Field of the Invention t
?-xrrp\~~ U'J i.bk3a.
The present invention relates to a novel synergistic water dispersible granular
composition containing an avermectin compound and a chloronicotynyl
compound and aprocess for preparation thereof to control a broad spectrum of
insect's attack on agricultural crops.
Background of the Invention
US 3639617(A) describes a process for preparation of pesticides in granular
form using sulfonatedlignins.
US 3954439(A) describes granular compositions comprising herbicidal agents
and one or more surfactants and process for production of the same.
US 2009208423 (Al) describes a synergistic insecticidal composition
containing a chloronicotinylcompound and a pyrethroid compound. The
invention describes a process for making a synergistic insecticidal composition
of imidachloprid plus cypermethrin and imidachloprid plus perrnethrin in
wettable powder form.
US 5,288,710 describes a relatively safe formulation of Emamectin benzoate in
soluble granule form comprising a water-soluble pesticides and a water soluble
filler. The invention provides pesticides formulation containing emamectin
benzoate in an amount which is soluble in water at the field application dose.
The formulation had efficacy equivalent to the corresponding liquid formulation
, yet with improved handling safety, such as lower eye irritation.
US 5532209A describes a dispersible granular formulation of propnil herbicide
which provides excellent suspensibility and dispersibility characteristics and
that resist attrition .
US 4,936,901 discloses a dry flowable water dispersible granular formulation
comprising a mixture of aggregates of microcapsules of water insoluble
pesticides encapsulated in a polymeric shell .The water dispersible granules are
prepared by mixing appropriate quantities of an aqueous dispersion of the
encapsulated component ,the non-encapsulated component and formulation
adjuvant to form a slurry which can be directly extruded or spray dried.
1
CN 102318636 describes an insecticidal composition of thiamethoxam a h 5
\i
emamectin benzoate having content percentage 0.1 to 50:20 to 0.1 respectively. ORIG NAI The synergistic insecticidal composition was made in the form of emulsifiable
concentrate, suspension concentrate, wettable powder, micro-emulsion and
water dispersible granules. I JP 20062 13664 describes plant disease pest control composition which contains
penthiopyrad as an ingredient and one or more compounds selected form the
group consisting of : imidacloprid, thiomethaxom, acetamiprid, clothinidin,
lufenuron,abamectin, emamectin benzoate as an ingredient I1
US 20090305889 relates to a granular formulation with enhanced biological
activity .The granular composition of the invention are obtained by coating ,
absorbing or impregnating a carrier material with a micro emulsifiable
concentrate .The dry granular composition may be applied to soil and /or
vegetation by spreading or broadcast application .
US 201 10306502 relates to a water dispersible granular composition comprising
of at least one solid agrochemically active substance , at least one liquid or
low melting agrochemically active substance and at least one sorptive filler.
CN 1836513, WO 2005096820, WO 2002028186, CN 1274530 and WO
9522902 declares composition comprising solid actives such as fipronil
,imidacloprid and liquid actives such as lambdacyhalothrin and chlorpyriphos
where in the composition are formulated as an oil emulsion , micro emulsion ,
wettable powder , water dispersible granules , suspension concentrate .While
these patents generally disclose various formulation of a combination of actives
including a water dispersible granules composition , the patents do not provide
or teach a method of preparing the water dispersible granule composition. The
standard processes for preparing a water dispersible granules for a combination
may not be feasible and would not provide a satisfactory composition which
could provide good dispersion , stability ,shelf life and other properties that a
wettable granules should possess.
WO 2008080542 discloses composition comprising solid active as fipronil and
liquid as lambdacyhalothrin . CN 1 186602 discloses a synergistic insecticidal
mixture comprising a liquid active such as chlorpyriphos and solid active as
deltamethrin . These patents do not provide or teach a composition of the
combination in a water dispersible granules form.
insects of the order Thysanoptera (thrips), which comprises treating pla@ 21 GI
propagation material thereof, with a nematicidally effective amount of a
nematicide selected from abamectin, emamectin benzoate and spinosad and at
least one insecticidally effective amount of an insecticide selected from
imidacloprid, clothianidin and thiamethoxam.
