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Field of the invention:
The present invention relates to a process for preparing stable formulations of low melting
agrochemicals. More particularly, the present invention relates to a granular formulation of low
melting agrochemicals.
Background and Prior Art:
Agrochemicals are used on a daily basis by farmers and farm workers. Handling and inhaling
such chemicals can be injurious to health. For this reason, agrochemical formulators have
developed various types of formulations which make handling of agrochemicals safer.
The use of agrochemical combinations is a widespread and documented practice in the
agricultural community. These agrochemical combinations offer significant advantages over
individual applications including improved and extended control, reduced application rates and
costs, shorter contact times for improved results, less stringent use restrictions, improved
selectivity, improved spectrum for fungi, insects, weeds etc. which are controlled, and reduced
residue problems. However, identifying appropriate agrochemical application rates and ratio of
the combinations is essential to achieve efficacious control. The selection of a particular
formulation type is more cumbersome for an agrochemical combination as the stability and
compatibility characteristics of both the agrochemicals need to be considered in selecting a
formulation type.
Generally, the low melting agrochemicals are usually presented as liquid formulations. However,
the prevalent agronomic practices lean more favorably towards use of a solid granular
formulation over a liquid formulation for various reasons.
The granular formulations offer significant advantages over the liquid formulations such as ease
of handling, ease of use, reduced worker exposure, reduced toxicity, reduced spillage and
waste disposal, less field drift and therefore offer a convenient form for the delivery of the
agrochemicals. These granules flow freely and cleanly from their containers and significantly
reduce the dust hazards. In order to be effective, these granules are required to maintain their
physical integrity until they are delivered to the carrier liquid, where they must disintegrate
rapidly to fine particles that can remain suspended in the liquid phase.
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Dispersants serve as suspending agents in wettable powders and perform the additional roles
of binders. These dispersants increase the physical strength of the granules by improving the
flow characteristics of the paste to reduce fissures and cracks, and by bridging between the
particles to bind them together. Dispersants are known to be generally soluble in water and are
counted as positive factors for rapid disintegration of the granules in water. However, the
selection of the best dispersing agent for a particular pesticide or combinations thereof is critical
and not certainly predictable.
An approach known to increase the attrition resistance of the granular formulation is by
increasing the amount of the dispersing agent present in the formulation, as one of the primary
roles of a dispersing agent in a wettable granular formulation is binding. However, increasing
the amount of a dispersing agent is not always feasible because a formulation having a greater
amount of a dispersing agent invariably requires a greater amount of time for dissolving. Thus,
there is always a need to strike a balance between the need for attrition resistance and rapid
dispersibility. There is always a need in the art for a wettable granular formulation of
agrochemicals wherein the formulation displays superior attrition resistance, disperses rapidly in
water and has good suspensibility in water once it is dispersed.
Another challenge to a formulator in preparing a granular formulation is the degree of chemical
inertness of the granule towards the agrochemical. Moreover, it is not always reasonably
predictable to select a carrier material that is simultaneously inert to two different agrochemicals
present in the preferred combination. It has been observed that even if the carrier surface is
mildly reactive to one of the agrochemical ingredients of the combination, it results into a
breakdown of the other pesticide thereby reducing the efficacy of the formulation. Thus, the
choice of an appropriate carrier for a granular formulation is often an undesired compromise
based on an informed consideration of these characteristics of the known carrier materials.
There are three main processes known in the art for the preparation of a wettable granular
formulation viz. spray drying, extrusion and fluid bed granulation. The formulations obtained by
spray drying are free flowing, possess good dispersibility and exhibit no tendency to dusting.
The spray drying process generally involves preparation of a slurry, spray drying of the prepared
slurry and drying of the resulted granules. The slurry is often prepared by mixing the
agrochemical ingredients with water, wetting and dispersing agents and other components
including a dispersant, anti-foam, and stabilizers. This mixture is then homogenized by strong
mechanical stirring or high shear mixer. The dispersion is then adjusted with water and milled in
4
wet mill equipment in order to obtain a slurry. At this stage, the dynamic rheology of the slurry
shows a pseudo-plastic behavior.
The slurry is thereafter sprayed through a bi-fluid nozzle or a pressure nozzle or an atomiser in
large/small droplets. The process parameters during the spray drying process such as the inlet
temperature, slurry flow rate, inlet air flow rate, type of nozzle etc. are critical and must be
carefully selected to get the right residence time of the individual particles within the spray dryer.
The dried spray granules are perfectly spherical. The granules are thereafter subjected to a
discontinuous or continuous drying to get desired residual moisture (between 0.5% to 2%).
Problems in formulating low melting agrochemicals are known in the art, particularly, problems
with preparing solid granular formulations of low melting agrochemicals. Most low melting
agrochemicals are usually formulated as liquid formulations as they are difficult to stabilize and
convert into solid formulations such as granules or dry flowable formulations. When formulated
into such solid formulations they form suspensions with low suspensibility, stability and
wettability, specifically in a dry flowable formulation. The most common method of formulating
low melting agrochemicals is to absorb the agrochemical onto an inert material.
US20090197765 (Gaytan et. al) discusses a solid formulation for low melting agrochemicals
however; the application discloses the use of additional free flowing agents such as silicates.
Such formulations, do not demonstrate higher levels of stability, or dispersibility or other
performance characteristics. Moreover, the application discloses the use of such formulations
for the herbicide fluroxypyr and its salts.
Another method known in the art is to mix surfactants with the agrochemical components, which
in turn increase the dispersion properties of the agrochemicals. US5688743 (Essinger, Jr.)
discusses a dry flowable composition for low melting solids and the use of nucleating agents
such as surfactants which are admixed with the agrochemical and carriers so as to stabilize the
agrochemical. However, such formulations do not demonstrate good dispersibility or
suspensibility.
US5846903 (Lloyd) discloses a water dispersible granular formulation for low melting solids,
which mixes surfactants with the agrochemicals and inert carriers. However, the drawback in
such a formulation is that when the surfactant is blended into the mixture of agrochemical and
carrier, the granules formed do not demonstrate good dispersibility or suspensibility.
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The present invention aims to overcome the problems in the prior art, namely, formulating a dry
flowable formulation for low melting agrochemicals, which can demonstrate excellent
dispersibility, suspensibility and physical stability.
Surprisingly, it has been found that at least partially surface-coating granules of a low melting
agrochemical with certain esters increases the physical stability of the agrochemical as well as
demonstrates excellent dispersibility and suspensibility profile.
Summary of the invention:
Therefore, in one aspect, the present invention provides a granular formulation comprising
particles of at least one low melting agrochemical wherein said particles of low melting
agrochemical are at least partially surface coated with an ester of a compound selected from the
group comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of
fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof.
In another aspect, the present invention provides a granular formulation comprising particles of
at least one low melting agrochemical admixed with particles of at least one co-agrochemical
wherein said particles of low melting agrochemicals and optionally particles of at least one other
agrochemical are at least partially surface coated with an ester of a compound selected from the
group comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of
fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof.
