STABLE AGROCHEMICAL OIL DISPERSIONS
FIELD OF THE INVENTION
[1] This disclosure concerns the use of dibenzylidene sorbitol (DBS)
or chemical derivatives of DBS as rheology modifiers useful in preparing stable
oil dispersion (OD) compositions of agrochemical products.
BACKGROUND AND SUMMARY OF THE INVENTION
[2] An agrochemical active ingredient, such as a herbicide, insecticide,
or fungicide, or a herbicide safener, can rarely be used in its originally
manufactured form. Agrochemical products generally consist of two parts, the
active ingredient and the co-formulants or inert ingredients combined together in a
formulation. The combination of these two parts into the final product is
conducted with two primary goals in mind: (1) maintaining the stability of the
product during storage and (2) providing an easy and effective way to use the
product upon dilution in a carrier such as water or oil, and spray application to an
area to be treated.
[3] Agrochemical formulations are generally designed based on
customer needs and the physiochemical properties of the active ingredient(s), for
example, the solubility of the active ingredient in water and other non-aqueous
solvents. There are two major categories of formulations, solid formulations and
liquid formulations. Liquid formulations include emulsifiable concentrates (EC),
suspension concentrates (SC), soluble liquids (SL), liquid flowables (F) and oil
dispersions (OD). EC formulations consist of oil-soluble active ingredient(s)
dissolved in non-aqueous solvent(s) to which are added emulsifying agents.
[4] The basic components of an agricultural OD formulation are the
solvent or oil phase and the dispersed solid phase. These basic components may
include active ingredients, petroleum or naturally derived solvents, safeners,
rheology additives, emulsifiers, dispersants and other co-formulants that help
deliver the desired attributes of the product. Rheology additives provide physical
stability to the formulation by increasing the viscosity of the liquid phase in order
to prevent insoluble active ingredient particles from falling out of suspension and
forming a layer at the bottom of the storage container. This phenomenum, known
as sedimentation, can result in difficulties in the delivery and use of the product if
the sedimented layer of particles forms a hard pack that is difficult to disperse and
re-suspend. A related physical instability of liquid formulations is syneresis.
Syneresis in an OD formulation is generally measured as the amount of topclearing
due to phase separation.
[5] The amount and severity of sedimentation that occurs in an OD
formulation over time may be measured with a pourability test. This test is
conducted by pouring the OD formulation out of a container in a controlled
manner and measuring the amount of the formulation remaining in the container.
The pourability value is the per cent by weight of material remaining in the
container.
[6] Rheology additives used to control sedimentation, also known as
thickeners, anti-caking agents, viscosity modifiers or structuring agents, generally
provide the increased viscosity to the OD formulation. In addition to increasing
the viscosity of the OD formulation, rheology additives have a shear thinning
capability that allows the gel network they form to easily breakdown upon
application of a small external force. This shear thinning allows the OD
formulation to maintain its viscosity and physical stability while at rest, but allows
this viscosity to quickly dissipate when external force is applied so that the
product can be easily poured or pumped from its container, mixed in a carrier such
as water and applied to an area where it is needed.
[7] Rheology additives used in products today to add viscosity come in
many forms and chemistries. They can be mineral or derived from minerals (e.g.,
organoclays, fumed silica), swellable polymers (e.g., polyamides or hydrogenated
caster oils), associative thickeners which form structures by themselves (e.g.,
EO/PO block co-polymers), or they can be steric dispersants (e.g., comb polymers
such as polyvinylpyrrolidinones or polyacrylates). These rheological or
structuring agents provide long term stability when the product is at rest or in
storage.
[8] Agrochemical products generally have to be diluted and properly
dispersed in water prior to application. An emulsifier system may be included in
the OD formulation to help disperse the oil-based, water immiscible formulation
in water. An emulsifier system commonly includes a mixture of non-ionic and
anionic surfactants in order to accommodate variations in water hardness and
temperature encountered in various locations.
[9] For polar interactions, clays, organoclays such as bentonite,
hectorite or gibbsite clays, which are also known as hydrophobically modified
clays, hydrogenated castor oils, castor oil derivatives, polyamides, polar, oxidized
waxes, and hydrophobized fumed silica may be used as rheology aids in non
aqueous solvents. For controlled pigment flocculation in paints, organic sulfates
are commonly used. High molecular weight polymers such as ethyl cellulose,
cellulose acetobutyrate and man-made polymers such as polyacrylates,
polystyrenes and polyisobutylenes may also be used to build viscosity in organic
solvents. Finally, soaps such as aluminum stearate and magnesium stearate may
be used to build viscosity.
[10] Natural clay products are generally layered silicates that can be
effective thickeners for a wide range of applications. In order to make them
dispersible in non-aqueous solvents, however, the clay surface is usually treated
with quaternary ammonium. These modified clays are known as organoclay
thickeners. These strongly agglomerated particles need to be wetted first and then
separated by shear forces. High shear mixing is desirable for this process.
