AU2018282387A1

AU2018282387A1 - Suspension concentrate composition

Info

Publication number: AU2018282387A1
Application number: AU2018282387A
Authority: AU
Inventors: Tung Ngoc Le; Philip Edward Pentland
Original assignee: Farmalinx Pty Ltd
Current assignee: Farmalinx Pty Ltd
Priority date: 2017-12-22
Filing date: 2018-12-20
Publication date: 2019-07-11

Abstract

Abstract An aqueous suspension concentrate composition comprising suspended particles of clofentezine and suspended particles of abamectin wherein the composition comprises a first surfactant component selected from the group consisting of naphthalene sulfonate-formaldehyde condensates that may optionally be alkyl substituted and salts thereof and mixtures thereof and a second surfactant component selected from the group consisting of polyarylether salts, polycarboxylates, alcohol ethoxylates, and comb-type graft copolymers.

Description

[0001] This invention relates to suspension concentrate formulations that include both clofentezine and abamectin. In particular this invention relates to storage stable suspension concentrate formulations of clofentezine and abamectin.

Background [0002] Clofentezine (also referred to as bisclofentezine, bisclofentezine and 3,6Bis(2-chlorophenyl)-1,2,4,5-tetrazine) has been sold under trade names such as Apollo, Acaristop, Ovation and Panatac. Clofentezine is a miticide/acaricide.

[0003] Abamectin (also referred to under trade names including Abba, Abathor, Affirm, Agri-Mek, Avid, Dynamec, Reaper, Zephyr and Cure) is an insecticide as well as an acaricide and a nematicide.

[0004] The use of abamectin and clofentezine together has the potential to provide enhanced control of insect and arachnid/mite pests as abamectin is primarily active against adults whereas clofentezine is particularly active against eggs, larvae and nymphs.

[0005] The use of the two pesticides has until now been carried out by separate application of the pesticides or by tank mixing (Cloyd, Greenhouse Patent News, December, 2008, 24-30). Tank mixing involves forming a dilute mixture by combining the two pesticides in a relatively large volume of water shortly before spray application.

[0006] Tank mixing requires the user to measure appropriate quantities of each pesticide so as to provide good activity of each and to ensure compatibility of the formulations to avoid ineffective application or blockage of spray equipment.

[0007] Tank mixing thus carries undesirable risks of inappropriate mixtures, ineffective pest control, spillage and contamination by the chemicals and risks to health and safety. Also, in some cases individual pesticide concentrates are not compatible on tank mixing or do not provide as effective control as when used in combination.

2018282387 20 Dec 2018 [0008] Coformulation of abumectin and clofentezine, while having the potential to avoid the shortcomings of separate application or tank mixing has not generally been successful due to the difficulty in achieving a shelf stable concentrate of the two pesticides. Each of abamectin and clofentezine is water insoluble and would require a mixture of components in the composition in which stability of both is maintained in the combination in a single carrier.

[0009] CN1391810 teaches a combination pesticide in which component A is abamectin and component B is one selected from clofentezine or azocyclotin. The preferred ratio of abamectin to clofentezine is in the range 1:20 to 1:80. The disclosed composition are wettable powder formulations. Wettable powder formulations contain the active agent and auxiliaries and are not mixed with water until immediately before use.

[0010] The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

Summary [0011] There is provided an aqueous suspension concentrate comprising suspended particles of clofentezine and suspended particles of abamectin wherein the composition comprises a first surfactant component selected from the group consisting of naphthalene sulfonate-formaldehyde condensates that may optionally be alkyl substituted and salts thereof and mixtures thereof and a second surfactant component selected from the group consisting of polyarylether salts such as polyarylether sulfates and phosphates, polycarboxylates, alcohol ethoxylates, and comb-type graft copolymers.

[0012] In a further aspect there is provided a process for preparation of the suspension concentrate comprising combining particulate abamectin and particulate clofentezine with an aqueous mixture comprising the first surfactant component and the second surfactant component and optionally milling the composition to reduce the

2018282387 20 Dec 2018 particle size of abamectin and clofentezine to provide an aqueous suspension concentrate comprising suspended particles of clofentezine and suspended particles of abamectin.

[0013] In a further set of embodiments there is provided a method of controlling pests comprising applying to the pests or locus of the pests the suspension concentrate described above.

Detailed Description [0014] The term “comb-graft” in relation to polymers is used herein to refer to those polymers the structure of which, similar to that of a comb, has a backbone polymer chain to which are appended polymer chains different from the backbone which can be the same or of different natures and lengths. In the preferred embodiment of the invention the comb-graft polymers have a backbone chain of a polymer such as (meth) acrylic polymer or copolymer to which are appended polyoxyalkylated lateral groups such as polyoxyethylene groups.

[0015] The term (meth) acrylate refers to acrylate and/or methacrylate.

[0016] The term polymer includes homopolymers, copolymers and oligomers.

[0017] A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from aggregating. Dispersing agents are added to agrochemical compositions to facilitate dispersion and suspension during manufacture, and to ensure the particles remain in homogeneous suspension when the formulation is diluted by adding it to the water in a spray tank.