In another aspect, the present invention provides a process for the preparation of a granular
formulation comprising a low melting agrochemical, said process comprising:
(a) melting an agrochemically effective amount of a low melting agrochemical and sorbing
the molten agrochemical on an absorbent to obtain particles of said low melting
agrochemical; and
(b) at least partially surface coating said particles of low melting agrochemical with an ester
of a compound selected from the group comprising (a) an alkyl or aryl alkoxylate, (b)
alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block co-polymers of
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alkyls, or ethylene oxides or propylene oxides, (e) polyaryl substituted aliphatic or
aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative
and/or mixtures thereof.
In another embodiment, the present invention provides a process for the preparation of a
granular formulation comprising a low melting agrochemical and at least a co-agrochemical,
said process comprising:
(a) melting an agrochemically effective amount of a low melting agrochemical and sorbing
molten low melting agrochemical on an absorbent to obtain particles of said low
melting agrochemical;
(b) mixing an agrochemically effective amount of at least a co-agrochemical with at least an
adjuvant to obtain particles of said co-agrochemical;
(c) optionally homogenously mixing said particles of low melting agrochemical and at least a
co-agrochemical; and
(d) at least partially surface coating said particles of low melting agrochemical and the
particles of co-agrochemical with an ester of a compound selected from the group
comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c)
alkoxylates of fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or
propylene oxides, (e) polyaryl substituted aliphatic or aromatic alkoxylate, (f)
alkoxylated polyaryl substituted phenol and their derivative and/or mixtures thereof.
In another aspect, the present invention provides a kit-of-parts for herbicidal treatment of plants,
its habitat, a crop field, the soil or any material thereabout, said kit-of-parts comprising:
(a) a first herbicidal component, said first herbicidal component comprising particles of at
least one low melting agrochemical, said particles being at least partially surface coated
with an ester of a compound selected from the group comprising (a) an alkyl or aryl
alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block copolymers
of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl substituted
aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof;
(b) a second herbicidal component, said second herbicidal component comprising of at least
a co-agrochemical, said particles being at least partially surface coated with an ester of a
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compound selected from the group comprising (a) an alkyl or aryl alkoxylate, (b)
alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block co-polymers of alkyls,
or ethylene oxides or propylene oxides, (e) polyaryl substituted aliphatic or aromatic
alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative and/or mixtures
thereof; and
(c) an instruction manual comprising instructions for mixing the first and second herbicidal
components in a predetermined ratio and treating the plants, its habitat, a crop field, the
soil or any material thereabout with said admixture.
Objects of the invention:
It is an object of the present invention to provide a granular formulation of low melting
agrochemicals.
It is another object of the present invention to provide a granular formulation that demonstrates
excellent dispersibility and suspensibility.
It is another object of the present invention to provide a process for preparing a granular
formulation comprising a low melting agrochemical.
It is yet another object of the present invention to provide an adjuvant system and process for
surface coating low melting agrochemicals.
It is an object of the present invention to provide a granular formulation of low melting
agrochemicals and at least a co-agrochemical.
It is another object of the present invention to provide a granular formulation of at least two
agrochemicals that demonstrates excellent dispersibility and suspensibility.
It is another object of the present invention to provide a process for preparing a granular
formulation comprising a low melting agrochemical and at least a co-agrochemical.
It is yet another object of the present invention to provide an adjuvant system and process for
surface coating of a mixture of low melting agrochemical and at least a co-agrochemical.
Detailed Description of the invention:
The present invention describes a dry flowable formulation for low melting agrochemicals and a
process for preparing the same. The invention also describes an adjuvant system and process
8
for surface-coating the granules with the adjuvant. The invention may also include another
agrochemical(s). The other agrochemical may be a high melting agrochemicals stated as coagrochemicals.
Accordingly, in one aspect, the present invention provides a granular formulation comprising
particles of at least one low melting agrochemical wherein said particles of low melting
agrochemical are at least partially surface coated with an ester of a compound selected from the
group comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of
fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof.
In another aspect, the present invention provides a process for the preparation of particles of a
low melting agrochemical. The process comprises:
(a) melting an agrochemically effective amount of a low melting agrochemical
and sorbing the molten agrochemical on an absorbent to obtain particles
of said low melting agrochemical; and
(b) at least partially surface coating said particles of low melting
agrochemical with an ester of a compound selected from the group
comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol,
(c) alkoxylates of fatty acids, (d) block co-polymers of alkyls, or ethylene
oxides or propylene oxides, (e) polyaryl substituted aliphatic or aromatic
alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative
and/or mixtures thereof.
The process thus involves melting an agrochemically effective amount of a low melting
agrochemical and absorbing the melted agrochemical onto an absorbent so as to obtain
particles of such a low melting agrochemical. Such particles may then be partially surface
coated with an adjuvant system.
A low melting agrochemical is known in the art, and may be defined as a compound that has a
melting point in the range of less than 1000 C. Conversely, high melting agrochemicals may be
defined as a compound that has a melting a point higher than 1000C.
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The adjuvant system according to the instant invention that is used to at least partially surface
coat the particles of agrochemicals comprises a phosphate ester of the compounds from the
group comprising:
(i) alkyl or aryl alkoxylate;
(ii) alkoxylates of fatty alcohol;
(iii) alkoxylate of fatty acids;
(iv) block co-polymers of ethylene oxide and propylene oxide;
(v) polyaryl substituted aliphatic or aromatic alkoxylate; and
(vi) alkoxylated polyaryl substituted phenol; and derivatives and mixtures thereof.
In an embodiment, the ester is selected such that it has a degree of esterification from about 5
to about 95% and a pH in range of about 1 to 6.9.
As used herein, the term "aryl" shall include, for example, phenyl, tolyl, naphthyl,
tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof.
The “alkoxylate” is preferably an ethoxylate though other alkoxylates are not excluded.
In yet another embodiment, suitable phosphated poly alkyl or aryl ethoxylate are styryl
containing ethoxylated and phosphorylated phenols. More preferred are phenols having three
styrene radicals and from about 16 to about 20 moles of ethylene oxide.
Without wishing to be bound by theory, the present inventors have surprisingly found that an
alkoxylated surfactant selected from alkyl or aryl alkoxylate; alkoxylates of fatty alcohol;
alkoxylate of fatty acids; block co-polymers of ethylene oxide and propylene oxide; polyaryl
substituted aliphatic or aromatic alkoxylate; and alkoxylated polyaryl substituted phenol; and
derivatives and mixtures thereof play an important role in the granular formulations comprising a
low melting herbicide preferably but not limited to an oxyphenoxy acid ester herbicide optionally
together with another agrochemical or co-agrochemical, preferably but not limited to a triazinone
herbicide. It has been found that these classes of surfactants surprisingly enhance the physical
performance such as dispersibility and suspensibility of the granular formulations envisaged
herein. Still more surprisingly, it was found that when these classes of surfactants were mixed
along with the remaining excipients and granulated to form particles comprising these
surfactants within the particles and not as a surface-coating, the improved performance was
absent.
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It has now surprisingly been found that at least partially surface coating of said low melting
agrochemical with an ester of a compound selected from the group comprising (a) an alkyl or
aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block copolymers
of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl substituted aliphatic or
aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative and/or
mixtures thereof with optionally at least one of the co-agrochemical exhibits a good dispersibility
and suspensibility which is capable of providing the low melting agrochemical with or without
high melting agrochemical along with quantitatively variable combination of adjuvants, in the
form of solid formulations, preferably granules, for controlling the majority of weeds occurring
preferably in useful plant cultivations, both in pre-emergence and in post-emergence, without
significantly damaging the useful plants.
