U.S. patent application number 13/540343 was filed with the patent office on 2013-07-04 for formulation.
This patent application is currently assigned to Syngenta Crop Protection LLC. The applicant listed for this patent is Gordon Alastair Bell, Guy Ramsay. Invention is credited to Gordon Alastair Bell, Guy Ramsay.
Application Number | 20130172190 13/540343 |
Document ID | / |
Family ID | 27839749 |
Filed Date | 2013-07-04 |
United States Patent
Application |
20130172190 |
Kind Code |
A1 |
Bell; Gordon Alastair ; et
al. |
July 4, 2013 |
FORMULATION
Abstract
Agrochemical concentrates having a continuous water-containing
single phase, where said continuous phase also comprises an
oil-based adjuvant and a hydrotrope capable of solubilising said
adjuvant in said continuous phase, a process for making these
concentrates and a method of using these concentrates.
Inventors: |
Bell; Gordon Alastair;
(Bracknell, GB) ; Ramsay; Guy; (Bracknell,
GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Bell; Gordon Alastair
Ramsay; Guy |
Bracknell
Bracknell |
|
GB
GB |
|
|
Assignee: |
Syngenta Crop Protection
LLC
Greensboro
NC
|
Family ID: |
27839749 |
Appl. No.: |
13/540343 |
Filed: |
July 2, 2012 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10567230 |
Feb 3, 2006 |
8211829 |
|
|
PCT/GB2004/003424 |
Aug 6, 2004 |
|
|
|
13540343 |
|
|
|
|
Current U.S.
Class: |
504/330 ;
504/343; 514/345 |
Current CPC
Class: |
A01N 35/10 20130101;
A01N 43/40 20130101; A01N 35/10 20130101; A01N 47/30 20130101; A01N
43/40 20130101; A01N 47/30 20130101; A01N 25/30 20130101; A01N
25/04 20130101; A01N 25/30 20130101; A01N 25/02 20130101; A01N
25/30 20130101; A01N 25/30 20130101; A01N 25/04 20130101; A01N
25/04 20130101; A01N 25/02 20130101; A01N 2300/00 20130101; A01N
2300/00 20130101; A01N 2300/00 20130101; A01N 25/02 20130101; A01N
25/04 20130101; A01N 35/10 20130101; A01N 47/30 20130101; A01N
43/40 20130101; A01N 25/02 20130101 |
Class at
Publication: |
504/330 ;
514/345; 504/343 |
International
Class: |
A01N 25/04 20060101
A01N025/04 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 6, 2003 |
GB |
0318448.8 |
Claims
1. An agrochemical concentrate having a continuous water-containing
phase said continuous phase comprising an oil-based adjuvant and a
hydrotrope capable of solubilising said adjuvant in said continuous
phase; and a second phase dispersed in the continuous phase where
the second phase is solid and comprises an agrochemical; and the
ratio of the adjuvant to the hydrotrope is from 1:10 to 10:1.
2. An agrochemical concentrate as claimed in claim 1 where the
oil-based adjuvant is present at a concentration of greater than or
equal to 10% of the agrochemical concentrate.
3. An agrochemical concentrate as claimed in claim 1 which contains
a third phase comprising a water-immiscible liquid dispersed in the
continuous phase.
4. An agrochemical concentrate as claimed in claim 1 comprising an
agrochemical dissolved in the continuous phase.
5. A continuous oil phase in which is dispersed an agrochemical
concentrate as claimed in claim 1.
Description
[0001] This application is a divisional application of U.S. Ser.
No. 10/567,230 filed Feb. 3, 2006, which is a 371 of International
Application No. PCT/GB2004/003424 filed Aug. 6, 2004, which claims
priority to GB 0318448.8 filed Aug. 6, 2003, the contents of which
are incorporated herein by reference.
[0002] This invention relates to a formulation and in particular to
an aqueous-based formulation concentrate, for example an
aqueous-based agrochemical formulation concentrate, to a process
for making these formulations and to a method of using these
formulations.
[0003] Agrochemical formulation concentrates are often sold as
aqueous-based compositions. A formulation concentrate is intended
to be diluted prior to application, for example by spraying.
Aqueous-based formulation concentrates are desirable since they may
avoid or reduce the need for solvents [used in formulation types
such as emulsifiable concentrates, EC5], have good handling
characteristics, are not flammable, generally have low toxicity,
low phyto-toxicity, have inexpensive raw materials, low
manufacturing costs and have a low odour.
[0004] It is known that aqueous-based compositions can be chosen
from a number of formulation types, including soluble concentrates
(SL), emulsions (both oil in water (EW) and water in oil (EO)),
micro-emulsions (ME), suspension concentrates (SC) and capsule
suspensions (CS). The formulation type chosen in any instance
depends upon the particular purpose envisaged and the physical,
chemical and biological properties of the components of the
composition.