[0018] As used herein, the terms “first”, “second”, etc in relation to components such as surfactants of the disclosed composition are arbitrarily assigned and are merely intended to differentiate between two or more such features of the composition. The terms do not of themselves indicate any particular orientation or sequence. Moreover, it is to be understood that the presence of a “first” component does not imply that a “second” component is present, the presence of a “second” component does not imply that a “first” component is present, etc.

2018282387 20 Dec 2018 [0019] Throughout the description and the claims of this specification the word “comprise” and variations of the word, such as “comprising” and “comprises” is not intended to exclude other additives, components, integers or steps.

[0020] The aqueous suspension concentrate composition comprises suspended particles of clofentezine and suspended particles of abamectin.

[0021] The weight ratio of clofentezine to abamectin in one set of embodiment is in the range 3:1 to 100:1. We have found the weight ratio of clofentezine to abamectin in the range 5:1 to 20:1 to be particularly efficacious. The most preferred ratio of clofentezine to abamectin is 7:1 to 14:1. The total content of abamectin and clofentezine in one set of embodiments is at least 50 g/L, such as 50 g/L to 600 g/L or 100 g/L to 500 g/L. In general high loading of the active component is preferred to minimise the water content and reduce storage and handling costs. In one set of embodiments the composition comprises 150 to 250 g/L clofentezine and 5g/L to 30 g/L abamectin such as 12 g/L to 30 g/L abamectin. In another set of embodiments the composition comprises 170 to 220 g/L clofentezine and 12 g/L to 25 g/L abamectin The composition enables excellent storage stability to be achieved by virtue of the combination of actives with the surfactant components.

[0022] The composition comprises a first surfactant component selected from the group consisting of naphthalene sulfonate-formaldehyde condensates that may optionally be alkyl substituted and salts thereof and mixtures thereof. The alkyl substituent, where present, may be a Ci to Ce alkyl substituent such as methyl or butyl.

[0023] In one set of embodiments the first surfactant comprises a naphthalene sulfonate condensate such as a sodium salt of alkylnaphthalene sulfonateformaldehyde condensate, for example the sodium salt of methyl naphthalene sulfonate acid-formaldehyde condensate, which we have found to be particularly useful.

[0024] A preferred dispersing agent is a naphthalene sulphonate condensate, for example sodium alkylnaphthalene sulfonate-formaldehyde condensate (e.g. Morwet® D425).

2018282387 20 Dec 2018 [0025] The first surfactant component typically acts as a dispersant and may also have wetting characteristics.

[0026] In one set of embodiments the first surfactant component is present in the suspension concentrate composition in an amount of 15g/L to 80 g/L of composition, preferably at a concentration of 20 to 80 g/L of composition, more preferably 20 g/L to 50 g/L and still more preferably from 35 g/L to 45 g/L.

[0027] The concentrate composition comprises a second surfactant component selected from the group consisting of polyarylether sulfates and phosphates, polycarboxylates, alcohol ethoxylates, and comb-type graft copolymers.

[0028] In one set of embodiments the second surfactant component is present in the suspension composition in an amount of 5g/L to 80 g/L of concentrate composition, preferably 5g/L to 60g/L, more preferably 8 g/L to 50 g/L and more preferably 30 g/L to 50 g/L.

[0029] In one embodiment the second surfactant component comprises a surfactant selected from the group consisting of sulphates and phosphates of polyarylphenol ethoxylates. These sulphates and phosphates may be in their acid forms, or as salts, such as the ammonium salt or amine salt such as the triethanolamine salt. Examples of such products include: Soprophor BSU', ‘Soprophor S25’, Soprophor TS/10, Soprophor 4D384, Soprophor 3D33, Soprophor FL.

[0030] In a particularly useful embodiment the second surfanctant comprises at least one surfactant selected from the group of polyaryl ether sulfates and phosphates. For example, excellent storage stability is provided by ethoxylated tristyrylphenol sulfates such as, for example, ethoxylated tristyrylphenol sulphate such as 2,4,6-Tris [1(phenyl) ethyl] phenyl- omega-hydroxypoly(oxyethylene) sulphate (Soprophor® 4D384), and ethoxylated tristyrylphenol phosphate such as polyethylene glycol 2,4,6tristyrylphenyl ether phosphate triethanolamine salt (Soprophor® FL). In one embodiment of the aqueous suspension concentrate the second surfactant component comprises a sulphated or phosphated di- or tristyrenephenol ethoxylate.

[0031] A more preferred second surfactant component comprises ethoxylated tristyrenephenol sulfate, such as, for example, Soprophor® FL or ethoxylated

2018282387 20 Dec 2018 tristyrylphenol sulphate, for example 2,4,6-Tris [1-(phenyl) ethyl] phenyl- omegahydroxypoly(oxyethylene) sulphate (Soprophor® 4D384).

[0032] In one embodiment the second surfactant comprises a salt of polyarlyether sulfate and/or phosphate such as an ammonium salt of tristyryl ether sulfate, and the second surfactant is present at a level of 20-80 g/L, preferably 30-50g/L.