It has been found that the combination of emamectin benzoate (1-5%) and
thiamethoxam (10-14%) in wettable granule form results in a quite
unexpectedly enhanced action against broad spectrum of insects and provides
other unexpected advantages when used in connection with plant propagation
materials. The increase in action and other valuable properties achieved with the
combination as per the invention is significantly superior than the activity to be
expected by the individual components, i.e. the activity is enhanced
synergistically which, inter alia, extends the limits of the pesticidal activity of
the compounds.
Thiomethoxam is a broad spectrum systemic insecticide having quick stomach
and contact action and effective against stem borer, gall midge,leaf folder,
brown plant hopper, white backed plant hopper, green leaf hopper , whorl
maggot, aphids, jassids and thrips on cotton and rice crop.Thiamethoxam is the
common name of (4z)-3-C(2-chloro-1,3- thiazol-5-y1)methyl) -5-methyl-Nnitro-
l,3,5-oxadiazine-4-imine . It is white to off white powder with the
following physio-chemical properties:
Melting Point - 139. l0c
Boiling Point - 200~~10m.1m Hg
V.P. - 2x 10-"mm Hg at 2 0 ' ~
Solubility in water (4250 mgll at 25'~) ,soluble in acetone ,methanol and
ethanol.
Stability-stable under normal temperature and pressure at pH 4, 5 and 7.
Thiomethoxam degrades slowly at pH 9 and 4 5 ' ~to simple compounds under
sunlight.
Emamectin benzoate is an avermetin class of insecticide similar to abamectin .
It is a non-systemic insecticide which penetrates leaf tissues by translaminar
t
movement. It is a novel semi synthetic derivative p
of avermectin family . It is very effective for controlling all lepidoptreus pest of _,
r -1 7- 7
cole crops at low usage rate of 8g a.i /ha, mites leaf miners and thrips on 'cd;i+ L
vegetable , maize, tea, cotton, peanuts, soyabean.Emamectin is the common
name of (4"R)-5-O-dimethyl-4"-deoxy-4"-(methyl amino)avermectin a,, +
(4"R)-5-O-demethy1-25-de(l-methpyrlo pyl) -4"-deoxy -4"(methyl amino )-25-
(1 -methyl ethyl )avermectin a,, (9: 1).
It is a white to light pale yellow powder with the following physico- chemical
properties:
Melting Point - 14 1 - 146'~
V.P. - 4x 10'~m~(2a 1 °C )
Solubility - in water - 0.024gll (pH 7,25'c), in organic solvent at 20'c (mgll) -
n Hexane - 77.0, toluene - 26000 , methanol - 270000, octanol - 48000
Boiling Point - decomposes before boiling
Stability - it rapidly degrades in soil .
Stable to hydrolysis in water at pH 5.2 -8.0 at 20 - 2 9 ' ~
Both thiamethoxam and emamectin benzoate have very poor solubility in water
and have high melting point . Emamectin benzoate has high solubility in
organic solvent and formulated as emulsifiable concertrate, suspension
concentrate and soluble granules.Thiamethoxam has very poor solubility in
water and aromatic solvent and this is formulated as wettable granules and flow
able suspension.
Hence there is a long felt need to develop altemative,simple and efficient
granulation process for developing a composition comprising of two solid active
substance where in the particle size of the solid active substance and the filler is
effectively controlled to ensure optimum bio-efficacy of the composition.Also
there is a need to develop a composition in the form of wettable granules ,
where in the composition is highly synergistic and exhibits increased bioefficacy
with reduced dosages, as compared to the individual use of the active
substance . The use of instant granular formulation is less risky to personal than
the corresponding liquid formulation . Risk of exposure is evaluated as: Risk=
hazard x exposure, because the instant granular formulation is less toxic , the
hazard is decreased. In addition the probability of contact is lower when the
material is in solid form as compared to a 1iquid.Hence the degree of exposure
is reduced. Hence there is a need to develop synergistic formulation of
Emamectin benzoate and Thiamethoxam which diminishes the risk of exposure
and provide greater handler safety and which exhibits increased bio- efficacy
with reduced dosages.
