SM: Water ratio of 1:2, 1:5, 1:10, 1:20, 1:40, 1:60, 1:100 and 1:200. The observations were recorded at specific time intervals viz., 0th Day (3h post application), 3rd, 5th, 7th, 10th, and 14th day after application for phytotoxicity symptoms such as leaf surface injury, wilting, epinasty, hyponasty, necrosis etc. The observations revealed that the SM formulations along with different AIs targeting different pests showed no phytotoxicity symptoms during the 14 days observation period.
, Claims:1. A sprayable microcapsule formulations of semiochemical/s comprising of
a) at least one component of core/active shell reservoir polymer microcapsules; and
b) at least one component of wax particle dispersion which is dispersed in the system,
wherein the said formulation is prepared using a core of semiochemical/s encapsulated in polymer shell as microcapsules dispersion and wax particle dispersion that are uniformly dispersed into the system, exhibits an improved features and can be used for mating disruption of insects or Push Pull strategy.

2. The sprayable microcapsule formulation as claimed in claim 1, wherein
a) the component of core/active shell reservoir polymer microcapsules comprises of:
i. core shell reservoir microcapsules in amount of 1 to 50 w/w% of total composition;
ii. semiochemical or mixture of semiochemical/s in an amount of 1 to 95% by weight of microcapsule;
iii. polymer shell of the microcapsules in an amount of 5 to 90 w/w % of microcapsule;
iv. release modifier oil in the ratio of 0.1:1 to 1:10 with respect to active agent; and
v. antioxidant in an amount of 0.01 to 3 % by weight of active,
b) component of wax particle dispersion is dispersed in the system; and
i. wax particles in an amount of 1 to 30 w/w % of formulation;
ii. an emulsifier in an amount of 0.2 to 10 w/w % of formulation; and
iii. a viscosity modifier in the amount of 0.01 to 0.5 w/w % of formulation.

3. A method of preparing a sprayable microcapsule formulation comprising the following steps:
i) Preparation of microcapsules-
(a) preparing solution A: stirring of emulsifier and aminoplast resin followed by adjusting the pH to 4-4.5 with 10% HCl solution;
(b) preparing core solution B: a predetermined quantity of Semiochemical/s, modifier oil and antioxidant were mixed under stirring to obtain core solution B;
(c) solution B of step b) is added into the solution A of step a) and homogenizing at 25-30°C;
(d) stirring the emulsion of step c) at 1000 RPM at a temperature of 25-30°C;
(e) addition of water to step d) followed by heating to the temperature of 55°C and maintaining at 1000 RPM; and
(f) cooling the obtained microcapsule dispersion at step e) to 27°C and adjusting the pH to 6-6.5 with triethanol amine,
ii) Preparation of wax particles-
Wax is melted at its melting point and separate aqueous phase is prepared by dispersing emulsifiers in water phase maintained at the wax melting temperature, then aqueous phase is added to wax medium to obtain emulsion, followed by addition of cold water were melted wax turns into solid wax particles;
iii) Wax particle dispersion - obtained in step ii) is added to the microcapsules dispersion obtained in step i) under stirring at 1000RPM followed by addition of viscosity modifier solution and adjust the pH of wax particle dispersion to 6 - 6.5;
wherein the semiochemical/s encapsulated in polymer shell are uniformly dispersed into the system, as the dispersion is used for mating disruption of insects or Push Pull strategy.

4. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the polymer shell or encapsulating agents are selected from the group consisting of synthetic and/or natural polymers.

5. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the polymer shell is selected from the group consisting of silicone resins or epoxy resin, amino resins; and biopolymers viz gelatine-gum, chitosan.

6. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the emulsifier is selected from the group consisting of hydrophilic polymers such as poly vinyl alcohol, poly vinyl pyrrolidone, poly styrene malic anhydride or selected from the group consisting of, soy oil, Brij50, Brij 52, Brij 30, Brij 35, Brij 90, Brij 92, Span 20, Span 40, Span 60, Span 80, tween 20, tween 40, tween 60 or tween 80, and mixtures thereof.

7. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the formulation additionally comprises of an antioxidant, selected from the group consisting of BHT (butylhydroxytoluene), BHA (butylhydroxyanisole), ethyl protocatechuate, isoamyl gallate, propyl gallate, NDGA (nor dihydroguauaretic acid), and guaicum gum.
8. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the formulation additionally comprises of modifier oil, selected from the group consisting of essential oil, vegetable oil, and mineral oil.

9. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the semiochemical/s is at least one of a pheromone/s, an allomone/s, a kairomone/s, or a synomone or mixtures thereof, preferably pheromone/s.

10. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the insect semiochemical/s are selected from the group consisting of the active blend of (Z, Z)-7, 11- hexadecadien-1-yl acetate and (Z, E)-7, 11- hexadecadien-1-yl acetate; the active blend of Z 9- Tetradecenyl acetate, Z7- Dodecenyl acetate and Z11- Hexadecenyl acetate; the active blend of E-11-hexadecen-1-yl acetate and (E)-11-hexadecen-1-ol; the active blend of 3E,8Z,11Z-Tetradecatrienyl acetate and 3E,8Z-Tetradecadienyl acetate; the active, (Z,Z,E)-7,11,13-Hexadeca trien-1-al; the active blend of Z-11-Hexadecenal, Z-11-Hexadecenyl-1-acetate and Z-11-Hexadecenol; the active blend of Z-11-Hexadecenal and Z-9- Hexadecenal; the active blend of Z-11-Hexadecenal and Z-9-Hexadecenal; the active blend of (Z,E)-9,11-Tetradecadienyl acetate and Z9,E-12-Tetradecadienyl acetate; the active blend of Cis-3-Hexenyl acetate and 2E- Hexen-1-ol; the active blend of Z-11-Hexadecenyl-1-acetate and Z-11-Hexadecenol; the active of Z-11-Hexadecenol; the active of (7Z,9E)-Dodeca-7,9,11-trien-1-yl formate; 11Z,13Z-Hexadeca dienal; the active blend of 4 methyl 5 nonanol and 4 methyl 5 nonanone; the active of Ethyl-4-Methyl octanoate; the active of Methyl eugenol; the active blend of Methyl eugenol and Cuelure; the active of (E,E) -8,10-Dodecadien-1-ol; the active blend of (Z)-8-Dodecen-1-yl acetate, (E)-8-Dodecen-1-yl-acetate and (Z)-8-Dodecen-1-ol; the active, (1R)-cis-4,6,6-Trimethylbicyclo [3.1.1]hept-3-en-2-one; the active trans-3,7-Dimethyl-2,6-octadien-1-ol & cis-3,7-Dimethyl-2,6-octadien-1-ol; the blend of Z-13-Octadecynyl acetate and Z-13-Octadecenol; the blend of (E,E)-10,12-hexadecadienal, (E,E)-10,12-hexadecadienol and E-10-hexadecenal; the blend of Z,E-9,12-Tetradecadien-1-yl-Acetate and Z-9 Tetradecenol; the blend of (Z)-8-Dodecen-1-yl acetate and (E)-8-Dodecen-1-yl-acetate; the active, (7E,9Z) dodeca- 7,9-dien-1-yl acetate, and the active 4-vinyl Anisole; Methyl Isonicotinate; Mono terpenes & Terpene alcohols and (+) Verbinone, (-) Verbinone; that are optionally used as blends or individually.
11. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the semiochemical/s is preferably selected from the group consisting of (Z, Z)-7, 11- hexadecadien-1-yl acetate and (Z, E)-7, 11- hexadecadien-1-yl acetate for Pink Bollworm; Z 9- Tetradecenyl acetate, Z7- Dodecenyl acetate and Z11- Hexadecenyl acetate for Fall armyworm; Methyl eugenol; Methyl eugenol and Culure for fruit fly; (E,E) -8,10-Dodecadien-1-ol for Codling Moth, Z-11-Hexadecenal and Z-9-Hexadecenal for Helico, for stink bug and Yellow stem borer, that are optionally used as blends or individually.

12. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the oil is selected from the group consisting of plant oil or synthetic oil, preferably sunflower oil, peanut oil, soybean oil, rapeseed oil, corn oil, olive oil, grape oil, walnut oil, linseed oil, palm oil, coconut oil, argan oil, avocado oil, almond oil, hazel nut oil, pistachio oil, rice oil, cotton seed oil, wheat germ oil, sesame oil, mineral oils and mixtures thereof.

13. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein wax is selected from natural waxes preferably from rice bran wax, sunflower wax, carnauba wax, candelilla wax, bee’s wax and synthetic waxes preferably from microcrystalline wax, fatty acid amide wax, polyolefin wax, paraffin wax.

14. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the microcapsules are spherical in shape, with a mean size of about 1 to 500 microns, preferably about 5 microns to 50 microns.

15. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the pH value of sprayable microcapsule dispersion is about 5 to 6.5 and is dispersible in water.

16. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the dispersion comprises of an active agent up to 150 grams per acre upon spray, with the release rate of pheromone from microcapsules is of about 0.1 to 5 mg per day per gm.

17. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the dispersion shows high physical and chemical stability at 540C temperature with controlled release of pheromone over an extended period of at least eight weeks.
18. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the dispersion is sticky to the surface of plant / foliage, thereby achieving and supporting the controlled release of pheromone or semiochemical/s for longer period and bio-efficacy towards insect species.

19. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the viscosity modifier or stabilizer is selected from xanthan gum, guar gum, acrylic acid copolymers, corn starch preferably xanthan gum solution.

20. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the microcapsules and sprayable formulation exhibits controlled release pattern along with the unique property of rain fastness by withstanding during all seasons or all types of weather conditions.

21. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the dispersion is used alone or in combination with insecticides or agricultural adjuvants for its application as a tank mix along with or without water.

22. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the sprayable dispersion formulation does not exhibit phytotoxicity effect upon spraying directly or at recommended dilution in water medium.

23. The sprayable microcapsule formulation as claimed in claims 1 and 2, wherein the dispersion is used with or without dilution as aerosol spray system, or non-aerosol spray system, or liquid spray, or hand applied dispensers optionally in combination with pesticides.