[0033] In one set of embodiments the second surfactant component of the suspension concentrate composition comprises a polycarboxylate or a salt thereof, and the polycarboxylate portion of the second surfactant is present in the range 3g/L to25 g/L, preferably in the range 4 g/L to 20 g/L, such as 7 g/L to 12 g/L. Polycarboxylates include acrylic and/or methacrylic acid polymers, and reaction products of unsaturated diacid or diacid derivatives and linear or branched alkenes such as polycarboxylates having a molecular weight in the range of about 600 to about 12,000. Examples of polycarboxylate surfactants include Geropon T/36, which is a reaction product of maleic anhydride and 2,4,4 trimethylpentene.

[0034] Examples of alcohol ethoxylates which may be present in the second surfactant component include polyoxyethylene alkylether or polyoxyalkylene surfactants. Nonionic surfactant used to prepare a suspension concentrate may include long or short chain alcohol ethoxylate surfactant. The alcohol ethoxylate surfactant may be branched or linear.

[0035] An example of a useful non-ionic polyoxyalkylene surfactant includes alcohol alkoxylate having the general formula:

R-O-(R¹O)_y-H wherein R may be “long” or “short” chain and “branched” or “linear” alkyl. R preferably can be a “short chain” branched or linear alcohol, meaning that it can have from about 3 to 23 or fewer carbon atoms. With respect to the oxyalkylene, R¹ can be alkylene2 to 5 carbon atoms, particularly 1,2-alkylene of 2 to 5 carbon atoms, preferably from about 2 to 4 carbon atoms (e.g., 2 or 3, for a polyoxyethylene or polyoxypropylene, respectively) and y can preferably be in the range from 5 to 25. In one specific example the composition comprises a (Ci2to 0¼ alcohol) ethoxylate.

[0036] Examples of useful short chain non-ionic polyoxyalkylenes include linear alcohol polyoxyethylenes having the general formula:

2018282387 20 Dec 2018

CH₃(C₂H₄)_mO(C₂H₄O)_nH wherein CH₃(C2H₄)_m is a short chain linear alkyl having from about 3 to 23 or fewer carbon atoms (i.e., m can be in the range from about 1 to 11 carbon atoms), and n is in the range from about 5 to 25.

[0037] Another example is short chain non-ionic polyoxypropylenes having the general formula:

CH₂(C₂H₄)_mO(C₃H₆O)_nH, wherein CH₃(C2H₄)m is a short chain linear alkyl having from about 3 to 23 or fewer carbon atoms (i.e., m can be in the range from about 1 to 11 carbon atoms), and n can preferably be in the range from about 5 to 25.

[0038] In one set of embodiments the composition comprises a second surfactant comprising an alcohol ethoxylate, preferably a C9-C11 alcohol ethoxylate, preferably with 4 moles EO -10 moles EO. In a further preference, the alcohol ethoxylate is present in the composition a 3g/L to 30 g/L, preferably 5 g/L to 15 g/L.

[0039] The second surfactant component may comprise a comb-graft polymer surfactant which is generally believed to act as a further dispersant for the particulate solid herbicides, although the surfactant may also function as a wetting agent. A comb-graft polymer is a material that has polymer or oligomer chains of one chemical composition branching out from a polymer backbone with a different chemical composition. The preferred comb-graft polymer surfactant for use in the present invention has a polymer backbone and polyether groups appended to the polymer backbone. Comb-graft polymers that can be used in accordance with this invention include but are not limited to, (meth)acrylic acid, (meth)acrylate or methyl (meth)acrylate polymers which have chains of another polymer, as for example, a polyether such as polyethylene glycol, extending from the (meth)acrylate polymer backbone.

[0040] In one set of embodiments the comb-graft polymer used in the composition may be described as comb-graft copolymer with a polymer backbone formed of polymers such as (meth)acrylic acid, acrylate, (meth)acrylate or methyl (meth)acrylate polymers and copolymers and polyethylene glycol (PEG) branches extending from

2018282387 20 Dec 2018 this backbone. In two-dimensional representations, the PEG branches are drawn perpendicular to the acrylate polymer backbone (usually linear) and resemble the teeth of a comb, giving rise to the description comb-graft polymer. The comb-graft polymers preferred for use in the present invention are proprietary materials;

therefore, specific details of their composition and manufacture are not known to the applicants.

[0041] Suitable comb-graft polymers include, but are not limited to Tersperse™. 2500 (about a 35% comb-graft copolymer solution from Huntsman Corp.), Atlox™. 4913 (about a 35% comb-graft copolymer solution from Croda Uniqema.), Ethacryl P™. (a 35-45% comb-graft copolymer solution from Lyondell Chemical Co.), and the like.

[0042] The comb-graft polymer portion of the second surfactant, where used, is preferably present in the suspension concentrate in an amount in the range of from 1 g/L to 80 g/L of concentrate and more preferably 2 g/L to 40 g/L. In one embodiment the composition comprises a second surfactant comprising an acrylic graft copolymer, present in the range 3 g/L to 60 g/L (weight of the acrylic graft copolymer based on the total weight of the composition), preferably 3g/L to 30 g/L and still more preferably in the range 5g/L to 15 g/L.

[0043] It should be noted that when weights of surfactants are given, and where the surfactant is a solid dissolved in a liquid to form a liquid concentrate, the weight of surfactant refers to the weight of the surfactant based on the total weight of the suspension concentrate composition.