Advantages of the Invention over prior art:
The advantages are:
- broadening of the spectrum of pesticidal activity to other pests;
- resistant to strains;
- reduction in the rate of application of the active ingredients;
- sufficient control of the pests with the aid of the compositions according to the
invention, even at a rate of application at which the individual compounds are
totally ineffective;
- beneficial behaviour during formulating and upon application, for example
upon grinding, sieving, emulsifling, dissolving or dispersing;
- increase in storage stability; improvement in stability to light;
- more profitable degradability;
- improvement in toxicological andlor ecotoxicologicalbehavior; improvement
in crop characteristics including: emergence, yield of crop, plant stand, tillering
increase, increase in height of plant, increase in leaf blade, more improved root
system, decrease in dead basal leaves, improvement in strength of tillers,
greener leaf colour, less fertilizers required, less seed requirement, more
productive tillers, earlier flowering, early grain maturity, less plant verse
(lodging), increase in shoot growth, improved plant vigor, and early
germination; or any other advantages known to a person skilled in the art.
04 Q
Objectives of the Invention
The main objective of the present invention is to provide a novel
synergisticwater dispersible granular composition of thiamethoxam and
emamectin and a process for preparation thereof to control attack of gall midge,
stem borer, brown plant hopper, green leaf hopper, whorl maggot ,boll worm,
fruit and shoot borers aphids, jassids and thrips on crops such as rice, cotton,
okra, etc.
Another objective of the present invention is to provide a safe non- dusty
granules formulation with diminished risk of exposure and exhibiting excellent
dispersibility, suspensibility and storage stability.
Yet another objective of the present invention is to provide a synergistic
composition which exhibits increased bio-efficacy with reduced dosages as
compared to the individual insecticide components.
Summary of the Invention
The present invention relates to a novel synergistic water dispersible granular
composition containing an avermectin compound and a chloronicotynyl
compound and a process for preparation thereof to control a broad spectrum of
insect's attack on agricultural crops. The combination formulation of emamectin
benzoate and thiamethoxam in the water dispersible granules form relates to the
composition comprising of emamectin benzoate , thiamethoxam , wetting and
dispersing agent , inert binder carbohydrates , extrusion softner, non-ionic
wetting agent , agglomeration suppressant, stabilizer and a silicon based antifoaming
agent.
The process for preparation of a novel synergistic water dispersible granular
composition comprises of certain steps. Emamectin benzoate, thiamethoxam ,
wetting agent, dispersing agent, diatomaceous earth, sodium benzoate, butylated
hydroxyl toluene, sodium citrate anhydrouslactose are thoroughly mixed in
parts by weight in a ribbon blender. Some parts by weight of the mass
istransferred to a dough mixer. A solution containing non-ionic emulsifier in
water and isopropyl alcohol mixture is sprayed over the mass that is taken in a
dough mixer. The wet mass produced is extruded through a low pressure basket
extruder and finally the extruded granules are dried in a continuous/ batch
fluidized bed drier.
Detailed Description of the Invention
- - -
The present invention relates to a novel synergistic water dispersible
composition and process for preparation thereof to control a broad spectrum of
insects attack on agricultural crops. The invention further relates to a method for
combination formulation of Emamectin benzoate and Thiamethoxam wherein
the chemical properties of both the compounds are retained but provide a
synergistic effect by controlling vide variety of insects at lower dosages.
According to a preferred embodiment of the present invention ,the objective is
to provide a synergistic effect of the combination formulation of emamectin
benzoate and thiamethoxam in the water dispersible granules form with a
composition comprising of emamectin benzoate 0.5-3.0 %, thiamethoxam 10-
15%, wetting and dispersing agent 5-20% , inert binder carbohydrates 30-70%,
extrusion softner 1-5%, non-ionic wetting agent 2-5%, agglomeration
suppressant 1 - 5% stabilizer 1-5% and a silicon based anti-foaming agent.
Proper selection of the wetting and dispersing agents, agglomeration
suppressant, extrusion softner, non-ionic wetting agent and stabilizer is most
important to prevent caking , good dispersion to provide broad crop coverage
area ,better disintegration of granules at the time of application and long term
stability of the formulation .The dispersing agent is a compound which ensure
that the particles remain suspended in the application mixture . The dispersing
agent can be an ionic or non-ionic agent or a mixture of such surface active
agents. The wetting agent is a compound which facilitates rapid wetting of the
granule when the granule is added in to the water.