It is highly surprising that the combination of a modified styrene acrylic polymer with at least one
of the following-mentioned surfactants selected from dialkyl naphthalene sulfonate
formaldehyde condensate, dialkyl naphthalene sulfonate sodium salt, ethoxylated tristryl phenol,
alkoxylate of fatty acids, sulphated poly aryl phenol ethoxylate, sodium sulphosuccinic acid diisooctyl
ester, sodium lauryl sulfate, polycarboxylate, sodium salt of naphthalene sulfonate
condensate and others surfactants surpasses the additional effect to be expected in principle on
the suspensibility for pests to be controlled, and thus extends the limits of activity of both active
ingredients in particular in two different respects.
It was thus found that the performance of the granular formulations according to the instant
invention was surprisingly enhanced when these surfactants were sprayed on the particles of
low melting agrochemicals immediately prior to wet mixing for preparing a
processable/granulable material. The enhanced performance characteristics were not found
when these surfactants were added to the low melting agrochemical prior to the granulation. It is
believed by the present inventors that spraying these surfactants on the particles of low melting
agrochemicals immediately prior to the wet mixing results into at least a partial surface coating
of the particles of low melting agrochemical and not within the particles. Without wishing to be
bound by theory, it is believed that the ionically charged moieties of these classes of
adjuvants/surfactants, when present within the particles, in close proximity to the low melting
agrochemical and/or the co-agrochemical, chemically interacts to the ionically charged moieties
of the agrochemicals and remains bound to the agrochemical molecules thereby failing to
exhibit the performance enhancement otherwise seen due to the surface coating. It is believed
that on surface coating of a low melting agrochemical, a portion of the surfactant releases and
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assists in dispersing the particles while a portion of the surfactant remains surface coated and
stabilizes the low melting agrochemical. These classes of surfactants were indeed surprisingly
selective in performing the dual role of dispersant as well as a stabilizer when present as at
least a partial coating on the surface of the particles comprising a low melting agrochemical.
In another embodiment, the granular formulation of the present invention comprises a coagrochemical,
which may be a high melting agrochemical. Thus, in this embodiment, the
present invention provides a granular formulation comprising particles of at least one low
melting agrochemical admixed with particles of at least one co-agrochemical wherein said
particles of low melting agrochemicals and optionally particles of at least one other
agrochemical are at least partially surface coated with an ester of a compound selected from the
group comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of
fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof.
The low melting agrochemicals in an embodiment of the invention includes herbicides,
insecticides and fungicides. Preferred classes include, amides, amidines, anilides,
anilinopyrimidine, aryloxycarboxylic acids, aryloxyplenoxypropionates, benzilates, benzofurans,
benzofuranylalkylsulfonates, benzothiazoles, benzoxazoles, benzoylpyrazoles, bipyridyliums,
carbamates, carboxamides, chloroacetamides, chloroacetanilides, chlorotriazines, cyclodienes,
cyclohexanediones, cyclohexane oximes, cyclopropylisoxazoles, dicarboximides, dinitroalilines,
dinitrophenols, diphenyl ethers, dithiocarbamates, glycines, halogenated aliphatics, imidazoles,
imidazolinones, isoazolidinones, neonicotinoids, nitroanilines, nitrophenylethers, Nphenylphthalimides,
organoarsenicals, organichlorine, organophosphates, organophosphorus,
oxadiazines, oxadiazolinones, oxazoles, oxyacetamides, phenoxyalkanoic acids, phenyl
carbamates, phenoxyacetics, phenoxybutyrics, phenoxycarboxylic acids, phenoxypropionics,
phenylamides, phenylpyrazoles, phenylpyridazines, phenylureas, phosphinic acids,
phosphorodithioates, phthalic acids, pyrazoles, pyrethroids, pyridazines, pyridazinones,
pyrimidines, pyridine carboxylic acids, pyrimidinamines, pyrimidinyloxybenzoic acids,
pyrimidinylthiobenzoic acids, quaternary ammoniums, quinazolinones, quinoline carboxylic
acids, strobilurins, sulfonamides, sulfonanilides, sulfonylaminocarbonyltriazolinones,
sulfonylureas, tetranoic acid, thiaphanate, tetrazolinones, thiadiazoles, thiadiazolylureas,
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thiocarbamates, thiocarbonates, thioureas, triazines, triazoles, triazolinone, triazolones,
triazinones, triazolopyrimidines, triketones, uracils, and ureas.
In another embodiment, the low melting agrochemical is selected from examples of
agrochemicals which may be used in the process of the present invention will occur to those
skilled in the art and include for example Alachlor, Alanycarb, Ametryn, Amitraz, Anilofos,
Azamethiphos, Azinophos-ethyl, Azinophos-methyl, Beflubutamid, Benalaxyl, Benfluralin,
Bensulide, Bensultap, Bifenox, Bifenthrin, Butralin, Butroxydim, Carboxin, Chlorpropham,
Chlorpyrifos, Chlorpyrifos-methyl, Clodinafop-propargyl, Clofop-isobutyl, Cloquintocet-mexyl,
Cyfluthrin, Beta-Cyfluthrin, Cyhalofop-butyl, Cypermethrin, Alpha-Cypermethrin, Beta-
Cypermethrin, Cyprodinil, Diclofop-methyl, Dicofol, Difenoconazole, Diphenylamine, Dithiopyr,
Ethofumesate, Etofenprox, Fenamiphos, Fenclorim, Fenfuram, Fenobucarb, Fenoxaprop,
Fenoxaprop-ethyl, Fenoxaprop-P-ethyl, Fenoxycarb, Fenpropathrin, Fenrtazamide, Fenvalerate,
Fluazinam, Fluazolate, Fluazifop-butyl, Fluchloralin, Flurenol, Fluroxypyr (-mepthyl),
Flurprimidol, Haloxyfop-methyl, Heptachlor, Imazalil, Indoxacarb, Isoprocarb, Lactofen, Lambdacyhalothrin,
Linuron, MCPA-thioethyl, Mefenpyr-diethyl, Metazachlor, Methidathion,
Methoxychlor, Monolinuron, Napropamide, Oxadiazon, Oxyfluorphen, Parathion-methyl,
Pendimethalin, Permethrin, 2-Phenylphenol, Phosalone, Phosmet, Propachlor, Propanil,
Propham, Pyrazophos, Quizalofop-P, Quizalopfop-methyl, Resmethrin, Pinosat, Temephos,
Triadimefon, Tri-allate, Triazamate, Trifloxystrobin, Trifluralin.
In an embodiment, the low melting agrochemical is preferably selected from the class of
oxyphenoxy acid ester herbicides selected from clodinafop-propargyl, fluazifop-butyl,
fenoxaprop-ethyl, diclofop-methyl, quizalofop-methyl, haloxyfop-methyl and clofop-isobutyl. In
yet another embodiment, the low melting agrochemical is clodinafop-propargyl.
In this embodiment, the preferred low melting compound is clodinafop-propargyl, which has the
following structure:
In one embodiment, the low melting agrochemical is clodinafop or its propargyl ester.