Activators like alcohols can penetrate in between the clay layers and help make
them form loose stacks for ease of application. The typical rheology curve of clay
particle modified OD formulation shows strong shear-thinning and thixotropic
behavior. At low shear stress, the clay structure may show some resistance to the
flow. With increasing shear stress, the applied shear force progressively destroys
the clay network and the layered clay particles start to move with the flow. When
the shear is removed, the clay network reforms and the viscosity builds up again.
Depending on the type and origin of the clay products, it is important to know that
the rheology building efficiency varies due to the difference in clay particle sizes
and shapes. Boehmite clay seems to be more effective in enhancing the rheology
properties of a fluid than the other type of clays due to its larger aspect ratio and
hence its surface area.
[11] The thickening mechanism of hydrogenated castor oils and their
derivatives, polyamides and polar, oxidized waxes is based on hydrogen bonding,
but these additives may be somewhat sensitive to temperature effects. The
procedure of activating hydrogenated caster oil products requires both shear
mixing and heat since these products are delivered as micronized powders.
Similar to the organo-clays, these micronized powders have to be dispersed into a
gel form without complete dissolution in the solvent. The first step is swelling of
the crystalline particles by the solvent using shear and heat to provide swollen
particles that become fully separated and dispersed. The activating temperature is
dependent on the solvent type. Care has to be taken not to exceed the activation
temperature otherwise the castor oil derivatives will completely dissolve, lose
their thickening properties and recrystallize upon cooling. Usually a pre-gel can
be made for easier use of these materials.
[12] The third type of rheology modifiers that require polar interactions
to build up a three-dimensional network are those based on fumed silica. Fumed
silica, either hydrophilic or hydrophobic, is composed of nano-size primary silica
particles connected together to form chain shaped segregates. Due to its
extremely high surface area and wide solvent compatibility, fumed silica products
are widely used in formulating industrial and consumer products. Although both
hydrophilic and hydrophobic fumed silica can be used in OD formulations as
thickening agents, hydrophobic silica generally provides rheology properties that
are easier to control in non-aqueous formulations than does hydrophilic silica.
[13] Rheology additives used in OD formulations to insure that
suspended particles of active ingredients are not susceptible to irreversible
sedimentation, may be used alone or in combination with other rheology
additives. It is very common to combine one or more rheology additives in a
single OD formulation to obtain the desired rheological properties and, at the
same time, minimize any adverse interactions that may occur between ingredients.
The proper choice and amounts of OD thickeners can enhance the thickening
efficacy and application range of a particular formulation. Factors to consider in
the selection of rheology additives for the design of a stable OD system are the
type of solvent, the interactions with emulsifiers, the robustness in activation of
the thickeners, and the temperature sensitivity of the final system.
[14] While there are many rheology modifiers available for use in
stabilizing agrochemical OD formulations to particle sedimentation, there is a
constant need for new ones owing to limitations with existing choices,
incompatibilities with surfactants, and the diversity in chemistry of new active
ingredients and solvents being discovered and developed today. In addition, the
increasing number of active ingredients included in a single formulation can also
present formulation challenges. These limitations may be overcome by finding
new rheology modifiers that act in new ways or at lower concentrations.
[15] Dibenzylidene sorbitol (DBS; CAS 32647-67-9 and 19046-64-1)
has the following structure
and is an organic molecule capable of inducing gelation or thickening in a variety
of organic solvents. DBS is derived from the sugar alcohol D-glucitol and
benzaldehyde and is marketed by Milliken Chemical as Millithix® 925s. DBS
has been investigated for use as a gelling agent in personal care products such as
antipersperants and cosmetics, and also in biomedical materials and electronic
devices. DBS has also seen use as a clarifying agent for polyolefin derived
plastics (Millad® 3905). The morphological characteristics of DBS have been
described by D. J . Mercurio and R. J . Spontak in, "Morphological Characteristics
of 1,3:2,4-Dibenzylidene Sorbitol/Poly(propylene glycol) Organogels," J . Phys.
Chem. B, 105 (11) pg. 2091-2098 (2001).
[16] Two simple analogs of DBS, known as methyl-DBS (CAS 54686-
97-4) and dimethyl-DBS (CAS 135861-56-2, Millad® 3988), are also available
from Milliken Chemical and their respective structures are shown below
methyl-DBS dimethyl-DBS
Recently, a new DBS-type product known as NX8000 (CAS 882073-43-0) has
been marketed by Milliken Chemical as a clarifying agent for plastics and its
structure is shown below
There are many other chemical analogs of DBS disclosed in the literature that
generally have seen utility as polyolefin additives to enhance the clarity and
aesthetics of plastics as disclosed, for example, in US 2007/0249850 Al, which is
incorporated by reference herein.
[17] DBS has now been found to be an effective rheology modifier in
OD formulations of agrochemical products and offers improved performance and
compatibility with the increasingly complex products being developed today. The
present disclosure provides new methods and compositions for producing stable
OD formulations of agrochemical products that are suitable in controlling
undesired vegetation, insects and plant diseases, the inventive composition
comprising a solvent, dibenzylidene sorbitol or an analog of dibenzylidene
sorbitol, and an agricultural active ingredient.