[0044] The suspension concentrate is an aqueous concentrate and water is typically the predominant liquid carrier for the suspension. Water will typically be at least 40% by weight of the liquid carrier for the composition such as at least 45% w/w such as at least 50% w/w of the liquid carrier of the composition. The amount of water in one embodiment is at least from 400 g/L to 800 g/L such as from 500 g/L to 750 g/L.

[0045] The composition may comprise an antifreeze. Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Typically these agents are present in an amount of no more than 30% w/w typically no more than 200 g/L such as 2 % to 20% w/w (typically 20 g/L to 100 g/L of the suspension

2018282387 20 Dec 2018 concentrate composition.In one embodiment glycerol is present in an amount of 40 g/L to 80 g/L such as 50 g/L to 70 g/L.

[0046] The composition may comprise one or more thickeners to provide the concentrate with a suitable viscosity such as a viscosity in the range of from 200 cP to 1500 cP (Brookfield viscosity measured using Spindle 2 at 20 RPM and room temperature such as 20°C). Examples of thickeners include polysaccharides such as xanthan gum, rhamsan gum, locust bean gum, carrageenan or welan gum; a synthetic polymer such as sodium polyacrylate; a semisynthetic polysaccharide such as carboxy methyl cellulose; a mineral fine powder such as aluminum magnesium silicate, smectite, bentonite, hectorite or fumed silica, or alumina sol. The amount of the thickener to be used in the suspension of the present invention is usually from 0.01 wt.% or more, preferably 0.05 wt.% or more, and typically at the same time 5.0 wt.% or less, and preferably 1.0 wt. % or less, with wt.% based on weight of the pesticide suspension concentrate composition. The amount of thickener is generally about 0.1 g/L to 20 g/L.

[0047] In one embodiment an inorganic thickener such as smectite clay is used at 325 g/L, preferably 3 g/L to 15 g/L and more preferably 8 g/L to 12 g/L. In a preferred embodiment an organic thickener, such as xanthan gum, is used at 0.5 g/L to 10 g/L , preferably 0.5 g/L to 5 g/L such as 1 g/L to 2.5 g/L.

[0048] The composition may and typically will include other additives such as preservative and antifoam. Preferred preservative agents can be used in accordance to some embodiments of the present invention include, for example, 1,2benzisothiazolin-3-one available commercially as Proxel GXL (tradename, Zeneca AG). The amount of the antiseptic to be used in the suspension of the present invention is usually from 0.01 wt.% or more, preferably 0.05 wt.% or more, and at the same time 1.0 wt.% or less, and preferably 0.3 wt.% or less, with wt.% based on the weight of the pesticide suspension concentration formulation. Typically the amount is about 0.5 g/L to about 8 g/L , preferably 1.5 g/L to 4 g/L.

[0049] Preferred antifoaming agents can be added for the purpose of suppressing formation of bubbles during the formation of the suspension concentrate. Such antifoaming agents can be, for example, a silicone type antifoaming agent containing

2018282387 20 Dec 2018 polydimethylsiloxane. For example, generally, a silicone type antifoaming agent containing silica is preferred. The amount of the antifoaming agent to be used in the suspension of the present invention is usually from 0.01 wt.% or more, preferably 0.1 wt.% or more and at the same time 10 wt. % or less, preferably from 1.0 wt. % or less, based on the weight of the pesticide suspension concentrate composition. Typically the antifoam is at a concentration of from 0.3 g/L to 10 g/L of concentrate, preferably 2 g/L to 6 g/L of concentrate.

[0050] In one set of embodiments of the invention the aqueous suspension concentrate comprises particulate clofentezine and abamectin in a total amount of 100 g/L to 300 g/L and weight ratio of clofentezine to abamectin of 5:1 to 20:1;

a salt of naphthalene sulfonic acid-formaldehyde condensates or alkylnaphthalene sulfonic acid-formaldehyde condensates (preferably sodium methylnaphthalene sulfonate-formaldehyde condensate in an amount of 15 g/L to 70 g/L;

at least one of sulphates of polyarylphenol ethoxylates and alkyl ethoxylates (preferably where alkyl is Ce-15 more preferably C9-11 alkyl ethoxylates and 5-8 EO units such as 6 EO units) in an amount of from 5 g/L to 60g/L;

optionally a polycarboxylate polymeric surfactant in a amount of from 5g/L to 25 g/L;

optionally a viscosity modifier or viscosity modifiers in a total amount of 0.5 g/L to 20 g/L; and optionally an antifreeze in an amount of no more than 100 g/L such as 20 g/L to 100 g/L.

[0051] In a preferred set of embodiments the first surfactant comprises at least one of a salt of naphthalene sulfonic acid-formaldehyde condensates or alkylnaphthalene sulfonic acid-formaldehyde condensates in an amount of 20 g/L to 60 g/L and the second surfactant comprises (a) sulphates of polyarylphenol ethoxylates in 20 g/L to 60 g/L and (b) polycaboxylates in an amount of 5g/L to 15 g/L.