Additionally, a safener may be used in combination with the low melting agrochemical. Such a
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safener may be selected from a list comprising of dymron, fenclorim, cumyluron, isoxadifenethyl,
mefenpyr-diethyl, cloquintocet-mexyl, cyprosulfamide, dietholate, disulfoton, 1,8-
naphthalic anhydride, fluxofenim, dichlormid, benoxacor, and flurazole .
In yet another embodiment, the safener is cloquintocet-mexyl.
In one embodiment the absorbing material may be precipitated silica or other silica based
absorbing material, kaolin, soapstone, talc, starch, or a mixture thereof.
A co-agrochemical may be added to the formulation, such a co-agrochemical may have a high
melting point. In an embodiment, the co-agrochemical may be selected from the list comprising
of agrochemicals which may be used in the process of the present invention will occur to those
skilled in the art and include for example Ametridione, Amibuzin, Ancymidol, Azaconazale,
Azoxystrobin, Bendiocarb, Benoxacor, Bifenazate, Buprofezin, Butafenacil, Cafenstrole,
Carbetamid, Chlordane, Chlorfenapyr, Chlozolinate, Cinidon-ethyl, Cyproconazole, 2,4-DB,
DDT, Deltamethrin, Desmedipham, Dichlofluanid, Dichlorprop, Dichlorprop-P, Diethofencarb,
Ethiozin, Ergocalciferol, Ethychlozate, Etoxazole, Fenarimol, Fenbuconazole, Fenchlorazoleethyl,
Fenclorim, Fenfuram, Fenpyroximate, Fentin, Fluazinam, Flumetralin, Fluthiacet-methyl,
Flutolanil, Haloxyfop, Gamma HCH, Hexaconazole, Hexazinone, Hexythiazox,
Imazamethabenz-methyl, Isoproturon, Isouron, Isomethiozin, Iprodione, Kinoprene, MCPA,
Metamitron, Metribuzin, Metconazole, Methabenzthiazuron, Methiocarb, Metobenzuron,
Neburon, Oxpoconazolefumerate, Pentoxazone, Picolinafen, Pindone, Polynactins, Prodiamine,
Prometryn, Pyrazolynate, Pyrazoxyfen, Herbicide, Pyridaben, Pyriminobac-methyl, Quinoxyfen,
Quizalofop, Sulfentrazone, Sulfur, Tebuconazole, Terbumeton, Terbutryn, Tralkoxydim,
Trietazine, Trimethacarb, Vinclozolin In one embodiment, the co- agrochemical may be selected
from the class of triazinone herbicides comprising ametridione, amibuzin, ethiozin, hexazinone,
isoproturon, isomethiozin, metamitron and metribuzin.
In another embodiment, co-agrochemical is metribuzin, having the following structure:
The present invention also provides a process for the preparation of particles of a low melting
agrochemical. The process comprises:
14
(a) melting an agrochemically effective amount of a low melting agrochemical and sorbing
the molten agrochemical on an absorbent to obtain particles of said low melting
agrochemical; and
(b) at least partially surface coating said particles of low melting agrochemical with an ester
of a compound selected from the group comprising (a) an alkyl or aryl alkoxylate, (b)
alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block co-polymers of
alkyls, or ethylene oxides or propylene oxides, (e) polyaryl substituted aliphatic or
aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative
and/or mixtures thereof.
In an embodiment, the coated particles of low melting agrochemical are mixed with
granulating/extruding aid to form an extrudable dough, which is thereafter extruded to form the
partially surface coated granular particles of the present invention.
In another embodiment, the particles of low melting agrochemical may be co-formulated with the
particles of at least a co-agrochemical. Thus, in this embodiment, the present invention provides
a process for the preparation of a granular formulation comprising a low melting agrochemical
and at leasta co-agrochemical , said process comprising:
(a) melting an agrochemically effective amount of a low melting agrochemical and sorbing
molten agrochemical on an absorbent to obtain particles of said low melting
agrochemical;
(b) mixing an agrochemically effective amount of at least a co-agrochemical with at least an
adjuvant to obtain particles of said co-agrochemical;
(c) optionally homogenously mixing said particles of low melting agrochemical and at least a
co- agrochemical; and
(d) at least partially surface coating said particles of low melting agrochemical and the
particles of the co-agrochemical with an ester of a compound selected from the
group comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c)
alkoxylates of fatty acids, (d) block co-polymers of alkyls, or ethylene oxides or
propylene oxides, (e) polyaryl substituted aliphatic or aromatic alkoxylate, (f)
alkoxylated polyaryl substituted phenol and their derivative and/or mixtures thereof.
15
In this aspect of the invention, the process may be used to formulate a low melting
agrochemical along with a co-agrochemical which may be a high melting agrochemical. The
process may be carried out by milling the high melting agrochemical to a desired size, mixing
the high melting agrochemical with excipients, melting the low melting agrochemical and
absorbing the said low melting agrochemical onto a suitable absorbing material, blending the
low melting and high melting co-agrochemicals, treating the blend with an adjuvant system,
mixing the adjuvant treated blend with a granulating/extruding aid and granulating/extruding or
drying the same.
Thus, in one embodiment, the high melting co-agrochemical may be ground to a desired particle
size using any one of the conventionally known milling equipment including air jet milling (AJM),
air classifying mill (ACM), Turbo mill, Ultra fine mill (UFM), Hammer mill, Pin mill, Raymond mill,
etc.
In an embodiment, the milled, the high melting co-agrochemical may be mixed with at least one
excipient selected from dispersing agents, wetting agents, defoamers inert fillers, absorbers etc.
In an embodiment the dispersing agent may be selected from anionic surfactants such as
modified styrene acrylic polymers.
In one embodiment, the formulation may contain ionic and nonionic dispersing agents to enable
disintegration of granules in water with ease, such as modified styrene acrylic polymers,
potassium polycarboxylates, salts of polystyrenesulphonic acids, salts of polyvinylsulphonic
acids, salts of naphthalenesulphonic acid/formaldehyde condensates, salts of condensates of
naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic
acid, polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of
linear alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide,
polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone
and copolymers of (meth)acrylic acid and (meth)acrylic esters, alkyl ethoxylates and
alkylarylethoxylates. In one embodiment, the dispersing agents include sodium naphthalene
sulfonate-formaldehyde condensate, or a combination thereof. In another embodiment, the
dispersing agent may include acrylic polymers or polycarboxylate potassium or a combination
thereof.
In an embodiment the wetting agents may be selected from dialkyl naphthalene sulphonate
sodium salt, sodium naphthalene sulfonate – formaldehyde condensate.
16
In another embodiment, the formulations of the present invention comprise at least one wetting
agent selected from soaps; salts of aliphatic monoesters of sulphuric acid including but not
limited to sodium lauryl sulphate, sulfoalkylamides and salts thereof including but not limited to
N-methyl-N-oleoyltaurate Na salt; alkylarylsulfonates including but not limited to
alkylbenzenesulfonates; alkylnaphthalenesulfonates and salts thereof and salts of ligninsulfonic
acid.
In another embodiment, the wetting agent includes a blend comprising an alkali metal salt of
alkylnaphthalenesulfonate or an alkali metal salt of dioctylsulphosuccinate or a combination
thereof.