DETAILED DESCRIPTION OF THE INVENTION
[18] The present invention relates to the use of dibenzylidene sorbitol or
analogs of dibenzylidene sorbitol as rheology additives with improved
performance to thicken or add viscosity to OD formulations containing
agricultural active ingredients in order to increase the stability of such
formulations, the composition comprising a solvent, at least one of dibenzylidene
sorbitol and an analog of dibenzylidene sorbitol, and an agricultural active
ingredient.
[19] The solvent of the present disclosure is generally an organic, water
immiscible solvent and may comprise one or more of petroleum distillates such as
aromatic hydrocarbons derived from benzene, such as toluene, xylenes, other
alkylated benzenes and the like, and naphthalene derivatives, aliphatic
hydrocarbons such as hexane, octane, cyclohexane, and the like, mineral oils from
the aliphatic or isoparaffinic series, and mixtures of aromatic and aliphatic
hydrocarbons; halogenated aromatic or aliphatic hydrocarbons; vegetable, seed or
animal oils such as soybean oil, rape seed oil, olive oil, castor oil, sunflower seed
oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil,
safflower oil, sesame oil, tung oil and the like, and Ci-C6 mono-esters derived
from vegetable, seed or animal oils; dialkyl amides of short and long chain,
saturated and unsaturated carboxylic acids; C -Cn esters of aromatic carboxylic
acids and dicarboxylic acids, and C C esters of aliphatic and cyclo-aliphatic
carboxylic acids.
[20] In addition, the above solvents may be mixed with one or more
polar solvents such as, but not limited to, ethers like tetrahydrofuran and the like,
alkylene glycol mono- or dialkyl ethers such as ethylene glycol monoethyl ether
and the like, amides such as dimethylacetamide or N-methylpyrrolidone and the
like, ketones such as methylethyl ketone and the like, nitriles such as butyronitrile
and the like, sulfoxides or sulfones such as dimethyl sulfoxide or sulfolane and the
like, mono- or polyhydric alcohols having 2 to 12 carbon atoms, and alkylene
carbonates such as propylene or butylene carbonate and the like.
[21] The solvent of the present disclosure may comprise, with respect to
the total composition, from about 200 g/L to 999 g/L, preferably from about 300
g/L to 950 g/L.
[22] The DBS of the present disclosure is used as a rheology additive to
build viscosity in agrochemical OD formations thru formation of a gel. This helps
keep the dispersed active ingredient suspended in the solvent and inhibits settling
and sedimentation of the active ingredient which can contribute to formulation
instability and inferior performance of the product. DBS may be dispersed and
properly activated in the solvent prior to the addition of other components. The
resulting mixture containing the activated DBS in the form of a gel generally
shows good shear thinning properties. DBS may comprise, with respect to the
total composition, from about 0.1 g/L to 100 g/L, preferably from about 0.1 g/L to
50 g/L.
[23] As a further embodiment of the present disclosure, DBS may be
used in combination with one or more existing rheology additives that are
commonly used in agrochemical OD formulations to provide improved physical
stability by inhibiting sedimentation. Suitable rheology additives to use with DBS
may comprise one or more of a clay, a modified clay, a silica or a fumed silica, a
hydrogenated castor oil, a castor oil derivative, a polyamide and a polyester. The
DBS used in a combination with suitable rheology additives may comprise, with
respect to the total composition, from about 0.1 g/L to 100 g/L, preferably from
about 0.1 g/L to 50 g/L. The suitable rheology additives used in combination with
DBS may comprise, with respect to the total composition, from about 0.1 g/L to
200 g/L, preferably from about 0.2 g/L to 100 g/L.
[24] As a further embodiment of the present disclosure, analogs of DBS
may be used alone, in combination with DBS, or in combination with one or more
existing rheology additives used in agricultural OD formulations to provide
physical stability by increasing the viscosity of such formulations. These analogs
may comprise the following structures
wherein A and Ar2 are the same or different mono- or polysubstituted phenyl
rings groups. The substituted phenyl groups may contain one or more substituents
selected from, but not limited to, C oalkyl, Ci-Cw haloalkyl, Ci-Cw alkoxy,
C Ciohaloalkoxy, Ci-Cw alkylthio, Ci-Cw haloalkylthio, Ci-Cw
haloalkylsulfinyl, -C haloalkyl-sulfonyl, hydroxyl, halo, nitro, carboxylic acid
and derivatives thereof, cyano, amino, -C alkylamino, -C dialkylamino,
C Cioalkylcarbonylamino, phenylcarbonylamino, Ci-Cw
alkylphenylcarbonylamino, Ci-Cw alkylsulfonylamino and phenylsulfonylamino.
[25] The agrochemical active ingredients of the present disclosure may
be selected from the groups of herbicides, insecticides and fungicides. The active
ingredients may be present as dispersed solids that have very low solubility in the
solvent or they may be completely soluble or partially soluble in the solvent.