2018282387 20 Dec 2018 [0052] Milling of the suspension from crude to fine particle sizes can be carried out by either recirculating the fluid or subjecting the fluid to multiple passes through the milling chamber, depending on the nature of the milling device. As the particle size of the solids is reduced, heat is generated, requiring cooling of the suspension. In one embodiment the milling involves ball milling with ceramic beads.

[0053] In one embodiment a substantial fraction (such 30% to 70 % or about half) of the water in the final formulation is added to a vessel with high-shear batch agitation and gradual addition of inorganic thickening agent (such as Veegum smectite) takes place. Thereafter surfactants are added and optionally also a portion of the anti-freeze agent such as glycerol are added with further mixing. Thereafter clofentezine and then abamectin technical material is added with further mixing and the resultant liquor is passed through a bead mill to form a mill base with D(v,0.9) less than 15 microns. A dispersion of organic thickening agent (such as xanthan gum) is made in glycerol in a separate vessel, and said xanthan dispersion is added gradually with the remaining water to the main dispersion vessel. It is important to avoid aeration after xanthan addition has commenced.

[0054] The process may comprise adding 30% to 70% of the water content prior to milling, and adding the remainder of the water with stirring following milling.

[0055] In one set of embodiments at least 20% of the anti-freeze agent is added following milling, preferably at least 30%, such as at least 40% or 50%.

[0056] We have found it to be particularly advantageous if at least 50% (preferably at least 60%, such as at least 70% or at least 80%) of the organic thickener is dispersed in the portion of the anti-freeze agent that is added following milling.

[0057] Once the desired particle size of this suspension, which may be monitored by measuring with a light scattering device, is achieved, it is either ready for subsequent additives to form the composition of the invention or can be further stabilized through use of a thickener. This suspension is referred to as a millbase. The final formulated suspension concentrate may be formulated with appropriate components such as further water, antifoam, antifreeze, preservatives, rheology modifiers and suspension aids, additional surfactants that serve to disperse the solids in concentration and when applied in dilute form.

2018282387 20 Dec 2018 [0058] In one embodiment, the particle size distribution of the suspension concentrate has a D(v, 0.9) less than 40, more preferably less than 20, even more preferably less than 15 microns. D(v,0.9) is the intercept (expressed as a diameter) where 90% of the volume distribution (or cumulative mass) is less than said intercept.

[0059] The invention further provides a method of protection of plants against insect and aracnid/mite pests such as spider mite or couch grass mite comprising applying to the plants, preferably by spray application, a suspension concentrate composition as hereinbefore described.

[0060] The composition is particularly useful in the control of spider mites and couch grass mite. Spider mites are members of the Acari family and couch grass mites include Aceria cynodoniensis (formerly Eriophyes cynodoniensis). The composition has been found to be particularly effective in the control of Couch Mite.

[0061] The invention will now be described with reference to the following examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.

2018282387 20 Dec 2018

Examples [0062] Example 1: Initial screening test [0063] The following compositions samples shown in Table 1 were prepared without milling and placed at 60°C to verify stability.

[0064] Table 1

Component	Purpose
F1	F2	F3

Clofentezine 98% tech	Active ingredient	191.3	191.3	191.3
Abamectin 97% tech	Active ingredient	18.56	18.56	18.56
Veegum T	Rheology modifying agent	5	5	5
Tersperse 2500	Dispersant	-	-	30
Tersperse 4894	Dispersant	-	-	-
Soprophor FL	Dispersant	-	-	-
Supragil MNS/90	Dispersant	40	40	-
Teric 9A6	Wetting agent		10	-
Soprophor 4D384	Dispersant	40	-	-
Geropon T/36	Wetting agent/dispersant	10	-	-
Morwet D-425	Dispersant			25
Proxel GXL	Preservative	2.5	2.5	2.5
Glycerol	Anti-freeze	60	60	60
CAF 300 antifoam	Antifoam	3	3	3
Water	Continuous phase	To 1L	To 1L	To 1L

[0065] Formulations F1, F2 and F3 were found to be quite stable with respect to particle homogeneity.

2018282387 20 Dec 2018 [0066] The Chemistry of surfactants from the composition of Table 1 are shown in Table 2.

[0067] Table 2

Dispersant/wetter	Chemistry
Supragil MNS/90	88%+ purity Methyl naphthalene sulfonic acid, polymer with formaldehyde, sodium salt
Soprophor 4D384	80%+ purity Ammonium salt of polyarylphenyl ether sulphate
Geropon T/36	2,5-furandione polymer with 2,4,4trimethylpentene, sodium salt (70-100%) Disodium maleate (10-20%)
*Teric 9A6	90%+ purity C9-11 synthetic alcohol reacted with 6 moles ethylene oxide
Tersperse 2500	33% Solution of an acrylic graft copolymer in water/propylene glycol
Morwet D425	Sodium alkylnaphthalenesulfonate, formaldehyde condensate (>88%) Sodium sulfate (<12%)
Tersperse 4894	Alcohols, C12-16, ethoxylated (10-30%) Polyoxyethylene-polyoxypropylene glycol ether (60-100%)
Atlox 4915	Polymerised fatty acid ester
Soprophor FL	Amine salt of polyarylphenyl ether phosphate

• Note: Teric®9A6 can be replaced with Teric® 10A6N [0068] Example 2: milled formulation (designated F4) with composition of F1 of Example 1.