In an embodiment, the formulations of the present invention comprise at least one further
surfactant selected from salts of polystyrenesulphonic acids; salts of polyvinylsulphonic acids;
salts of naphthalenesulphonic acid/formaldehyde condensates; salts of condensates of
naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde; salts of lignosulphonic
acid; polyethylene oxide/polypropylene oxide block copolymers; polyethylene glycol ethers of
linear alcohols; reaction products of fatty acids with ethylene oxide and/or propylene oxide;
polyvinyl alcohol; polyvinylpyrrolidone; copolymers of polyvinyl alcohol and polyvinylpyrrolidone;
copolymers of (meth)acrylic acid and (meth)acrylic esters; and alkyl ethoxylates and
alkylarylethoxylates.
In an embodiment the defoamers may be selected from silicone based defoamers.
In an embodiment, the formulations of the present invention may comprise at least one
antifoaming agent which is usually employed for this purpose in agrochemical compositions.
In an embodiment, the preferred antifoaming agents are selected from silicone oil and
magnesium stearate or a suitable combination thereof.
In an embodiment inert carrier may be selected form kaolin, titanium dioxide, bentonite,
soapstone, talc, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth,
sand, clay, dolomite, calcite, magnesium oxides, magnesium carbonates, sucrose, corn starch,
citric acid and its salts, and mixtures thereof.
In an embodiment absorbers may be selected form silicates, precipitated silica, alumina,
cellulose, activated carbon, graphite, silica gel, zeolites, bentonite, soapstone, talc etc, and
mixture thereof.
17
In an embodiment, the low melting agrochemical and optionally a safener may be melted and
absorbed onto a suitable absorbing material. The low melting agrochemical and safener may be
absorbed onto an absorbent material by pouring, spraying or by using any suitable method and
then allowed to rest for at least one hour after spraying. This is to allow proper absorption and
even distribution of the agrochemical within the absorbing particles.
The process of absorbing may be carried out in a plough shear mixer, mixer grinder, kitchen
mixer or any other conventional mixing equipment. In an embodiment the melted low melting
agrochemical may be sprayed onto the absorbent material.
In an embodiment the co-agrochemical in an effective amount is mixed with at least an adjuvant
to obtain particles of high melting agrochemical.
In an embodiment, homogenously mixing said particles of low melting agrochemical and at least
a co-agrochemical of high melting group to have a blended mixture.
In an embodiment the blended mixture of the low and high melting agrochemicals may be at
least partially coated with an adjuvant system.
In an embodiment the adjuvant system may be sprayed onto to the blended mixture in a
suitable mixer like plough shear mixer, kitchen mixer, mixer grinder or so. The inventors of the
present invention have found that adjuvant system when mixed with a low melting agrochemical
and then granulated, gave very poor inversion and suspensibility profiles (as demonstrated in
the examples below.) The inventors used various emulsifiers such as sodium lauryl sulphate,
sodium ligosulphonates, and anionic surfactants that were mixed with the agrochemicals,
specifically low melting agrochemicals which were present in concentrations of up to 25%. It has
surprisingly been found that, when treated with an adjuvant system post mixing with
dispersants, as well as other co-formulants, the granules demonstrated an excellent inversion
and suspensibility profile.
In an embodiment, the coated blended powder may then be wet mixed with
granulating/extruding aid and the subjected to known methods of granulation.
In an embodiment the solvents used in the process may include aqueous solvents or non
aqueous solvents as granulating/extruding aid.
In an embodiment, the granules may be formed using any of the methods known in the art, such
as pan granulation, high speed mixing agglomeration, extrusion granulation, fluid bed
18
granulation, fluid bed spray granulation, spray drying. The preferred method is extrusion
granulation. The extrusion granulation can be performed by using axial extruder, basket
extruder, Fuji Paudal extruder, roller extruder, twin shaft extruder, low compact extruder, Eirich
granulator, Oscillating granulator or any other suitable extruder to obtain the required quality of
the granular product.
In an embodiment, the quantity of the agrochemicals, both the low melting and the high melting
co-agrochemicals may be in the range of 1 to 25 % for low melting agrochemicals, whereas the
high melting co-agrochemical may be in range of 5 to 50%. The term “agrochemically effective
amount” as used herein shall be understood to define the above preferred amounts of the
agrochemicals, although such amounts are not to be construed as limiting. It is within the reach
of a person skilled in the art to determine the agrochemically effective amounts of one or more
herbicide depending upon the crop, the infestation sought to be prevented, the environmental
conditions etc.
The dry flowable granules formulated through the process mentioned above demonstrate
excellent properties for both single agrochemicals such as low melting solids as well as
combinations, wherein, a second high melting agrochemical may be a co-formulated.
The process is particularly useful for formulating low melting agrochemical in concentrations
higher than 1 % by mass individually or in combination with the co-agrochemicals.
The process may be used to prepare dry flowables which are also known as water dispersible
granules, as well as wettable granules. These granules can also be used either by direct
broadcasting in the field (crop and or grass) or after dilution (with water or any other suitable
diluents) to control the pest. The amount of formulation added to water to prepare a spray
mixture may depend on the type of application. Usually a 0.1 to 10% by weight aqueous
dispersion is prepared.
The invention therefore relates to a composition for controlling weeds and grasses in crops of
cultivated plants, which composition contains a biologically effective amount of the novel
formulation in water.
The dry flowable or water degradable granules of the present invention may be packaged as a
kit of parts, wherein, the pre-formulated granules, which may be readily mixed with water, or in
an embodiment, the kit of parts may contain such components such as a vial, bottle, can,
pouch, bag or canister. In one embodiment, the kit of parts may contain pre-formulated granules
19
of a low melting active and a high melting active packed separately, which may then be mixed in
a vial or container or tank and sprayer before spraying. In one embodiment, the kit of parts may
contain pre-formulated low melting active or high melting active, which may be readily mixed
with water, and may include such components such as a vial, bottle, can, pouch, bag or
canister.
Thus, in this aspect, the present invention provides a kit-of-parts for herbicidal treatment of
plants, its habitat, a crop field, the soil or any material thereabout, said kit-of-parts comprising:
(a) a first herbicidal component, said first herbicidal component comprising particles of at
least one low melting agrochemical, said particles being at least partially surface coated
with an ester of a compound selected from the group comprising (a) an alkyl or aryl
alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block copolymers
of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl substituted
aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof;
(b) a second herbicidal component, said second herbicidal component comprising of at least
a co-agrochemical, said particles being at least partially surface coated with an ester of a
compound selected from the group comprising (a) an alkyl or aryl alkoxylate, (b)
alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block co-polymers of alkyls,
or ethylene oxides or propylene oxides, (e) polyaryl substituted aliphatic or aromatic
alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative and/or mixtures
thereof; and
(c) an instruction manual comprising instructions for mixing the first and second herbicidal
components in a predetermined ratio and treating the plants, its habitat, a crop field, the
soil or any material thereabout with said admixture.
The first and second herbicidal components may be prepared by separately surface coating the
particles of the low melting agrochemical and the particles of at least co-agrochemical with the
adjuvant system of the present invention using a process described hereinabove.
The kit-of-parts according to an embodiment of the invention comprises an instruction manual.