Preferred dispersible active ingredients are generally higher melting solids (>50
°C) with low solubility (<10 g/L) in the solvent phase. Preferred soluble or
partially soluble active ingredients are generally lower melting solids (< 150 °C)
with moderate to high solubility in the solvent phase (> 10 g/L).
[26] The dispersed solid herbicide active ingredients of the present
invention include, but are not limited to sulfonamides, sulfonylureas, arylpyridine
carboxylic acids and analogs, arylpyrimidine carboxylic acids and analogs,
anilides, imidazolinones and carbazones. Also, alkali metal salts or amine salts of
benzoic acids, phenoxyalkanoic acids, pyridinecarboxylic acids and
pyridyloxycarboxylic acid herbicides may also comprise the dispersed active
ingredients of the present invention.
[27] Herbicides which are especially suitable for dispersion in the
solvent phase are triasulfuron, tribenuron, metasulfuron, thifensulfuron,
flupyrsulfuron, iodosulfuron, rimsulfuron, nicosulfuron, cinosulfuron,
bensulfuron, trifloxysulfuron, foramsulphuron, mesosulphuron, sulphosulphuron,
tritosulphuron and derivatives, furthermore flumetsulam, metosulam,
chloransulam, florasulam, diclosulam, penoxsulam, pyroxsulam and derivatives,
diflufenican, also imazethabenz, imazethapyr, imazaquin, imazamox and
derivatives, and fhicarbazone, propoxycarbazone, amicarbazone and derivatives,
and compounds of the following generic structures, or their derivatives,
as disclosed in US73 14849 B2 and US7300907 B2 wherein Ar is a
polysubstituted phenyl group, R is H or halo and X is halo.
[28] Additional herbicides which are especially suitable for dispersion
in the solvent phase are alkali metal or amine salts of dicamba, 2,4-D, MCPA, 2,4-
DB, aminopyralid, picloram, clopyralid, fluroxypyr and triclopyr, and alkali metal
salts of bromoxynil and ioxynil. The amines are comprised of primary, secondary
or tertiary alkylamines, alkanolamines, alkylalkanolamines or
alkoxyalkanolamines wherein the alkyl and alkanol groups are saturated and
contain C C4 alkyl groups individually. The alkali metals are comprised of
sodium and potassium.
[29] For an OD formulation of the present disclosure which may be
further diluted at the point of use, the solvent dispersible herbicide may comprise,
with respect to the total composition, from about 1 g/L to 700 g/L, preferably from
about 5 g/L to 500 g/L. It is commonly known that this concentrated formulation
may be diluted from 1 to 2000 fold at point of use depending on the agricultural
practices.
[30] A further embodiment of the present disclosure comprises the
addition of solvent soluble or partially solvent soluble active ingredients and
safeners. These active ingredients and safeners may include one or more of a
herbicide, an insecticide, a fungicide and a herbicide safener, but are not limited
to, esters of carboxylate, phosphate, or sulfate pesticides.
[31] Suitable soluble or partially soluble herbicide active ingredients of
the present invention include, but are not limited to benzoic acid herbicides such
as dicamba esters, phenoxyalkanoic acid herbicides such as 2,4-D, MCPA or 2,4-
DB esters, aryloxyphenoxypropionic acid herbicides such as clodinafop,
cyhalofop, fenoxaprop, fluazifop, haloxyfop and quizalofop esters,
pyridinecarboxylic acid herbicides such as aminopyralid, picloram and clopyralid
esters, pyridyloxycarboxylic acids such as fluroxypyr and triclopyr esters, and
nitrile herbicides such as bromoxynil and ioxynil and esters thereof.
[32] Suitable soluble or partially soluble herbicide safeners of the
present disclosure may comprise, but are not limited to, cloquintocet mexyl,
benoxacor, cyometrinil, cyprosulfamide, dichlormid dicyclonon, dietholate,
fenchlorazole ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen ethyl,
mefenpyr diethyl, mephenate, naphthalic anhydride, oxabetrinil and derivatives
and analogs thereof.
[33] The solvent soluble or partially solvent soluble herbicide active
ingredients or herbicide safeners of the present invention may comprise, with
respect to the total composition, from about 1 g/L to 700 g/L, preferably from
about 5 g/L to 500 g/L.
[34] Additional agricultural active ingredients of the present disclosure
may include insecticides and fungicides. These active ingredients may be present
as dispersed solids, or soluble or partially soluble active ingredients.