[0005] Soluble Concentrates (SL) may be prepared by dissolving a
compound, for example an agrochemical, in water. These solutions
may contain a surface active agent (for example to improve water
dilution or prevent crystallisation in a spray tank).
[0006] Oil-in-water emulsions (EW) may be prepared by dissolving a
compound, for example an agrochemical, in an organic solvent
(optionally containing one or more wetting agents, one or more
emulsifying agents or a mixture of said agents). Preparation of an
agrochemical EW may involve obtaining an agrochemical either as a
liquid (if it is not a liquid at room temperature, it may be melted
at a reasonable temperature, typically below 70.degree. C.) or in
solution (by dissolving it in an appropriate solvent) and then
emulsifying the resultant liquid or solution into water containing
one or more surface active agents [SFAs], under high shear, to
produce an emulsion. Suitable solvents for use in EWs include
vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes),
aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and
other appropriate organic solvents that have a low solubility in
water. Water-in-oil emulsions (EO) may be prepared in a similar way
to EWs and if a very high oil loading is required or if the nature
of the components dictate then they may be more suitable than an
EW; the EO formulation is two-phase and is designed to phase-invert
upon addition to a spray-tank of water.
[0007] SFAs are chemicals that are able to modify the properties of
an interface (for example, liquid/solid, liquid/air or
liquid/liquid interfaces) by lowering the interfacial tension and
thereby leading to changes in other properties (for example
dispersion, emulsification and wetting).
[0008] Microemulsions (ME) may be prepared by mixing water with a
blend of one or more solvents with one or more SFAs, to produce
spontaneously a thermodynamically stable liquid formulation. To
prepare an agrochemical ME, an agrochemical is present initially in
either the water or the solvent/SFA blend. Suitable solvents for
use in MEs include those hereinbefore described for use in EWs. An
ME may be either an oil-in-water or a water-in-oil system (which
system is present may be determined by conductivity measurements)
and may be suitable for mixing water-soluble and oil-soluble
agrochemicals in the same formulation. An ME is suitable for
dilution into water, either remaining as a microemulsion or forming
a conventional oil-in-water emulsion. Suspension concentrates (SC)
may comprise aqueous or non-aqueous suspensions of finely divided
insoluble solid particles. Agrochemical SCs may be prepared by ball
or bead milling a solid agrochemical in a suitable medium,
optionally with one or more dispersing agents, to produce a fine
particle suspension of the agrochemical. One or more wetting agents
may be included in the composition and a suspending agent may be
included to reduce the rate at which the particles settle.
Alternatively, an agrochemical may be dry milled and added to
water, containing agents hereinbefore described, to produce the
desired end product.
[0009] Capsule suspensions (CS) may be prepared in a manner similar
to the preparation of EW formulations but with an additional
polymerisation stage such that an aqueous dispersion of oil
droplets is obtained, in which each oil droplet is encapsulated by
a polymeric shell and contains an agrochemical and, optionally, a
carrier or diluent therefor. The polymeric shell may be produced by
either an interfacial polycondensation reaction or by a
coacervation procedure. Agrochemical compositions may provide
controlled release of an agrochemical, reduce operator exposure to
an agrochemical or they may be used for seed treatment.
[0010] Some compositions may contain a mixture of an agrochemical
with one or more other agrochemicals or other additives. Some
mixtures may comprise agrochemicals or additives that have
significantly different physical, chemical or biological properties
such that they do not easily lend themselves to the same
conventional formulation type. In these circumstances other
formulation types may be prepared. For example, where one
agrochemical is a water insoluble solid and another agrochemical is
a water insoluble liquid, it may nevertheless be possible to
disperse each agrochemical in the same continuous aqueous phase by
dispersing the solid agrochemical as a suspension (using a
preparation analogous to that of an SC) but dispersing the liquid
agrochemical as an emulsion (using a preparation analogous to that
of an EW). The resultant composition is a suspoemulsion (SE)
formulation.
[0011] The term "agrochemicals" includes herbicides, fungicides and
insecticides.
[0012] Dispersing aids are generally used to maintain solids or
liquids in dispersion and adjuvants are commonly used to enhance
the bioperformance (activity) of an agrochemical. Adjuvants can
vary in complexity from simple surfactants to multi-component
blends of oils. Such adjuvants may be "tank-mix" adjuvant systems
which are added to agricultural spray tanks separately from an
agrochemical formulation but it is more convenient to provide a
formulation where all necessary dispersing aids and adjuvants are
incorporated directly in ("built-in") to a formulation concentrate,
such as an SC, EW, SE, SL, CS or ME. This ensures that the farmer
will use the correct adjuvant, and also controls the ratio of
adjuvant to agrochemical. Oil-based adjuvants are particularly
useful in enhancing the bioperformance of an agrochemical but are
also inherently difficult to build-in to an aqueous concentrate at
a desirably high concentration. As used herein, the term "oil-based
adjuvant" means a liquid adjuvant or mixture of adjuvants that is
substantially insoluble in the aqueous continuous phase of the
agrochemical concentrate.