In an another embodiment , the dispersing agents are selected from group
comprising polycarboxylates, alkyl naphthalenesalfonate condensates , phenol
sulphonic acid condensates , lignosulfonates, methyl oleyltaurates and poly
vinyl alcohols.The binders are selected from a group comprising
polysaccharides , sucrose , dextrose , starch , partially hydrolysed polyvinyl
acetate or dissacharides such as sucrose , lactose , trehalose and maltose.The
wetting agent are selected from a group comprising sulfosuccinates, sulphated
esters , phosphate esters , sulfated alcohol and alkyl benzene sulfonates .
The emulsifiers that can be used in accordance with the invention should
provide wetting of the dough and also help in solubilization and suspension of
the granules when added to water.The emulsifiers can be selected from a group
comprising ethoxylated alcohols ethopropoxylated alcohols
ethoxylatednonylphenolsioctyl phenols, ethoxylatedtristeryl phenol; 1
ethoxylatedtristrylphenol phosphate, ethoxylated and ethopropxylated
oil and proprietary blend of emulsifier .
The water soluble agglomeration suppressant used in the formulation are ionic
compound such as inorganic salt and organic acid nitrogen containing
compound such as nitrogen fertilizers. For example ammonium sulphate , urea,
ammonium nitrate, mono-di- and triammonium phosphate ,alkali metal,
magnesium calcium and ammonium salt of nitrogen and organic acid such as
hydrochloric acid, sulphuric acid , nitric acid , phosphoric acid , carbonic acid,
acetic acid, propanic acid .
The extrusion flow improvers used for smooth extrusion of the granules are
compound such as stearic acid ,calciurn/magnesium salt of stearic acid and
sodium benzoate , sodium tripoly phosphate ,magnesium carbonate or
potassium benzoate .
The preservatives useable in the present invention can be potassium sorbate,
butylated hydroxyl toluene, butylatedhydroxy anisole, ascorbic acid,
benzisothiazilones ,tall oil rosin, natural tocopherol, and tert-butyl
hydroquinone.
The present invention will be illustrated in more detail with reference to the
following formulation examples and product test results. These examples are
just illustrative and are not meant to be limiting.
The following examples illustrate the basic methodology and versatility of the
invention .
According to a preferred embodiment the process for preparation of a water
dispersible granule of Emamectin benzoate3% + Thiamethoxam 12% comprises
of the following steps:
Step 1
3.0 parts by weight of emamectin benzoate technical, 12.0 parts by weight of
thiamethoxam technical , 4 parts by weight of wetting agent, 8 parts by weight
of dispersing agent, 5 parts by weight of diatomaceous earth, 1 part by weight of
sodium benzoate, 1 part by weight of butylated hydroxyl toluene, 2 parts by
weight of sodium citrate and 62 parts by weight of anhydrous lactose were
thoroughly mixed in a ribbon blender. The mixed mass was air jet milled to
particle size less than 15 microns and thor
blender.
Step 2
98.0 parts by weight of the mass from step 1 was transferred to a dough mixer.
A solution containing 2 parts by weight of non-ionic emulsifier in water -
isopropyl alcohol mixture was sprayed over the mass taken in dough mixer
under continuous mixing. The material was mixed till completely homogenized.
The wet mass of step 2 was extruded through a low pressure basket extruder.
The extruded granules were dried in a continuous/ batch fluidized bed drier till
the moisture in the granules is less than 2% d m .
The following tables illustrate the various combinations of emamectin benzoate
(0.5 - 3.0%dm) and thiamethoxam ( 12 - 15%dm) that were prepared and
evaluated for synergistic effect. The below table also illustrate the compositions
prepared to achieve best suspension, dispersion, attrition and storage stability.