The instruction manual comprises instructions for an user of the kit to mix the first and second
herbicidal components in a predetermined ratio. The preferred ratio is not particularly limiting
and may be selected by skilled artisan according to the preferred dosage of the herbicides, the
intensity of the infestations etc. The instruction manual also comprises instructions to disperse
20
the admixture in a required quantity of water to prepare an aqueous suspension. The aqueous
suspension is thereafter instructed to be sprayed to the plants, its habitat, a crop field, the soil or
any material thereabout with said admixture.
The present examples demonstrate the excellent improvement in the suspensibility and
dispersion profile of the granules obtained after treatment with an adjuvant system just prior to
wet mixing or dough preparation, as well as decreased suspensibility and dispersion when
adjuvants were mixed with the agrochemicals and formed into a homogenous powder that was
then subjected to prepare wet extrudable dough for further subjection to granulation.
These and other advantages of the invention may become more apparent from the examples
set forth herein below. These examples are provided merely as illustrations of the invention and
are not intended to be construed as a limitation thereof.
Examples:
The present Example demonstrates the process for the preparation of particles of a low melting
agrochemical and finally converting them into granules having good dispersibility and
suspensibility. The compositions are as follows:
Example 1
Process A: -
Preparation of particles with low melting agrochemical and their respective granule:
a) Low melting agrochemical – Clodinafop propargyl
b) Safener – Cloquintocet mexyl
c) Dispersant– Dialkyl naphthalene sulfonate formaldehyde condensate or its sodium salt
d) Absorbent – Kaolin
Other ingredients:
Adjuvant system - sulphated polyarylphenolethoxylate.
Inert filler – Lactose, ammonium sulphate
The above composition was prepared by following the present process as follows:
Step a) Clodinafop-propargyl technical and cloquintocet-mexyl safener were melted in a melting
pot to obtain a homogenous mixture of these two.
21
Step b) Melted clodinafop propargyl and safener mixture was sprayed on to kaolin in a Ploughshear-
mixer (PSM). The sprayed mix was then allowed to mix with a top-up quantity of
precipitated silica to have a free flowing material free from lumps.
Step d) Homogenous mixture was then partially coated with adjuvant and/or stabilizer system
prior to wet mixing.
Step e) Wet dough was prepared by mixing water (having defoamer) with the product of step
(d), above, in required quantity to have the homogenous wet dough.
Step f) Dough from step (e), above, was then granulated using suitable granulator to obtain
granules.
Step g) The granules, obtained from step (f) above, were then dried so as to ensure that the
moisture content was below 5 %.
Ingredients Clodinafop Propargyl WP
1% WG 5% WG 10%
WG
15%
WG
20%
WG
25%
WG
% by mass
Clodinafop propargyl technical 1.16 5.79 11.05 16.00 21.58 26.32
Cloquintocet mexyl (safener) 0.26 1.32 2.64 4.05 5.40 6.58
Kaolin / Silica 7.00 28.00 48.50 60.63 54.55 45.90
Dialkyl naphthalene sulfonate
salts (Supragil WP)
1.50 5.00 8.50 9.00 10.50 10.50
Lactose 43.89 28.28 14.00 4.00 2.67 3.00
Ammonium sulphate 41.89 30.00 11.11 - - -
Dimethyl polysiloxane (SAG
1572)
0.20 0.21 0.20 0.32 0.30 0.20
Sulphated polyarylphenol
ethoxylate
4.10 2.30 4.00 6.00 5.00 7.50
Total 100.0 100.0 100.0 100.0 100.0 100.0
Process A
No. of inversions 25 16 10 15 20 24
Suspensibility (active) % by
mass
82.80 85.30 92.40 90.25 88.34 86.48
Suspensibility (active) after 14
d-AHS
80.37 84.65 92.00 92.51 85.94 88.22
Process B: To study the effect of adjuvant and/or stabilizer system when these adjuvant and/or
stabilizer system was added in step (b) of Process A and rest steps were same.
Ingredients Clodinafop Propargyl WP
1% WG 5% WG 10%
WG
15%
WG
20%
WG
25%
WG
% by mass
Clodinafop propargyl technical 1.16 5.79 11.05 16.00 21.58 26.32
Kaolin / precipitated silica/ 7.00 28.00 47.64 60.68 55.54 36.48
22
silica powder
Styrene acrylic polymer (Atlox
Metasperse 550S)
1.50 5.00 8.50 9.00 10.50 10.50
Lactose 43.89 27.78 14.00 4.00 2.67 3.00
Ammonium sulphate 41.89 30.00 11.11 - - -
Sulphated polyarylphenol
ethoxylate
4.30 2.51 4.20 6.32 5.30 6.70
Total 100.0 100.0 100.0 100.0 100.0 100.0
Process B
No. of inversions 35 22 21 25 35 39
Suspensibility (active) % by
mass
72.00 70.40 78.23 76.58 73.00 75.00
Suspensibility (active) after 14
d-AHS
54.00 45.00 59.00 64.00 61.08 60.00
Process C: To study the effect of adjuvant and/or stabilizer system when these adjuvant and/or
stabilizer system was added in step (a) of Process A and rest steps were same.
Ingredients Clodinafop Propargyl WP
1% WG 5% WG 10%
WG
15%
WG
20%
WG
25%
WG
% by mass
Clodinafop propargyl technical 1.16 5.79 11.05 16.00 21.58 26.32
Cloquintocet mexyl (safener) 0.26 1.32 2.64 4.05 5.40 6.58
Kaolin/ Silica 7.00 28.00 48.50 60.63 54.55 45.90
Polycarboxylate derivative
(Geropon SC-213)
1.50 5.00 8.50 9.00 10.50 10.50
Lactose 41.89 25.28 10.00 - - -
Ammonium sulphate 43.89 32.50 15.11 4.00 2.67 3.00
Sulphated polyarylphenol
ethoxylate
4.30 2.51 4.20 6.32 5.30 6.70
Total 100.0 100.0 100.0 100.0 100.0 100.0
Process B
No. of inversions 45 31 30 34 >50 >50
Suspensibility (active) % by
mass
53.15 56.00 49.00 44.00 38.57 40.27
Suspensibility (active) after 14
d-AHS
40.20 44.11 38.75 36.46 30.21 29.70
Example 2: Metribuzin 42% + Clodinafop-Propargyl (12%) (DF)
Preparation of particles with high melting agrochemical:
a) High melting agrochemical – Metribuzin (42%)
b) Dispersing agent – sodium naphthalene sulfonate-formaldehyde condensate (7%)
c) Wetting agent –sodium naphthalene sulfonate (4%)
23
d) Inert carrier – TiO2 (Q.S)
Preparation of particles with low melting agrochemical:
e) Low melting agrochemical – Clodinafop propargyl (12%)
f) Safener – Cloquintocet mexyl (3%)
g) Absorbent – Kaolin.
Other ingredients:
Adjuvant added - sulphated polyaryl phenolethoxylate.
The above composition was prepared by following the present process as follows:
Step a) Metribuzin technical was ground to desired size using an Air-jet-mill.
Step b) Metribuzin technical was mixed with dispersing agent comprising sodium naphthalene
sulfonate-formaldehyde condensate , Wetting agent comprising sodium naphthalene sulfonate
and TiO2 in a blender, this formed a premix of high melting co-agrochemical.