[0013] SC, EW, SE, SL, CS or ME formulation concentrates may be
formulated with surfactants and oil blends but this often leads to
problems of incompatibility, particularly since the concentrates
are required to be physically stable over extended periods of time
and under the extremes of temperature encountered during commercial
use. Stability problems may include flocculation,
heteroflocculation, crystal growth of a dispersed solid, creaming
of a dispersed liquid, creaming of an adjuvant/surfactant system,
phase separation and chemical decomposition.
[0014] Canadian Patent 1186217 discloses the use of a hydrotrope to
solubilise a liquid agrochemical in to water, optionally in the
presence of a small concentration of a functional aid.
[0015] It is desirable therefore to provide a physically stable
agrochemical concentrate whether it is a "tank-mix" or a "built-in"
formulation containing a bioperformance enhancing oil-based
adjuvant at high loading. The present invention meets this need
through the use of hydrotropes.
[0016] In the context of the present invention an agrochemical
concentrate does not necessarily contain an agrochemical compound;
the agrochemical concentrate may simply be an adjuvant system
intended for "tank-mixing" with another agrochemical concentrate
which does contain an agrochemical compound.
[0017] According to the present invention there is provided an
agrochemical concentrate having a continuous water-containing
single phase which is characterised in that said continuous phase
also comprises an oil-based adjuvant and a hydrotrope capable of
solubilising said adjuvant in the continuous phase.
[0018] In another aspect, the present invention provides an aqueous
agrochemical suspension concentrate comprising an oil-based
adjuvant and a hydrotrope capable of solubilising said adjuvant in
the aqueous phase.
[0019] A hydrotrope is a substance that, at high concentrations,
enhances the solubility of non-polar compounds (oils) in water. In
the literature, there are some inconsistent discussions of the
properties of hydrotropes; for the purpose of the present
invention, hydrotropes are considered to be substances which are
highly water soluble and amphiphilic and which do not form micelles
when present alone in water at concentrations below 50% by weight.
Solubilisation of oils by hydrotropes is characterised by the
relatively high concentrations of the hydrotropes needed and the
larger amount of oil solubilised compared with that observed for
conventional micellar surfactants. Examples of hydrotropes which
may be used in the present invention include anionic benzoates,
anionic benzosulphonates, anionic phosphates and phosphonates,
anionic benzophosphates, alkylarylphosphates and phosphonates,
neutral phenols such as catechol and resorcinol, aliphatic
glycolsulfates, alicyclic bile salts, aliphatic carboxylates,
aromatic carboxylates, naphthalene sulphonates, alkynaphthalene
sulphonates, polymeric naphthalene sulphonates and their
copolymers, alkyl aryl sulphonates and carboxylates and their
polymers and copolymers, naphthalene and alkylnaphthalene
phosphates and phosphonates and their polymers and copolymers,
glycol and glycerol ethers and the amino acid proline. In general a
given hydrotrope will solubilise a specific group of oils or oil
blends. Simple test tube experiments enable a potential
hydrotrope/oil mixture to be assessed quickly and easily;
hydrotropic mixtures form a single phase which can be detected by
eye.
[0020] As examples of oil-based agrochemical adjuvants suitable for
use in combination with the above hydrotropes there may be
mentioned seed oils, methylated seed oils, triglycerides of fatty
acids and fatty amines, methyl esters of fatty acids and fatty
amines, mineral oils which can be linear, branched or mixtures of
linear and branched, aromatic oils, fatty alcohols, fatty acids,
fatty amines, aliphatic alcohols, aliphatic amines, aliphatic
esters, aliphatic carboxylic acids, aliphatic ketones, aliphatic
aldehydes, aliphatic amides, aromatic carboxylic acids, aromatic
alcohols and phenols, aromatic ketones, aromatic aldehydes,
aromatic amines or anilines or anilides, aromatic amides, natural
products such as terpenes, sesquiterpenes and diterpenes, alkyl or
aryl or alkylaryl phosphates and phosphonates. Included also are
halogenated variants of the forementioned oils. Similarly
ethoxylated variants of the alcohols, amines and acids mentioned
are also suitable providing the degree of ethoxylation is not too
long, for example having an average degree of ethoxylation below 4.
Brij 92 [BRIJ is a trademark], oleyl alcohol ethoxylate with an
average of 2 moles of ethoxylate is an example of a suitable
ethoxylated fatty alcohol and Ethomeen S12 [ETHOMEEN is a
trademark] is an example of a short chain ethoxylated fatty amine.