Table 1
Preparation 1 2 3 4
Emamectin benzoate 0.5 1.0 2.0 3.0
Thiamethoxam 15.0 14.0 13.0 12.0
Wetting agent 4.0 4.0 4 .O 4.0
Dispersing agent 8.0 8.0 8.0 8.0
Diatomeceous earth 5.0 5.0 5.0 5.0
Sodium benzoate 1 .O 1.0 1.0 1.0
Sodium citrate 2.0 2.0 2.0 2.0
Non ionic surfactant 2 .O 2.0 2.0 2.0
Butylated hydroxyl toluene 1.0 1.0 1.0 1 .O
Anhy. Lactose 61.5 62.0 62.0 62.0
TOTAL 100.0 100.0 100.0 100.0
Table 2
Preparation 5 6 7
Emamectin benzoate 3 .O 3 .O 3 .O
Thiamethoxam 12.0 12.0 12.0
Wetting agent 2.0 4.0 6.0
Dispersing agent 8.0 8.0 8.0
Diatomeceous earth 3.0 5.0 4.0
Sodium benzoate 1 .O 1 .O 1 .O
Sodium citrate 2.0 2.0 2.0
Non ionic surfactant 2.0 2.0 2.0
Butylatedhydroxy toluene 1 .O 1 .O 1 .O
Anhy. Lactose 66.0 62.0 61 .O
TOTAL 100.0 100.0 100.0
Table 3
Emamectin benzoate 3.0 3 .O 3 .O
Thiamethoxam 12.0 12.0 1.2.0
Wetting agent 4.0 4.0 4.0
Dispersing agent 8. 0 8.0 8.0
1 Diatomeceous earth 3 .O 4.0 5 .O 1
Sodium benzoate 1 .O 1 .O 1 .O
Sodium citrate 2.0 2.0 2.0
Non-ionic surfactant 0.0 1 .O 2.0
Butylated hydroxyl toluene 1 .O 1 .O 1 .O
Anhy.Lactose 65.0 64.0 62.0
1 TOTAL 100.0 100.0 100.0
All the above preparations are in masslmass.
Evaluation of physico- chemical properties - active ingredients,
suspensiberility, dispersibility and attrition after heat stability
,To evaluate the physico - chemical properties the granular formulations were
kept in 100 ml of glass bottles, closed and stored in hot air oven maintained at
54(&2)C for two weeks and then the active ingredients, suspensibility,
dispersibility and attrition were measured. The results are as shown in the below
table:
Preparation > 1 2 3 4 5 6 7 8 9 1 0
Tests
a.i. Emamectin 0.45 0.8 1.8 2.9 3.0 3.05 2.9 2.8 2.9 3.05
a.i.Thiamethoxam 13.0 14.0 12.5 12.1 11.9 12.2 11.9 12.2 11.8 12.2
Suspensibility 75 78 80 85 79 92 85 60 68 93
Dispersibility 60 72 78 85 65 82 75 70 76 85
Attrition 5.0 4.2 3.2 1.2 1.0 1.3 2.4 2.2 2.6 1.5
All the results are expressed in mass/mass.
Bio-efficacy of Emamectin benzoate 3% + Thiamethoxam 12% WG against tea looper
(Buzurasuppressariaguenee) and tea mosquito bug (Helopeltistheivora)
S.N I Treatment I Dose /
1
2
3
(g/ml)
h a
18750
250 00
312.50
800.00
3% + Thiamethoxam
12%WG
Emamectin 3% +
Thiamethoxam 12%
WG
Emamectin 3% +
Thiamethoxam 12%
WG
Profenofos 5O%EC
Control
Mean of No. of Loopers 15 Bush
Pre
21.66
22.32
23.40
26.40
23.00
No. of Helopeltis fresh punchersheaf
(Mean of 3 leaves 15 bush)
24Hrs
of
spray
0.00
0.00
0.00
0.00
5.2
24Hrs
of
Spray
19.20
16.60
15.40
23.20
25.40
48 hrs
of
spray
0.00
0.00
0.00
0.00
14.2
48 Hrs
of
spray
1740
3.20
2.80
17.60
25.40
7DAS
0.40
0.00
0.00
8.20
17.6
7DAS*
14.20
1.40
1.20
15.40
27.32
IODAS
1.20
0.00
0.00
14.60
21.20
Yo
Mortaility
over pre
34.16
93.72
94.87
41.66
(+) 18.78
I SDAS
15.40
1.20
0.80
19.20
34.40
%
Mortaility
over pre
28.90
94.62
96.58
27.27
(+) 49.56
Result
Emamectin benzoate 3% + Thiamethoxam 12% WG @ 250 glha has given t* 5 J ~ W
mortality of 93.72% and 94.62 % which is at par with Emamectin benzoate 3% ? + Thiamethoxam 12% WG @ 312.5 glha shown the mortality of 94.87% and : ,,..J.