[0069] The composition F4 shown inTable 3 was prepared and milled by ball milling with ceramic beads, using a Dispermat SL mill and zirconium beads.

2018282387 20 Dec 2018 [0070] Table 3

Component	Purpose	F4
Clofentezine 98% tech	Active ingredient	191.3
Abamectin 97% tech	Active ingredient	18.56
Veegum T	Rheology modifying agent	5
Tersperse 2500	Dispersant	-
Tersperse 4894	Dispersant	-
Supragil MNS/90	Dispersant	40
Soprophor 4D384	Dispersant	40
Geropon T/36	Wetting agent/dispersant	10
Proxel GXL	Preservative	2.5
Glycerol	Anti-freeze	60
CAF 300 antifoam	Antifoam	3
Water	Continuous phase	To 1L

[0071] Samples were split into 2 and placed at ambient and 60°C x 1 week.

[0072] Composition F4 - showed very little separation, no caking after storage at 60°C. Very little change in appearance compared to room temperature sample.

[0073] Example 3: Further modification of formulation F4 (designated F5).

[0074] The composition F4 was further refined to provide composition F5 shown in Table 4.

2018282387 20 Dec 2018 [0075] Table 4. The composition of a 187.5g/L clofentezine and 18g/L abamectin SC formulation (F5).

Component	CAS. No	Chemical name	Concentration (g/L)
Clofentezine (98%)*	74115-24-5	3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine	191.3
Abamectin (97%)*	71751-41-2	a mixture containing > 80% (10E,14E,16E,22Z)- (1 R,4S,5’S,6S,6’R,8R,12S,13S,20R,21 R,24 S)-6’-[(S)-sec-butyl]-21,24-dihydroxy5’, 11,13,22-tetramethyl-2-oxo-3,7,19trioxatetracyclo[15.6.1.1^4,8.0^20,24]pentacosa10,14,16,22-tetraene-6-spiro-2’-(5’,6’dihydro-2’H-pyran)-12-yl 2,6-dideoxy-4-Omethyl-4-O-(2,6-dideoxy-3-O-methyl-alphaL-arabino-hexopyranosyl)-3-O-methylalpha-L-arabino-hexopyranoside and less than 20% of (10E,14E,16E,22Z)- (1 R,4S,5’S,6S,6’R,8R,12S,13S,20R,21 R,24 S)-21,24-dihydroxy-6’-isopropyl- 5’, 11,13,22-tetramethyl-2-oxo-3,7,19trioxatetracyclo[15.6.1.1^4,8.0^20,24]pentacosa10,14,16,22-tetraene-6-spiro-2’-(5’,6’dihydro-2’H-pyran)-12-yl 2,6-dideoxy-4-Omethyl-4-O-(2,6-dideoxy-3-O-methyl-alphaL-arabino-hexopyranosyl)-3-O-methylalpha-L-arabino-hexopyranoside	18.55
Soprophor® 4D384	119432-41- 6	Sulfated polyarylphenol ethoxylated, ammonium salt	40
Supragil® MNS-90	81065-51-2	Polycondensate of sodium methylnaphthalene sulfonate and formaldehyde	40
Geropon® T/36	37199-81-8	Sodium salt of polycarboxylic acid	10
Glycerol	56-81-5	Propan-1,2,3-triol	60
Gensil® 2030	63148-62-9	Polydimethylsiloxane emulsion	3
Proxel® GXL	2634-33-5	1,2-benzisothiazolin-3-one	2.5
Veegum® T	12199-37-0	Smectite clay	10
Rhodopol® 50MC	11138-66-2	Xanthan gum	1.5
Water	7732-18-5	Water	699.8
			1076.8

Concentration should be based on technical purity.

2018282387 20 Dec 2018 [0076] Composition F5 was subject to CIPAC Testing and the results are shown in

Table 5.

[0077] Table 5

Test Method	CIPAC Method	Specification	Ambient	54°C x 2 weeks
Appearance	Visual	Magenta liquid suspension	Magenta liquid suspension	Magenta liquid suspension
pH (1%)	MT75.3	4.9-5.9	8.52	8.25
Viscosity (cP) (Spindle 2, 20RPM)	MT192	600-900	448.5	559.5
Suspensibility on dilution with water (%)	MT184	60-105%	81.4	89.9
Spontaneity of dispersions (%)	MT160	60-105%	92.8	86.7
Wet sieve test (%)	MT185	<2% retained on a 75pm sieve	0.09	0.1
Pourability (%)	MT148.1	<5% residue	2.4	2.8

[0078] Example 4: Further modification of formulation F5 (designated F6) [0079] Composition F5 was further modified to provide Composition F6 shown in Table 6.