Silicone oils are also suitable. Oil blends may also be used, for
example Turbocharge (Turbocharge is a tradename of Syngenta
Limited), which is a proprietary blend of oils and short chain
ethoxylates. Other commercially available blends of oils and short
chain ethoxylates include Merge, Dash, BreakThru 464 and Agridex
[these are all trademarks]. The commercial product Agral 90 [AGRAL
is a trademark] is a blend of ethoxylated nonylphenols.
[0021] Another group of oil adjuvants includes the long chain
ethoxylate versions of synthetic or fatty acids, alcohols and
amines. These adjuvants are unusual in that they from viscous,
hexagonal or cubic phases at high concentrations in water.
Hydrotropes may be used to prevent this from happening, thus
allowing high loadings to be achieved in agrochemical concentrates
of the present invention. As examples of preferred combinations of
hydrotrope and oil-based adjuvants suitable for use to improve the
bioperformance of agrochemicals, there may be mentioned:
[0022] (a) Benzosulphonate hydrotropes such as ammonium cumene
sulphonate and ammonium xylene sulphonate in combination with fatty
alcohols, fatty acids or fatty amines and simple derivatives
thereof such as methyl esters and adjuvant oils derived from plant
terpenes.
[0023] Anionic alkylaryl carboxylatehydrotropes such as the
potassium salt of 5(6)-carboxy-4-hexyl-2-cyclohexene-1 octanoic
acid (commercially available under the trade name WESTVACCO H240)
in combination with fatty alcohols, fatty acids or fatty amines and
simple derivatives thereof such as methyl esters and short chain
ethoxylates, especially when these materials are also blended with
linear or branched mineral oils.
[0024] Phenol type hydrotropes, such as sodium salicylate, in
combination with long chain ethoxylate versions of synthetic or
fatty acids, alcohols and amines.
[0025] As preferred examples of combinations of type (a) above
there may be mentioned the hydrotrope ammonium cumene sulphonate in
combination with oleyl alcohol or the plant terpene phytol or the
plant terpene geraniol and the hydrotrope ammonium xylene
sulphonate in combination with the plant terpene geraniol. As
preferred combinations of type (b) above there may be mentioned the
hydrotrope 5(6)-carboxy-4-hexyl-2-cyclohexene-1 octanoic acid in
combination with oleyl alcohol or the commercially available
adjuvant Turbocharge. As preferred combinations of type (c) above
there may be mentioned the hydrotrope sodium salicylate in
combination with ETHOMEEN T25 [a tallow amine ethoxylate; ETHOMEEN
is a Trademark]. We have found that for agrochemicals such as
selective herbicides, insecticides and fungicides that are not
intended to harm the target plant, the built-in combination of the
oil-based adjuvant and the hydrotrope may often be less phytotoxic
to target plants than the conventional tank-mixed adjuvant system,
whilst delivering equivalent biological activity. The hydrotrope
system also offers biological advantages in that the agrochemical
concentrates of the present invention may also deliver equivalent
biological activity to conventional formulation concentrates
despite using smaller amounts of the oil-based adjuvant. Therefore,
in another aspect of the invention, there is provided the use of an
agrochemical concentrate of this invention to provide low
phytotoxicity.
[0026] It is to be understood that the hydrotrope solubilises the
oil-based adjuvant into the aqueous medium in which an agrochemical
is optionally dispersed in the concentrate of the present
invention. The aqueous medium need not necessarily be a true
solution in the physical sense but will appear to be a single phase
to the eye and under the microscope and will remain as such over
extended storage periods, and in many instances essentially
indefinitely. It is a further advantage of the hydrotrope
solubilised systems of the present invention, not only that
relatively high levels of oil-based adjuvant may be incorporated
but also that the resultant composition has a relatively low
viscosity. Such compositions are poured from a container without
difficulty and without leaving excessive residues in the container.
The composition is readily diluted in the spray tank and any
residues remaining in an empty container are simply and easily
rinsed out. The compositions of the invention are typically
Newtonian fluids with viscosity less than 1000 cP at room
temperature.
[0027] The present invention does not depend critically on the
nature of the agrochemical present in the formulation concentrate.
Those skilled in the art will be well aware of the criteria for a
given agrochemical to be suitable for a specific formulation type.
As examples of herbicides suitable for formulation as a concentrate
there may be mentioned mesotrione, fomesafen, tralkoxydim,
napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene,
toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop, clodinafop,
clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop,
quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid,
isoxaben, tebutam, chlorthal dimethyl, benomyl, benfuresate,
dicamba, dichlobenil, benazolin, triazoxide, fluazuron,
teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor,
pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim,
cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb,
bifenox, oxyfluorfen, acifluorfen, fluoroglycofen-ethyl,
bromoxynil, ioxynil, imazamethabenz-methyl, imazapyr, imazaquin,
imazethapyr, imazapic, imazamox, flumioxazin, flumiclorac-pentyl,
picloram, amodosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron,
triasulfuron, triallate, pebulate, prosulfocarb, molinate,
atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine,
terbutryn, sulcotrione, isoproturon, linuron, fenuron,
chlorotoluron and metoxuron.