Step c) Clodinafop-propargyl technical and cloquintocet-mexyl safener were melted in a melting
pot to obtain a homogenous mixture of the two.
Step d) Melted clodinafop propargyl and safener mixture was sprayed on to precipitated silica
or kaolin in a Plough-shear-mixer (PSM). The spray dried mix obtained formed a premix of low
melting agrochemical.
Step e) The premix of both the high melting co-agrochemical and low melting agrochemical
obtained in steps c and d were blended together in mixer like a plough-shear-mixer (PSM) with
the additives to obtain a homogenous powder.
Step f) The homogenous powder obtained in step e was then treated with adjuvant system
comprising polyaryl phenolethoxylateusing a plough-shear-mixer (PSM) to obtain a
homogenous granulating mixture.
Step g)The homogenous granulating mixture of step f was mixed with water and a defomer,
such as silicone based deformers to form a homogenous wet dough.
Step h) The homogenous wet dough from step g, was then granulated using suitable granulator
to obtain granules.
Step i) Granules, obtained from step h were then dried such that the moisture content was
below 5 %.
Example 3: Metribuzin 42% + Clodinafop-Propargyl (12%) (DF)
Preparation of particles with high melting agrochemical:
24
a) High melting agrochemical – Metribuzin (42%)
b) Dispersing agent – Modified styrene acrylic polymer (9%)
Preparation of particles with low melting agrochemical:
a) Low melting agrochemical – Clodinafop propargyl (12%)
b) Safener – Cloquintocet mexyl (3%)
c) Absorbent – precipitated silica.
d) Wetting agent- sodium naphthalene sulfonate (4%)
Other ingredients:
Adjuvants such as alkyl EO-PO block surfactant.
The above composition was prepared by following the present process as follows:
Step a) Metribuzin technical was ground to desired size using an Air-jet-mill.
Step b) Ground Metribuzin technical was mixed with dispersing agent comprising modified
styrene acrylic polymer, which formed a premix of high melting co-agrochemicals.
Step c) Clodinafop-propargyl technical and cloquintocet-mexyl safener were melted in a melting
pot to obtain a homogenous mixture of the two.
Step d) Melted clodinafop propargyl and safener mixture was sprayed on to precipitated silica
mixed with wetting agent sodium naphthalene sulfonate in a plough-shear-mixer (PSM). The
spray dried mix obtained formed a premix of low melting agrochemical.
Step e) The premix of both the high melting co-agrochemical and low melting
agrochemical obtained in steps c and d were blended together in mixer like a plough-shearmixer
(PSM) with the additives to obtain a homogenous powder.
Step f) The homogenous powder was then treated with adjuvant comprising alkyl EO-PO block
surfactant and their derivatives using a plough-shear-mixer (PSM) to obtain a homogenous
granulating mixture.
Step g)The homogenous mixture obtained in step f, was then milled in a pin miller to obtain a
homogenous free flowing powder.
Step h) The homogenous free flowing powder obtained in step g, was then mixed with a diluent
such as water to obtain dough.
Step i) The dough obtained step h was then extruded and dried to obtain granules that have a
moisture content was below 5 %.
Example 4: Comparison of adjuvants.
25
Ingredients SET- A SET – B SET- C SET - D
06/275 10/281 27B/308 32B/317 10BP/305 10CP/305
Metribuzin technical 44.30 46.67 44.50 44.50 43.30 43.30
Precipitated Silica 10.00 - 5.00 16.40 - -
Modified styrene acrylic
polymer
6.00 7.33 7.00 7.00 10.00 10.00
Dialkyl naphthalene
sulfonate formaldehyde
condensate / sodium
salt
14.70
3.00 - - 4.00 4.00
Citric acid (CA) - - 5.00 4.00 5.00 5.00
Sodium bicarbonate
(SBC)
- - 5.00 6.00 5.00 5.00
Kaolin 2.79 26.34 9.24 - 11.07 14.07
Clodianfop propargyl 12.95 13.33 13.00 13.68 13.00 13.00
Cloquintocet mexyl 3.26 3.33 3.26 3.42 3.26 3.26
Ethoxylated
tristyrylphenol
6.00 - - - - -
Sulphated
polyarylphenolethoxylate
- - 5.00 4.00 - -
Sodium sulphosuccinic
acid di-isooctyl ester
- - - 1.00 - -
Extrusion aid 8.00
(Water)
10.00
(Water)
2.00
(MEG)
6.7
(MEG)
3.00
(MEG)
4.15
(water)
Inversion (in no.) a) (0 d) 39 56 32 42 35 25
b) after 14 days
AHS
40 > 60 37 >60 >60 >60
Suspensibility
(gravimetric)
a) % (0d) Ambient
82.00 21.61 88.00 81.50 45.62 24.58
b) AHS (14 d) 59.81 14.03 63.10 43.29 49.17 39.57
26
Example 5:
S.
No
.
Ingredients
SET E SET F SET G
Sprayed
adjuvant
Adjuvant
mixed with
agrochemi
cal
Adjuvant
sprayed
on powder
No Adjuvant sprayed or
added to the formulation.
(20+6)
02/271
(42+12)
06/275
(30+8)
03/272
(42+12)
09/280
(42+12)
10/281
(42+1
2)
11/282
1 Metribuzin
technical
21.0 44.3 32.0 43.59 46.68 44.30
2 Precipitated
Silica
- 10.0 5.0 4.65 - 4.00
3 Dialkyl
naphthalene
sulfonate
sodium salt
14.0 16.0 14.0 9.94 10.33 10.00
4 Kaolin 30.0 5.49 32.0 22.60 26.33 10.22
5 Clodinafop
propargyl
7.0 12.95 8.3 12.82 13.33 13.00
6 Cloquintocet
mexyl
1.5 3.26 2.2 3.19 3.33 3.26
7 Ethoxylated
tristyrylphenol
- 6.0 6.5 - - -
8 Castor oil
ethoxylate
8.5 2.0 - - - -
9 Ammonium
sulphate
18.0 - - - - -
10 sodium alkyl
naphthalene
sulfonate blend
- - - 3.21 -
27
11 sodium salt of
naphthalene
sulfonate
condensate
- - - - - 15.22
Remarks AJM –No
melting
AJM –
No
melting
AJM –
No
meltin
g
A Extrusion aid Water 8.00
(Water)
Water 6.8 Water 9.5
Water
9.0
Water
B Inversion (no.)
(0 d)
28 39 24 >30 56 43
AHS N/A 40 N/
A
N/
A
N/
A
N/
A
C Suspensibility
(gravimetric) %
(0d) Ambient
82.61 (0d) 62.0 (0d) 95.50/
97.42
26.42 21.61 46.76
AHS (14 d) N/A 59.81 N/A N/A N/A N/A
Sets E, F and G clearly demonstrate the effect of the adjuvant system on the suspensibility. Set
E was divided into two parts; one part was formulated by spraying the adjuvant system onto the
homogenous powder, and the other half was formulated by mixing the adjuvant system mixed
with agrochemical whilst blending. The results demonstrate that sprayed adjuvant or a coating
of the adjuvant onto the homogenous powder, resulted in superior suspensibility.
Set F also demonstrated that spraying adjuvant onto the homogenous powder gave granules
with excellent suspensibility as compared to those formulations prepared in Set G(No adjuvant)
and Set E (part one).