[0080] Table 6

Component	CAS. No	Constituent Standard	Concentration (g/L)	Function
Clofentezine (98%)*	74115-24-5		191.3	Active ingredient
Abamectin (95%)*	71751-41-2		18.95	Active ingredient
Soprophor® 4D384	119432-41-6	MS	40	Dispersant
Supragil® MNS-90	81065-51-2	MS	40	Dispersant
Geropon® T/36	37199-81-8	MS	10	Wetting agent
Glycerol	56-81-5	MS	62.5	Anti-freeze
Gensil® 2030	63148-62-9	MS	4	Antifoam
Proxel® GXL	2634-33-5	MS	2.5	Antimicrobial

2018282387 20 Dec 2018

Veegum® T	12199-37-0	MS	10	Rheology modifier
Rhodopol® 50MC	11138-66-2	MS	1.78	Viscosity modifying agent
Water	7732-18-5	n/a	728.8	Diluent
		Total (grams)	1109.83

[0081] Optimisation factors were as follows: Antifoam was increased, water was changed to match S.G and Rhodopol (Xanthan gum), added after milling, was increased to adjust viscosity.

[0082] Formulation F6 (characteristics) [0083] The particle size was measured using laser diffraction (Mastersizer) and with the refractive index of both abamectin and clofentezine.

[0084] The particle size distribution is shown in Table 7.

[0085] Table 7

Test method	CIPAC Method	Specification	1 week at 0°C	Ambient	2 weeks at 54°C
Particle size distribution (pm)	MT187	D(v,0.9) <15	Abamectin R.l.	10.55	10.16	9.81
Clofentezine R.l.	11.65	10.91	10.54

[0086] The composition was milled using a horizontal bead mill (Dyno-mill MULTILAB/Dispermat SL) with Zirconox beads.

[0087] Milling Options [0088] Horizontal bead mill:

• Dispermat SL using Zirconox beads (1.0-1,4mm) OR • Dyno-mill MULTI LAB using Zirconox beads (0.4 - 0.6mm OR 0.8 -1mm) • Ceramic ball mill using ceramic beads (most crude method).

[0089] Formulation process for formulation F6 [0090] A typical manufacturing batch size would be 1,000L.

2018282387 20 Dec 2018

Step 1. To prepare the mill base blend, fill a 1,000L stainless steel mixing vessel with approximately 50% of the water required. Mix with the Silverson® high shear batch mixer to form a vortex and gradually add Veegum® T. Mix for 15 minutes.

Step 2. Gradually add Gensil® 2030, Soprophor® 4D384, Supragil® MNS-90, Geropon® T/36, Proxel® GXL and 50% of required glycerol (leaving a sufficient amount for the dispersion of Rhodopol® 50MC). Mix until homogeneous or for another 15 minutes, whichever is longer.

Step 3. Gradually add clofentezine technical material to the 1,000L vessel whilst constantly mixing. Continue mixing until the technical is uniformly dispersed or for another 15 minutes, whichever is longer.

Step 4. Gradually add abamectin technical material to the 1,000L vessel whilst constantly mixing. Continue mixing until the technical is uniformly dispersed or for another 15 minutes, whichever is longer.

Step 5. Continue mixing slowly, to avoid settling of active ingredient whilst the liquid contents are passed through a suitable bead mill to produce a particle size of D(v,0.9) <15pm (in the pilot plant a Dyno-mill MULTI-LAB was used). The mill-base is collected in a 1,200-1,500L stainless steel mixing vessel. The mill-base must be stirred after it exits the mill to avoid settling.

Note 1. It is essential that the mill-base is de-aerated if required, as it is very difficult to remove air bubbles once the thickener is added in later steps.

Step 6. Gradually add the remaining glycerol into the 70L stainless steel vessel. Add the Rhodopol® 50MC and disperse using a paddle mixer (the Dispermat® was used in the pilot plant). Mix until Rhodopol® 50MC powder is completely wetted.

Note 2. The Rhodopol® dispersion must be used up immediately as it thickens to a rubber-like consistency over time.

Step 7. Gradually add the Rhodopol® 50MC dispersion and the remaining water to the 1,200-1,500L vessel whilst mixing and continue mixing until homogeneous or for another 30 minutes, whichever is longer.

Note 3. Avoid aerating the product by fully submerging the mixer head in the bulk liquid.

2018282387 20 Dec 2018 [0091] The stability testing results for formulation F6 are shown in Table 8 and Table 9.

[0092] Table 8 - Physical stability

Test method	CIPAC Method	Specification	1 week at 0°C	Ambient	2 weeks at 54°C
Appearance (colour, odour, physical state)	Visual	Magenta liquid suspension	Magenta liquid suspension	Magenta liquid suspension	Magenta liquid suspension
pH (1%)	MT75.3	8.0-9.0	8.61	8.52	8.25
Viscosity (cP) (LV spindle 2, 20RPM)	MT192	400 - 600	436.5	448.5	559.5
Particle size distribution (pm)	MT187	D(v,0.9) <15	Abamectin R.L	10.55	10.16	9.81
Clofentezine R.L	11.65	10.91	10.54
Suspensibility on dilution with water (%)	MT184	60-105	86.2	81.4	89.9
Spontaneity of dispersion (%)	MT160	60-105	92.8	88.6	86.7
Wet sieve test (%)	MT185	<2% retained on a 75pm sieve	0.09	0.04	0.11
Pourability (%)	MT148	<5% residue	2.4	2.4	2.8
Persistent foam (mL)	MT47.2	<60mL after 1 minute	44	51	56
Low temperature stability	MT39.3	Magenta liquid suspension	Magenta liquid suspension	n/a	n/a
Packaging stability (HDPE)	Observation of packaging stability	No changes to bottle, labels and closure	No changes to bottle, labels and closure	No changes to bottle, labels and closure	No changes to bottle, labels and closure

2018282387 20 Dec 2018 [0093] Table 9 - Active ingredient stability:

Active ingredients	Specification (g/L)	FMX2-110-1
Ambient	2 weeks at 54°C
Abamectin	15.3-20.7	18.7	17.8
Clofentezine	176.25-198.75	195.1	188

[0094] Example 4 - Bioassay Information [0095] Two couch mite (Aceria cynodoniensis) field trials were established at a Golf Course in a rough area on a fairway and at a trial plot both in the Sydney area of New South Wales.