[0028] As examples of fungicides suitable for formulation as a
concentrate there may be mentioned azoxystrobin, trifloxystrobin,
kresoxim methyl, famoxadone, metominostrobin and picoxystrobin,
cyprodanil, carbendazim, thiabendazole, dimethomorph, vinclozolin,
iprodione, dithiocarbamate, imazalil, prochloraz, fluquinconazole,
epoxiconazole, flutriafol, azaconazole, bitertanol, bromuconazole,
cyproconazole, difenoconazole, hexaconazole, paclobutrazole,
propiconazole, tebuconazole, triadimefon, triticonazole,
fenpropimorph, tridemorph, fenpropidin, mancozeb, metiram,
chlorothalonil, thiram, ziram, captafol, captan, folpet, fluazinam,
flutolanil, carboxin, metalaxyl, bupirimate, ethirimol,
dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin and
prothioconazole.
[0029] As examples of insecticides suitable for formulation as a
concentrate there may be mentioned thiamethoxam, imidacloprid,
acetamiprid, clothianidin, dinotefuran, nitenpyram, fipronil,
abamectin, emamectin, bendiocarb, carbaryl, fenoxycarb, isoprocarb,
pirimicarb, propoxur, xylylcarb, asulam, chlorpropham, endosulfan,
heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos
methyl, aldicarb, methomyl, cyprmethrin, bioallethrin,
deltamethrin, lambda cyhalothrin, cyhalothrin, cyfluthrin,
fenvalerate, imiprothrin, permethrin, halfenprox and tefluthrin.
The foregoing lists are not intended to be exhaustive and other
examples will occur to those skilled in the art.
[0030] The agrochemical concentrate of the present invention may
also incorporate one or more surfactants or dispersing agents to
assist the dispersion of an agrochemical in the aqueous medium
(dispersant system). The dispersant system will not generally
contribute to enhancement of the bioperformance of the agrochemical
and is present primarily to assist in maintaining the dispersed
agrochemical in dispersion. Conversely the oil-based adjuvant will
not generally assist directly in maintaining the agrochemical in
dispersion. Many individual dispersants and mixtures thereof
suitable for forming a dispersant system for a concentrate are
known to those skilled in the art and a very wide range of choices
is available. Typical dispersants that may be used to form a
dispersant system include copolymers of ethylene oxide and
propylene oxide, aryl and alkyl aryl sulphonate copolymers with
formaldehyde such as naphthalene sulphonate formaldehyde
copolymers, salts of the copolymers of acrylic acid with
diisobutylene or ethylene oxide or styrene or vinyl pyrrolidone,
salts of copolymers of styrene sulphate with ethylene oxide or
diisobutylene or vinyl pyrrolidone or propylene oxide,
tristyrylphenol type dispersants where the phenol has been
ethoxylated and optionally sulphonated or phosphated, alkylphenol
ethoxylates, polyvinyl alcohol and substituted or sulphated
polyvinyl alcohols, polyvinyl pyrrolidone and its copolymers.
[0031] The agrochemical is conventionally present in the
concentrate at a concentration between 5 and 60% and typically of
about 10 to 35% by weight. The hydrotrope is suitably present in
the concentrate at a concentration of from 5 to 50% and typically
from about 15 to 30% by weight. The oil-based adjuvant is suitably
present at a concentration of greater than or equal to 10%,
conveniently from 10 to 60% and typically from 10 to 40% by weight.
The dispersant system is typically present at a concentration of
total dispersant of from 0 to 40% and preferably from 0 to 20% by
weight. The dispersant system may comprise a mixture of
dispersants. A typical example of a mixture of dispersants includes
a copolymer of ethylene oxide and propylene oxide, such as Atlox
4894 or Atlox 4896 [ATLOX is a trademark], in a quantity from 0 to
20% for example from 1 to 8% w/w combined with a further dispersant
such as Atlox 10/5 or Brij 96 in a concentration of 0 to 20%, for
example from 1 to 9% w/w. The ratio of oil-based adjuvant to
hydrotrope suitably varies from 1:10 to 10:1, for example from 1:3
to 3:1.
[0032] In a further aspect, the present invention provides an
agrochemical concentrate as described above which contains a second
phase dispersed in the continuous single phase. In one aspect, the
second phase is a solid [this aspect includes SC formulations of
the invention]. In another aspect, the second phase comprises a
water-immiscible liquid [this aspect includes EW formulations of
the invention]. Conveniently, the second phase is
micro-encapsulated [this aspect includes CS formulations of the
invention].
[0033] Alternatively, the second phase may be a micro-emulsion
[this aspect includes ME formulations of the invention].
[0034] In a still further aspect, the present invention provides an
agrochemical concentrate as described above which contains a third
phase comprising a water-immiscible liquid dispersed in the
continuous single phase [this aspect includes SE formulations of
the invention].