[35] Suitable insecticide active ingredients of the present disclosure
include, but are not limited to, antibiotic insecticides, macrocyclic lactone
insecticides (for example, avermectin insecticides, milbemycin insecticides, and
spinosyn insecticides), arsenical insecticides, botanical insecticides, carbamate
insecticides (for example, benzofuranyl methylcarbamate insecticides,
dimethylcarbamate insecticides, oxime carbamate insecticides, and phenyl
methylcarbamate insecticides), diamide insecticides, desiccant insecticides,
dinitrophenol insecticides, fluorine insecticides, formamidine insecticides,
fumigant insecticides, inorganic insecticides, insect growth regulators (for
example, chitin synthesis inhibitors, juvenile hormone mimics, juvenile hormones,
moulting hormone agonists, moulting hormones, moulting inhibitors, precocenes,
and other unclassified insect growth regulators), nereistoxin analogue insecticides,
nicotinoid insecticides (for example, nitroguanidine insecticides, nitromethylene
insecticides, and pyridylmethylamine insecticides), organochlorine insecticides,
organophosphorus insecticides, oxadiazine insecticides, oxadiazolone insecticides,
phthalimide insecticides, pyrazole insecticides, pyrethroid insecticides,
pyrimidinamine insecticides, pyrrole insecticides, tetramic acid insecticides,
tetronic acid insecticides, thiazole insecticides, thiazolidine insecticides, thiourea
insecticides, urea insecticides, as well as, other unclassified insecticides.
[36] Some of the particular insecticides that can be employed
beneficially in combination with the invention disclosed in this document include,
but are not limited to, the following 1,2-dichloropropane, 1,3-dichloropropene,
abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,
alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alphacypermethrin,
alpha-endosulfan, amidithion, aminocarb, amiton, amitraz,
anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphosmethyl,
azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb,
bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,
bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, borax, boric acid,
boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophosethyl,
bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,
butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor,
carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride,
carbophenothion, carbosulfan, cartap, chlorantraniliprole, chlorbicyclen,
chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin,
chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos,
chromafenozide, cinerin I, cinerin II, cismethrin, cloethocarb, closantel,
clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper
oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite,
cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT,
decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton,
demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl,
demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon,
dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin,
diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin,
dimethylvinphos, dimetilan, dinex, dinoprop, dinosam, dinotefuran, diofenolan,
dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, J-limonene, DNOC,
doramectin, ecdysterone, emamectin, EMPC, empenthrin, endosulfan, endothion,
endrin, EPN, epofenonane, eprinomectin, esfenvalerate, etaphos, ethiofencarb,
ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD,
ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos,
EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin,
fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin,
fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,
flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,
flufenprox, fluvalinate, fonofos, formetanate, formothion, formparanate,
fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin,
gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos,
heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide,
hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane,
IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isoprocarb,
isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II,
jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III,
kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,
lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox,
mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos,
metaflumizone, methacrifos, methamidophos, methidathion, methiocarb,
methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl
bromide, methylchloroform, methylene chloride, metofluthrin, metolcarb,
metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime,
mipafox, mirex, monocrotophos, morphothion, moxidectin, naftalofos, naled,
naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron,
noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos,
oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron,
pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate,
phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim,
phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl,
potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I,
precocene II, precocene III, primidophos, profenofos, profluthrin, promacyl,
promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos,
prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin,
pyrethrin I, pyrethrin II, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon,
pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphosmethyl,
quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan,
selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium
hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,
spiromesifen, spirotetramat, sulcofuron, sulfoxaflor, sulfluramid, sulfotep, sulfuryl
fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad,
tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos,
tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thetacypermethrin,
thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam,
thiodicarb, thiofanox, thiometon, thiosultap, thuringiensin, tolfenpyrad,
tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos,
trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb,
triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin,
zolaprofos, and a-ecdysone.
[37] Additionally, any combination of the above insecticides can be
used.
[38] Suitable fungicide active ingredients of the present disclosure may
also be combined with other fungicides to form fungicidal mixtures and
synergistic mixtures thereof. The fungicidal compounds of the present disclosure
are often applied in conjunction with one or more other fungicides to control a
wider variety of undesirable diseases. When used in conjunction with other
fungicide(s), the presently claimed compounds may be formulated with the other
fungicide(s), tank mixed with the other fungicide(s) or applied sequentially with
the other fungicide(s). Such other fungicides may include 2-
thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline
sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis,
azaconazole, azoxystrobin, Bacillus subtilis, benalaxyl, benomyl, benthiavalicarbisopropyl,
benzylaminobenzene- sulfonate (BABS) salt, bicarbonates, biphenyl,
bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture,
boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan,
carbendazim, carboxin, carpropamid, carvone, chloroneb, chlorothalonil,
chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper
oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid,
cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb,
diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen,
diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat
ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,
dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate,
dodine, dodine free base, edifenphos, enestrobin, epoxiconazole, ethaboxam,
ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole,
fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin,
fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,
flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,
flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, folpet, formaldehyde,
fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine,
guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol,
imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate,
iminoctadine tris(albesilate), ipconazole, iprobenfos, iprodione, iprovalicarb,
isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride
hydrate, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb,
mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride,
metalaxyl, mefenoxam, metalaxyl-M, metam, metam-ammonium, metampotassium,
metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl
isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin,
myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic
acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate,
oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,
pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury
acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins,
polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate,
probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride,
propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin,
pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb,
pyrifenox, pyrimethanil, pyroquilon, quinoclamine, quinoxyfen, quintozene,
Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-
phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide,
spiroxamine, sulfur, SYP-Z071, SYP-Z048, tar oils, tebuconazole, tebufloquin,
tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram,
tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,
tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,
validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide,
Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea,
Streptomyces griseoviridis, Trichoderma spp., (R )-N-(3,5-dichlorophenyl)-2-
(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro- 1,1,3,3-
tetrafluoroacetone hydrate, l-chloro-2,4-dinitronaphthalene, l-chloro-2-
nitropropane, 2-(2-heptadecyl-2-imidazolin-l-yl)ethanol, 2,3-dihydro-5-phenyl-
1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-
methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-
chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop- l-enyl)phenyl thiocyanateme,
ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil,
benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,
bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium
copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,
chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-
phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate,
cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone,
dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon,
dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem,
ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil,
furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,
halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione,
mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury
dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-
dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, Nethylmercurio-
4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH,
phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen,
prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor,
pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole,
salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen,
thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol,
triazbutil, trichlamide, urbacid, XRD-563, and zarilamid, IK- 1140, and any
combinations thereof.