96.58 % at 7 and 15 days of spray respectively and at the same time both the
treatment given good control of tea mosquito bug upto 10 days of spray due to
better synergy.
Emamectin benzoate 3% + Thiamethoxam 12% WG @ 250 g and 312.5 gha
has found superior for controlling both Tea looper and Tea mosquito bug as
compared to standard check Profenofos @ 800 mlha
Emamectin benzoate 3% + Thiamethoxam 12% WG due to better synergy is
found excellent combination and given phyto-tonic effect on tea.
Although the present invention has been disclosed in terms of a preferred
embodiment, it will be understood that numerous additional modifications and
variations could be made thereto without departing from the scope of the
invention as defined by the following claims:

We Claim:
1.Aninsecticidal composition , comprising;
- emamectin benzoate , wherein said emamectin benzoate amount ranges from 0.5 to 3% by weight of said composition;
- thiamethoxam, wherein said thiamethoxam amount ranges from 10-
15% by weight of said composition.
- awetting and dispersing agent (5-20%);
- aninert binder carbohydrate(30-70%);
- anextrusion softner(1-5%);
- anon-ionic wetting agent (2-5%);
- an anticaking agent;
- anagglomeration suppressant(1-5 %); and
- a stabilizer 1-5%.
to obtain a synergistic composition in a wettable granular form.
2. An insecticidal composition as claimed in Claim 1, wherein said
wetting agent is 4% by mass of anionic surfactant and said dispersing
agent in is 8% by mass of anionic sulphate surfactant.
3. An insecticidal composition as claimed in Claim 1, wherein said
stabilizer is 1 % by mass of butylated hydroxyl toluene.
4.An insecticidal composition as claimed in Claim 1, wherein said inert
binder is a disaccharide.
6. An insecticidal composition as claimed in Claim 1 , wherein said anti
caking agent 5% by mass of diatomaceous earth.
7.An insecticidal composition as claimed in Claim 1 and 2 , wherein said
wetting agent is selected from a group comprising sulfosuccinates,
sulphated esters , phosphate esters , sulfated alcohol and alkyl benzene
sulfonates.
8. An insecticidal composition as claimed in Claim 1 and 2 ,wherein said
dispersing agent is selected from group comprising polycarboxylates,
alkyl naphthalenesalfonate condensates, phenol sulphonic acid
condensates , lignosulfonates, methyl oleyltaurates and poly vinyl
alcohols. 1 5 JAN
9. A process for preparing wettable granule insecticidal compositionas.
claimed in any of the above preceding claims, comprising steps of: ORIE
- mixing emamectin benzoate , thiamethoxam , wetting agent, dispersing
agent, diatomaceous earth, sodium benzoate, butylated hydroxyl toluene,
sodium citrate and anhydrous lactose parts by weight in a blender to form
a mixed mass
- adding said mass on a dough mixer and spraying a solvent on said mass
to produce a liquid form of said mass.
- extruding said liquid form with the help of a low pressure extruder
- drying the extruded granules using a bed dryer.
10.A process for preparing wettable granule composition, as claimed in
Claim 9, wherein said solvent is composed of a non-ionic emulsifier,
aliphatic alcohol and water.
11. A process for preparing wettable granule composition , as claimed in
Claim 9, wherein the components are air milled to average particle size of
less than 15 microns.
12. An insecticidal composition as claimed in any of the proceeding
claims substantially as herein described with reference to foregoing
examples.
13. A process for preparing wettable granule insecticidal composition as
claimed in any of the proceeding claims substantially as herein described
with reference to foregoing examples.