[0035] In yet another aspect, the present invention provides an
agrochemical concentrate comprising an agrochemical dissolved in
the continuous phase.
[0036] In another aspect, the present invention provides an
agrochemical concentrate where the second phase comprises an
agrochemical.
[0037] In yet another aspect, the present invention provides an
agrochemical concentrate as described above where the second phase
comprises an agrochemical or the third phase comprises an
agrochemical or both these phases each comprise an agrochemical
which may be the same or different agrochemicals.
[0038] In an additional aspect, the present invention provides
which a continuous oil phase in which is dispersed an agrochemical
concentrate as described above [this aspect includes EO
formulations of the invention].
[0039] The formulation concentrates of the present invention may be
prepared by conventional techniques. However, previously,
conventional techniques have not permitted an oil-based adjuvant
readily to be introduced early in the process, mainly due to
viscosity-related problems. Since the use of a hydrotrope with the
oil-based adjuvant reduces these viscosity problems it has now been
found that it is possible to prepare the continuous phase of the
present invention first and then for any subsequent processing to
take place in that said continuous phase. This enables preparation
of high concentration products, faster production, use of fewer
production vessels and leads to overall process cost reduction.
[0040] Therefore, according to another aspect of the present
invention there is provided a process for the manufacture of an
agrochemical concentrate of the present invention where the
continuous phase is prepared first and then any subsequent
processing takes place in that said continuous phase.
[0041] A suspension concentrate may be made using conventional
techniques. Typically in commercial practice, a solid herbicide is
milled in water until the desired particle size is reached. The
particle size is typically from 0.5 to 15 microns, for example from
1 to 5 microns volume median diameter. A dispersant system is
generally added before milling so that it is present during the
milling process. The stage at which the hydrotrope and oil-based
adjuvant are added is not critical. It is generally convenient to
add the hydrotrope together with the oil to the aqueous system
before, during or after milling.
[0042] According to another aspect of the present invention there
is provided a process for the manufacture of a suspension
concentrate which comprises milling a solid agrochemical in water,
optionally in the presence of a dispersant system, characterised in
that there is incorporated in the composition a hydrotrope and an
oil-based adjuvant for the agrochemical.
[0043] The invention is illustrated by the following non-limiting
Examples in which all parts and percentages are by weight unless
otherwise stated. Whilst the majority of the Examples relate to an
aqueous agrochemical suspension concentrate, they could be modified
readily to other formulation types.
[0044] The composition of the products used in the Examples was as
follows:--
Morwet D425--A commercially available anionic naphthalene
sulphonate formaldehyde condensate copolymer, sold by Crompton
Corporation Synperonic 10/5--A commercially available surfactant
comprising a short chain branched alcohol with five moles of
ethylene oxide. Sold by Uniqema Ltd Atlox 4896--A copolymer
condensate of ethylene and propylene oxide, sold by Uniqema Ltd.
Atlox 4913--A copolymer condensate of ethylene oxide with methyl
methacrylate, sold by Uniqema Ltd. Atlox 4894--A copolymer
condensate of ethylene and propylene oxide, sold by Uniqema Ltd.
Brij 96--A fatty alcohol condensed with an average of 10 moles of
ethylene oxide. Sold by Uniqema Ltd Eltesol AC 60--Ammonium cumene
sulphonate supplied by Albright and Wilson Ltd.
EXAMPLE 1
[0045] The herbicide tralkoxydim (10%) having a particle size of
about 50 microns, Morwet D425 (8%), Westvacco H240 (29%),
Turbocharge (30%), Synperonic 10/5 (6%) and water (17%) to a total
weight of 5 g was added to a glass vial. The Westvacco H240 was the
hydrotrope and the Turbocharge was the oil-based adjuvant. Morwet
D425 and Synperonic 10/5 together formed the dispersant system. The
mixture was gently swirled and sheared for one minute using an
Ystral mixer, which reduced the particle size of the tralkoxydim to
a volume mean of 25 microns. An equal volume of No 4 zirconia beads
was added to the vial which was then shaken for 30 minutes in a
laboratory shaker.
[0046] The sample could be both poured and pipetted easily and this
was taken as an indication that the viscosity was satisfactory
(viscosity test). The sample dispersed readily in water without
agitation, at a dilution of 1% and a standing time of one minute
(dilution test). The sample also passed a standard flocculation
test. In this test a 1% dilution of the sample was made using CIPAC
standard hard water C. The sample was inverted to ensure
homogeneity and was left to stand for one hour. After this time it
was examined by microscope to observe any signs of flocculation. If
there were no signs of flocculation the sample met the flocculation
test.
EXAMPLES 2 TO 5
[0047] The procedure described in example 1 was repeated for the
samples shown in Table 1. These samples all contained the
commercial herbicide tralkoxydim with the commercial tank mix
adjuvant Turbocharge. All samples passed the viscosity, dilution
and flocculation tests.