[39] The insecticide or fungicide active ingredients of the present
disclosure may comprise, with respect to the total composition, from about 1 g/L
to 700 g/L, preferably from about 5 g/L to 500 g/L.
[40] It is usually desirable to incorporate one or more surface-active
agents into the compositions of the present invention. The surface-active agents
can be anionic, cationic or nonionic in character and can be employed as
emulsifying agents, wetting agents, suspending agents, or for other purposes.
Surfactants conventionally used in the art of formulation and which may also be
used in the present formulations are described, inter alia, in "McCutcheon's
Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New
Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I-III, Chemical publishing
Co., New York, 1980-81. Typical surface-active agents include salts of alkyl
sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such
as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition
products, such as nonylphenol-Cig ethoxylate; alcohol- alkylene oxide addition
products, such as tridecyl alcohol-C^ ethoxylate; soaps, such as sodium stearate;
alkylnaphthalene-sulfonate salts, such as sodium dibutylnaphthalenesulfonate;
dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate;
sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl
trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as
polyethylene glycol stearate; block copolymers of ethylene oxide and propylene
oxide; salts of mono and dialkyl phosphate esters; vegetable oils such as soy bean
oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil,
cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil
and the like; and esters of the above vegetable oils.
[41] The composition of the present disclosure may optionally include
one or more additional inert ingredients such as antifoam agents, adjuvants,
stabilizers, fragrants, sequestering agents, neutralizing agents, buffers, corrosion
inhibitors, dyes, odorants and other commonly used ingredients.
[42] The effective amount of the OD formulation of the present
disclosure to be employed in a typical agricultural application often depends upon,
for example, the type of plants, the stage of growth of the plant, severity of
environmental conditions, the weeds, insects or fungal pathogens to be controlled
and application conditions. Typically, a plant in need of protection from weeds or
insects, or disease pathogen control or elimination, is contacted with an amount of
the OD formulation diluted in a carrier such as water that will provide an amount
from about 1 to about 40,000 ppm, preferably from about 10 to about 20,000 ppm
of the active ingredient. The contacting may be in any effective manner. For
example, any exposed part of the plant, e.g., leaves or stems may be sprayed with
the active ingredient in mixture with a suitable amount of a diluent or carrier such
as water.
[43] The aforementioned compositions of the present invention may be
applied to the plant foliage or the soil or area adjacent to the plant. Additionally,
the compositions of the present invention may be mixed with or applied with any
combination of agricultural active ingredients such as herbicides, insecticides,
bacteriocides, nematocides, miticides, biocides, termiticides, rodenticides,
molluscides, arthropodicides, fertilizers, growth regulators, and pheromones.
[44] In a typical procedure for preparing an OD formulation of the
present invention, a pre-gel of DBS is first prepared by dispersing and activating
the DBS in the solvent with shear mixing and heat. Following cooling to room
temperature, the pre-gel of DBS is then added with mixing to a mixture previously
formed by shear mixing the active ingredient and any other ingredients with the
solvent.
[45] An example of a stable OD formulation of the present disclosure in
which sedimentation of the dispersed active ingredient is retarded by DBS
comprises:
a) a solvent comprising, with respect to the total composition,
from about 200 g/L to about 999 g/L of Aromatic 200ND;
b) a rheology additive comprising, with respect to the total
composition, from about 0.1 g/L to about 100 g/L of dibenzylidene
sorbitol;
c) an active ingredient comprising, with respect to the total
composition, from about 1 g/L to about 200 g/L of pyroxsulam;
d) optionally, other inert formulation ingredients.