Although the present invention has been disclosed in full, it will be understood that numerous
additional modifications and variations could be made thereto without departing from the scope
of the invention.
28
WE CLAIM:
1. A granular formulation comprising particles of at least one low melting agrochemical
wherein said particles of low melting agrochemical are at least partially surface coated
with an ester of a compound selected from the group comprising (a) an alkyl or aryl
alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block copolymers
of alkyls or ethylene oxides or propylene oxides, (e) polyaryl substituted
aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted phenol and their
derivative and/or mixtures thereof.
2. The granular formulation as claimed in claim 1, wherein the low melting agrochemical
has a melting point less than about 1000C.
3. The granular formulation as claimed in claim 1 or claim 2, wherein the particles of low
melting agrochemical are at least partially surface coated with a phosphate of
polystyryl phenol ethoxylate.
4. A granular formulation comprising particles of at least one low melting agrochemical
admixed with particles of at least one co-agrochemical wherein said particles of low
melting agrochemicals and optionally particles of at least one co-agrochemical are at
least partially surface coated with an ester of a compound selected from the group
comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c)
alkoxylates of fatty acids, (d) block co-polymers of alkyls or ethylene oxides and
propylene oxides, (e) polyaryl substituted aliphatic or aromatic alkoxylate, (f)
alkoxylated polyaryl substituted phenol and their derivative and/or mixtures thereof.
5. The formulation as claimed in claim 4, wherein the low melting agrochemical is
selected from the group consisting of oxyphenoxy acid ester compounds selected from
the group consisting of clodinafop-propargyl, fluazifop-butyl, fenoxaprop-ethyl,
diclofop-methyl, quizalofop-methyl, haloxyfop-methyl and clofop-isobutyl.
6. The formulation as claimed in claim 5 further comprising at least one safener selected
from the group consisting of dymron, fenclorim, cumyluron, isoxadifen-ethyl, mefenpyrdiethyl,
cloquintocet-mexyl, cyprosulfamide, dietholate, disulfoton, 1,8-naphthalic
anhydride, fluxofenim, dichlormid, benoxacor, and flurazole.
7. The formulation as claimed in claim 4, wherein the co-agrochemical is a triazinone
herbicide selected from ametridione, amibuzin, ethiozin, hexazinone, isomethiozin,
metamitron and metribuzin.
8. The formulation as claimed in claim 4, wherein the particles of low melting
agrochemical or the particles of at least a co-agrochemical comprise at least one
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excipient selected from dispersing agents, wetting agents, defoamers, inert fillers and
absorbers.
9. The formulation as claimed in claim 8, wherein the dispersing agent is modified
styrene acrylic polymer or polycarboxylate potassium.
10. The formulation as claimed in claim 8, wherein the wetting agent is selected from
dialkyl naphthalene sulphonate formaldehyde condensate, dialkyl naphthalene
sulphonate sodium salt and sodium naphthalene sulfonate – formaldehyde
condensate.
11. The formulation as claimed in claim 8, wherein the defoamer is a silicon based
defoamer.
12. The formulation as claimed in any one of the preceding claims, wherein the particles of
low melting agrochemical are absorbed on an absorbent selected from silicate,
precipitated silica, kaolin, bentonite and a mixture thereof.
13. The formulation as claimed in any one of the preceding claims comprising the low
melting agrochemical in an amount of 1% to 25%.
14. The formulation as claimed in claims 4-13 comprising at least a co-agrochemical in an
amount of about 5% to 50%.
15. A process for the preparation of a granular formulation comprising a low melting
agrochemical, said process comprising:
(a) melting an agrochemically effective amount of a low melting agrochemical
and sorbing the molten agrochemical on an absorbent to obtain particles
of said low melting agrochemical; and
(b) at least partially surface coating said particles of low melting
agrochemical with an ester of a compound selected from the group
comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol,
(c) alkoxylates of fatty acids, (d) block co-polymers of alkyl or ethylene
oxides or propylene oxides, (e) polyaryl substituted aliphatic or aromatic
alkoxylate, (f) alkoxylated polyaryl substituted phenol and their derivative
and/or mixtures thereof.
16. A process for the preparation of a granular formulation comprising a low melting
agrochemical and at least a co-agrochemical, said process comprising:
(a) melting an agrochemically effective amount of a low melting agrochemical and sorbing
molten agrochemical on an absorbent to obtain particles of said low melting
agrochemical;
(b) mixing an agrochemically effective amount of at least a co-agrochemical with at least an
adjuvant to obtain particles of said co-agrochemical;
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(c) optionally homogenously mixing said particles of low melting agrochemical and at least a
co-agrochemical; and
(d) at least partially surface coating said particles of low melting agrochemical and the
particles of a co-agrochemical with an ester of a compound selected from the group
comprising (a) an alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c)
alkoxylates of fatty acids, (d) block co-polymers of ethylene oxides and propylene
oxides, (e) polyaryl substituted aliphatic or aromatic alkoxylate, (f) alkoxylated
polyaryl substituted phenol and their derivative and/or mixtures thereof.
17. The process as claimed in claim 15 or claim 16, wherein the particles of low melting
agrochemical or the particles of co-agrochemical are surface coated by spraying the
esters of said compounds on the particles prior to wet mixing.
18. The process as claimed in claim 15 or claim 16 wherein the low melting point
agrochemical is selected from clodinafop-propargyl, fluazifop-butyl, fenoxaprop-ethyl,
diclofop-methyl, quizalofop-methyl, haloxyfop-methyl and clofop-isobutyl.
19. The process as claimed in any one of the claims 15 – 18 wherein the process
comprising admixing the partially surface coated particles of low melting
agrochemicals and optionally particles of at least co-agrochemical with an aqueous
solvent to obtain a wet mix.
20. The process as claimed in claim 19, wherein the process comprises (a) granulating
/extruding the obtained wet mix and drying the granulated/extruded wet particles so
obtained.
21. The process as claimed in any one of the preceding claims 15-20, wherein sorbing the
low melting agrochemical on an absorbent comprises spraying the molten low melting
agrochemical on the absorbing material in a plough shear mixer.
22. A kit-of-parts for herbicidal treatment of plants, its habitat, a crop field, the soil or any
material thereabout, said kit-of-parts comprising:
(a) a first herbicidal component, said first herbicidal component comprising particles of
at least one low melting agrochemical, said particles being at least partially surface
coated with an ester of a compound selected from the group comprising (a) an
alkyl or aryl alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids,
(d) block co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted
phenol and their derivative and/or mixtures thereof;
(b) a second herbicidal component, said second herbicidal component comprising of
at least a co-agrochemical, said particles being at least partially surface coated
with an ester of a compound selected from the group comprising (a) an alkyl or aryl
alkoxylate, (b) alkoxylates of fatty alcohol, (c) alkoxylates of fatty acids, (d) block
co-polymers of alkyls, or ethylene oxides or propylene oxides, (e) polyaryl
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substituted aliphatic or aromatic alkoxylate, (f) alkoxylated polyaryl substituted
phenol and their derivative and/or mixtures thereof; and
(c) an instruction manual comprising instructions for mixing the first and second
herbicidal components in a predetermined ratio and treating the plants, its habitat,
a crop field, the soil or any material thereabout with said admixture.