TABLE-US-00001 TABLE 1 Composition in % by weight Example Tralk-
Morwet Westvacco Turbo- Synperonic No oxydim D425 H240 charge 10/5
Water 2 12 4 25 38 0 21 3 16 5 27 25 0 27 4 15 5 25 25 5 25 5 16 2
25 22 0 35
EXAMPLES 6 TO 11
[0048] The compositions listed in Table 2 were prepared using the
procedure of Example 1. In each case however the dispersant Morwet
D425 has been replaced with Atlox 4894. All samples passed the
viscosity, dilution and flocculation tests.
TABLE-US-00002 TABLE 2 Composition in % by weight Example Tralk-
Westvacco Turbo- Synperonic Atlox No oxydim H240 charge 10/5 4894
Water 6 10 25 17 9 8 31 7 10 30 25 8 6 21 8 10 20 30 3 8 29 9 13 19
26 3 8 31 10 10 22 11 5 0 52 11 20 31 20 7 8 14
EXAMPLES 12 TO 15
[0049] The compositions listed in Table 3 were prepared using the
procedure of Example 1. The Examples illustrate the use of
different dispersant systems. All samples passed the viscosity,
dilution and flocculation tests. In Table 3, D1 is Atlox 4896, D2
is Atlox 4913, D3 is Atlox 4894 and D4 is Morwet D425
TABLE-US-00003 TABLE 3 Composition in % by weight Ex- West- Syn-
ample Tralk- vacco Turbo- peronic No oxydim H240 charge 10/5 Water
D1 D2 D3 D4 12 20 31 20 7 14 8 0 0 0 13 20 31 20 7 14 4 4 0 0 14 20
31 20 7 14 0 0 4 4 15 20 31 20 7 14 0 0 8 0
EXAMPLES 16 AND 17
[0050] The compositions listed in Table 4 were prepared using the
procedure of Example 1. The Examples illustrate the use of
different dispersant systems. All samples passed the viscosity,
dilution and flocculation tests. In Table 4, C1 is Synperonic 10/5,
C2 is Brij 96.
TABLE-US-00004 TABLE 4 Composition in % by weight Example Morwet
Westvacco Turbo- No Tralkoxydim D425 H240 charge Water C1 C2 16 15
5 25 25 25 0 5 17 15 5 25 25 25 5 0
EXAMPLES 18 AND 19
[0051] The compositions listed in Table 5 were prepared using the
procedure of Example 1 but used the commercial herbicide diuron in
place of tralkoxydim. All samples passed the viscosity, dilution
and flocculation tests.
TABLE-US-00005 TABLE 5 Composition in % by weight Example Atlox
Westvacco Synperonic No Diuron 4894 H240 Turbocharge 10/5 Water 18
13 8 19 26 3 31 19 10 8 20 30 3 29
EXAMPLES 20 TO 23
[0052] The compositions listed in Table 6 were prepared using the
procedure of Example 1 but used the commercial fungicide
picoxystrobin in place of tralkoxydim. All samples passed the
viscosity, dilution and flocculation tests.
TABLE-US-00006 TABLE 6 Composition in % by weight Example Atlox
Westvacco Turbo- Synperonic No Picoxystrobin 4894 H240 charge 10/5
Water 20 21 6 27 19 4 23 21 24 5 27 17 3 24 22 19 8 26 17 3 27 23
30 8 31 17 3 11
EXAMPLE 24
[0053] This example illustrates the formation of a hydrotrope
formulation containing the oil oleyl alcohol with the hydrotrope
ammonium cumene sulphonate.
[0054] Tralkoxydim (10%), Atlox 4894 (8%), Eltesol AC 60 (13%),
Oleyl alcohol (30%), Synperonic 10/5 (3%) and water (36%) to a
total weight of 5 g was added to a glass vial. The mixture was
gently swirled and sheared for one minute using an Ystral mixer. An
equal volume of no 4 zirconia beads was added to the vial which was
then shaken for 30 minutes in a laboratory shaker.
[0055] The resulting sample passed the viscosity, dilution and
flocculation tests.
EXAMPLE 25
[0056] Three hydrotrope formulations were prepared using the method
outlined in Example 1. Table 7 shows the ingredients that were
used.
TABLE-US-00007 TABLE 7 Composition in % by weight Com- Westvacco
Atlox Turbo- Synperonic position Tralkoxydim H240 4894 charge 10/5
Water H 1 20 31 8 20 7 14 H 2 13 19 8 26 3 31 H 3 10 20 8 30 3
29
[0057] These samples passed the viscosity, dilution and
flocculation tests, and were used for biological testing.