Examples
[46] In order to properly activate DBS, a 1.5% pre-gel solution of DBS
in an aromatic solvent (e.g., Aromatic 200 naphthalene depleted from
ExxonMobil) was made by dispersing 1.5g of DBS into 98.5g of Aromatic 200
under high shear, heating the mixture to 50-55°C for 15 minutes, and cooling the
mixture to room temperature under low shear mixing. The resulting mixture
should be semi-clear to clear in appearance and show highly thixotropic gel
properties.
[47] The compositions of the present disclosure shown in Table 1 were
prepared using the following procedure: 1) the amount of solvent shown in Table
1 was charged into a glass beaker equipped with a mechanic stirrer; 2) the 1.5%
DBS pre-gel was added into the beaker under constant mixing; 3) the active
ingredient was then added to the mixture; 4) the mixture was stirred until
homogeneous and then sonicated for 10 minutes to furnish the test sample. All
samples were stable to sedimentation after 24 hours at room temperature by visual
inspection.
Table 1. Compositions of the present disclosure for evaluation of stability to
sedimentation.
As indicated in Table 2 below, samples 7 and 8 were prepared with the ingredients
shown and by the following procedure. Aromatic 200ND was first charged into a
glass beaker equipped with a mechanic stirrer. Bentone 38 powder was then added
to the beaker under high shear to ensure complete dispersion of the powder.
Tensiofix N9824HF and propylene carbonate were then added under constant
mixing. Finally the 1.5% DBS pre-gel was added to the mixture to furnish sample
7. No DBS was added to sample 8. Both samples 7 and 8 were then packaged into
100 mL glass bottles for storage stability assessment. The samples were stored
undisturbed at room temperature for seven months. The percentage of syneresis
was measured visually in both samples and Formulation 7 showed 8.7% top
clearing while Formulation 8 showed 57.1% top clearing. The effect of including
DBS was evident by the differing amount of phase separation in each sample.
Table 2. Stability of OD formulations with and without added DBS to syneresis
after seven months storage at room temperature
[48] As indicated in Table 3 below, samples 9 and 10 were prepared
with the ingredients shown and by the following procedure. Aromatic 200ND
was first charged into a glass beaker equipped with a mechanic stirrer. The
Bentone 34 powder was then added to the beaker under high shear to ensure
complete dispersion of the powder. The Tensiofix surfactants and propylene
carbonate were then added under constant mixing. The active ingredient
pyroxsulam and safener cloquintocet-mexyl were added and fully dispersed with
high shear mixing. The rest of the ingredients were then added in no particular
order except that the DBS was added as the last ingredient as a 1.5% pre-gel in
Aromatic 200ND to furnish formulation 10. Both samples were then packaged
into glass bottles for storage stability assessments.
Table 3. Compositions of formulation samples 9 and 10.
[49] Samples 9 and 10 were exposed to a variety of temperature
conditions including 54 °C and 40 °C constant temperatures, and -10 °C /40 °C
cycling over one day, in order to evaluate their storage stability. The chemical
assays were measured after storage for 2 weeks and formulations 9 and 10 were
found to be chemically stable with no loss of the active ingredient being detected
under all storage conditions. The samples were also compared on the basis of
their yield stress which is known to be an indicator of rheology structure strength
and hence the stability of the formulations. The higher the yield stress value the
stronger the gel strength and hence better formulation stability. The yield stress
was measured using an AR1000 rheometer from TA Instruments equipped with a
4 mm cross-hatched plate. The viscosity-stress curve was obtained by running the
steady state shear by operating the rheometer from the lowest torque possible with
the equipment up to 10,000 micro Newton meters (mNih) . The yield stress was
then calculated by the software on the rheometer as the onset stress value
measured in Pascals (Pa) to drive the sample to flow. The yield stress
measurements of samples 9 and 10 are shown in Table 5. The results show that
formulations 9 and 10 had very stable high yield stress values when subjected to a
variety of storage conditions indicating a stable rheology structure was present in
each formulation.
Table 5. Yield Stress Measurements of Formulations 9 and 10 after Storage
[50] The pourability of a particular OD formulation is a measure of the
amount of sedimentation that occurs over time and how resistant that sediment is
to being poured from the container in which it is stored. The pourability value
can be measured by use of CIPAC method MT 148.1, Pourability of Suspension
Concentrates. In this method, the suspension concentrate is allowed to stand for a
defined period of time and then subjected to a standardized pouring procedure.
The amount of material remaining in the container after pouring is determined and
reported as the wt of material remaining in the container. The wt of material
remaining after pouring is known as the pourability value. A glass bottle
containing a sample of Formulation 10 was allowed to stand at room temperature
for 24 hours and then the contents of the bottle were poured out following CIPAC
method MT 148.1. The residual amount of Formulation 10 remaining in the bottle
after pouring was found to be 1.77 wt of the original amount, thereby giving a
pourability value of 1.77% for Formulation 10.
[51] While the invention has been described with respect to a limited
number of embodiments, the specific features of one embodiment should not be
attributed to other embodiments of the invention. No single embodiment is
representative of all aspects of the invention. In some embodiments, the
compositions or methods may include numerous compounds or steps not
mentioned herein. In other embodiments, the compositions or methods do not
include, or are substantially free of, any compounds or steps not enumerated
herein. Variations and modifications from the described embodiments exist.
Finally, any number disclosed herein should be construed to mean approximate,
regardless of whether the word "about" or "approximately" is used in describing
the number. The appended embodiments and claims intend to cover all those
modifications and variations as falling within the scope of the invention.

What is claimed:
1. A mixture comprising:
a) a solvent;
b) at least one of dibenzylidene sorbitol and analogs of
dibenzylidene sorbitol; and
c) an agricultural active ingredient.
2. The composition of Claim 1 further comprising ingredients
selected from dispersing agents, emulsifying agents, wetting agents, antifoam
agents, adjuvants and safeners.
3. The composition of Claim 1 wherein the composition includes
more than one thickening agent.
4. The composition of claim 3 wherein the thickening agent is one of
a clay, a modified clay, a silica, a hydrogenated castor oil, a castor oil derivative, a
polyamide and a polyester.
5. The composition of Claim 1 wherein the agricultural active
ingredient comprises one or more dispersed solids.
6. The composition of claim 5 wherein the dispersed solid is a
herbicide from the chemical classes comprised of sulfonamides, sulfonylureas and
derivatives, arylpyridine carboxylic acids and derivatives, arylpyrimidine
carboxylic acids and derivatives, anilides, imidazolinones and carbazones.
7. The composition of claim 6 wherein the herbicide is at least one of
or a derivative of one of pyroxsulam, florasulam, penoxsulam, diflufenican,
thifensulfuron, tribenuron, mesosulfuron, clopyralid, aminopyralid, fluroxypyr,
triclopyr, picloram and compounds of the following structures
and their derivatives wherein Ar is a polysubstituted phenyl group, R is H or halo
and X is halo.
8. The composition of claim 5 wherein the dispersed solid is a
herbicide from the chemical classes comprised of alkali metal salts or amine salts
of benzoic acids, phenoxyalkanoic acids, nitriles, pyridinecarboxylic acids and
pyridyloxycarboxylic acids.
9. The composition of claim 8 wherein the herbicide is at least one of
dicamba, 2,4-D, MCPA, 2,4-DB, aminopyralid, picloram, clopyralid, bromoxynil,
ioxynil, fluroxypyr and triclopyr.
10. The composition of claim 1 wherein the agricultural active
ingredient is at least one of an insecticide and a fungicide.
11. The composition of Claim 1 wherein the agricultural active
ingredient comprises at least one of a dissolved and a partially dissolved
agricultural active ingredient.
12. The composition of claim 11 wherein the at least one of the
dissolved and the partially dissolved agricultural active ingredient is at least one of
a fluroxypyr ester, an MCPA ester, a 2,4-D ester, a bromoxynil derivative, an
ioxynil derivative, a dicamba ester, a 2,4-DB ester, an aminopyralid ester, a
picloram ester, a clopyralid ester, a triclopyr ester, a clodinafop ester, a cyhalofop
ester, a fenoxaprop ester, a fluazifop ester, a haloxyfop ester and a quizalofop
ester.
13. The composition of claim 1 further comprising a herbicide safener.
14. The composition of claim 13 wherein the herbicide safener is one
of cloquintocet mexyl, benoxacor, cyometrinil, cyprosulfamide, dichlormid
dicyclonon, dietholate, fenchlorazole ethyl, fenclorim, flurazole, fluxofenim,
furilazole, isoxadifen ethyl, mefenpyr diethyl, mephenate, naphthalic anhydride
and oxabetrinil, and analogs and derivatives thereof.
15. The composition of claim 1 utilized for controlling insects, plant
diseases or weeds including the steps of:
providing a formulation including the composition of claim 1, and
diluting the formulation containing the composition of claim 1 in a suitable
agricultural carrier such as water
applying at least one of a formulation including the composition of claim 1
to at least one of the plant, the area adjacent to the plant, plant foliage, blossoms,
stems, fruits, soil, seeds, germinating seeds, roots, liquid and solid growth media,
and hydroponic growth solutions.
16. A method of controlling insects, plant diseases or weeds including
the steps of:
providing a formulation including the composition of claim 1, and
applying an agriculturally effective amount of the formulation in
mixture with one or more conventional formulations of agricultural active
ingredients or nutrients to at least one of the following: the plant, plant foliage,
blossoms, stems, fruits, the area adjacent to the plant, soil, seeds, germinating
seeds, roots, liquid and solid growth media, and hydroponic growth solutions.
17. An oil dispersion having a pourability value of less than 5%, the oil
dispersion comprising:
a) a solvent;
b) one of dibenzylidene sorbitol and analogs of
dibenzylidene sorbitol; and
c) an agricultural active ingredient
18. A non-aqueous suspension concentrate comprising:
a) a solvent;
b) one of dibenzylidene sorbitol and analogs of
dibenzylidene sorbitol; and
c) an agricultural active ingredient