[0058] A sample of a commercial tralkoxydim suspension concentrate
available under the tradename `Achieve 25 SC` was used as a
reference material. The strength of the suspension concentrate was
25% w/w. The reference material was tank mixed with commercial
Turbocharge at two rates, these being 0.2% and 0.5% v/v of the
spray tank volume. The ratio by weight of Turbocharge to
tralkoxydim in the compositions is given below in Table 11 at an
application rate of 50 g/ha. Plant species (weeds against which
tralkoxydim is effective) were grown and tested under glasshouse
conditions. Alopecuius myosuroides (ALOMI), Avena fatua (AVEFA),
Echinochloa crus-galli (ECHCG) and Lolium rigidum (LOLRI) were
grown to the 2.3 leaf stage and Setaria viridis (SETVI) to stage
3.3, and were sprayed with 100 litres/hectare of spray solution
using a laboratory track sprayer. The agrochemical application rate
was 50 g/ha. Tralkoxydim is a selective herbicide for use on wheat
and barley and phytotoxicity against these species is therefore
undesirable. The wheat species Triticum aestivum (TRZAS) cultivar
`Barrie`, and the barley variant Hordeum vulgaris (HORVU) `Bonanza`
were sprayed at rates of 50, 100, 200 and 400 g/ha. The percentage
crop damage was assessed at 11 and 22 days after application, and
the weed control at 22 days after application.
[0059] Table 8 shows the phytotoxicity of each formulation scored
as percentage leaf damage on two crop species 11 days after
treatment. The score represents the mean value taken from all of
the rates, with three replicated of each rate.
TABLE-US-00008 TABLE 8 Leaf Damage 11 DAT % TRZAS HORVU Composition
`Barrie` `Bonanza` H1 5 2 H2 3 4 H3 10 2 Achieve SC' + 0.2%
Turbocharge 13 7 Achieve SC' + 0.5% Turbocharge 15 12
[0060] Table 9 shows the percentage kill for each formulation on
five weed species. The top rate of tralkoxydim (50 g/ha) was used
and results are the mean of three replicates. At this application
rate the ratio of Turbocharge to tralkoxydim for the five
formulations is shown in Table 10.
TABLE-US-00009 TABLE 9 % Kill against Weed Species Formulation
ALOMY AVEFA LOLRI SETVI H 1 75.0 80.0 63.3 61.7 H 2 88.3 85.0 43.3
46.7 H 3 86.7 93.3 68.3 73.3 Achieve SC' + 0.2% 86.7 86.7 68.3 65.0
Turbocharge Achieve SC' + 0.5% 86.7 90.0 83.3 66.7 Turbocharge
TABLE-US-00010 TABLE 10 Ratio of Turbocharge to Tralkoxydim
Formulation Ratio Turbocharge/Tralkoxydim H1 1 H2 2 H3 3 Achieve
SC' + 0.2% Turbocharge 3.5 Achieve SC' + 0.5% Turbocharge 8.75
[0061] The biological efficacy of each formulation as a weed killer
is statistically the same. As the hydrotrope formulations all
contained less Turbocharge relative to the tralkoxydim than the
tank mixed formulations they were therefore as good as, or better
than, the tank mixed formulations, while at the same time being
less phytotoxic to crop species.
EXAMPLE 26
[0062] This example illustrates the formation of a hydrotrope
formulation containing the oil-adjuvant oleyl alcohol with the
hydrotrope Westvacco H240. Oleyl alcohol and Westvacco H240 were
mixed together at room temperature in the ratio 1:1 by weight,
leading to a mixture of water, oleyl alcohol and the potassium salt
of 5(6)-carboxy-4-hexyl-2-cyclohexene-1 octanoic acid [the
hydrotrope of Westvacco H240] in the ratio 30:50:20 by weight; a
homogeneous single phase liquid formed spontaneously.
EXAMPLE 27
[0063] This example illustrates the formation of a hydrotrope
formulation containing the oil-adjuvant Ethomeen T25 with the
hydrotrope sodium salicylate. Water, Ethomeen T25 and sodium
salicylate were mixed together at room temperature in the ratio
25:50:25 by weight; a homogeneous single phase liquid formed
spontaneously. This hydrotrope formulation could be diluted with
water, becoming less viscous but retaining its hydrotropic nature.
By contrast Ethomeen T25 alone, when diluted with water formed
viscous gel phases.
EXAMPLE 28
[0064] This example illustrates the formation of a hydrotrope
formulation containing the oil-adjuvant Turbocharge with the
hydrotrope Westvacco H240. Turbocharge and Westvacco H240 were
mixed together at room temperature in the ratio 1:1 by weight,
leading to a mixture of water, Turbocharge and the potassium salt
of 5(6)-carboxy-4-hexyl-2-cyclohexene-1 octanoic acid [the
hydrotrope of Westvacco H240] in the ratio 30:50:20 by weight; a
homogeneous single phase liquid formed spontaneously. This
hydrotrope formulation could be diluted with water, retaining its
hydrotropic nature until at high dilution it formed a fine
emulsion.
* * * * *