[0096] The objective of the study was to evaluate the efficacy and safety of various insecticides for couch mite (Aceria cynodoniensis) control on couch grass (Cynodon dactylon).

[0097] The treatments applied in the trial were as follows (see Product Information for full description):

1. Untreated

2. Apollo @250mL/ha + Gymnast @2L/ha

3. Apollo @500mL/ha + Gymnast @2L/ha

4. Apollo @250mL/ha

5. Apollo @500mL/ha

6. Composition F6 @675mL/ha

7. Composition F6 @1.35mL/ha

8. Higran @500mL/ha

9. Gymnast @2L/ha

10. Thumper @1L/ha

11. Thumper @2L/ha

2018282387 20 Dec 2018

Results [0098] The research findings were as follows:

• Deformed/lnfested turf terminal symptom results has displayed all treatments to be statistically superior to the untreated control in both trials. Composition F6 @675mL/ha displayed the best result at the Golf Course by achieving 87.10% reduction, while at the trial plot the highest result was displayed by Composition F6 @1.35L/ha at 85.65% reduction.

• Visual turf quality ratings differed between trial sites, with the highest values at trial completion being achieved by Compoaition F6 @1.35L/ha at the golf course and Apollo @500mL/ha +Gymnast @2L/ha at the trial plot.

• Composition F6 formulations have proved statistically similar to the key industry standards for couch mite (Aceria cynodoniensis) control and safety on couch grass (Cynodon dactylon).

• No phytotoxicity was observed at any time within the trial, hence indicating that couch grass (Cynodon dactylon) is tolerant of all tested products at their highest rates.

[0099] Commercial products used in testing are listed in Table 10.

[0100] Table 10 - Product Information

No	product	APVMA number	Active ingredient	Formulation type
1	Apollo®	59818	500g/L clofentezine	SC
2	Gymnast®	68979	18g/L Abamectin	EC
3	Higran®	68340	500g/L Diafenthiuron	SC
4	Thumper®	85539	20g/L Abamectin	EC
5	Composition F6	N/A	187.5 g/L clofentezine plus 18g/L Abamectuin	SC

[0101] Composition F6 is listed in Example 4

2018282387 20 Dec 2018 [0102] Table 11 - Treatments

Treatment	Product	Rate ai per ha	Rate product per ha
1	Untreated control (UTC)	n/a	n/a
2	Apollo+Gymnast	125g+36g	250ml+2L
3	Apollo+Gymnast	250g+36g	500ml+2L
4	Apollo	125g	250ml
5	Apollo	250g	500ml
6	Composition F6, (Example 4 of the invention)	126.6g+12.15g	675ml
7	Composition F6	253.2g+24.3g	1.35L
8	Higran	250g	500ml
9	Gymnast	36g	2L
10	Thumper	20g	1L
11	Thumper	40g	2I

Claims

Claims

1. An aqueous suspension concentrate composition comprising suspended particles of clofentezine and suspended particles of abamectin wherein the composition comprises a first surfactant component selected from the group consisting of naphthalene sulfonate-formaldehyde condensates that may optionally be alkyl substituted and salts thereof and mixtures thereof and a second surfactant component selected from the group consisting of polyarylether salts, polycarboxylates, alcohol ethoxylates, and comb-type graft copolymers.
2. The aqueous suspension concentrate composition of claim 1 wherein the weight ratio of clofentezine to abamectin in one set of embodiment is in the range 3:1 to 100:1.
3. The aqueous suspension concentrate composition of claim 1 wherein the weight ratio of clofentezine to abamectin in the range 5:1 to 20:1.
4. The aqueous suspension concentrate composition of claim 1 wherein the weight ratio of clofentezine to abamectin in the range 7:1 to 14:1.
5. The aqueous suspension concentrate composition of any one of the previous claims wherein the total content of abamectin and clofentezine in one set of embodiments is 50 g/L to 600 g/L.
6. The aqueous suspension concentrate composition of any one of the previous claims wherein the composition comprises 150 to 250 g/L clofentezine and 12 g/L to 30 g/L abamectin.
7. The aqueous suspension concentrate composition of any one of the previous claims wherein the first surfactant component comprises the sodium salt of naphthalenesulfonate-formaldehyde condensate or alkylnaphthalenesulfonateformaldehyde condensate.
8. The aqueous suspension concentrate composition of any one of the previous claims wherein the first surfactant component is present in the suspension composition in an amount of 15g/L to 80 g/L.

2018282387 20 Dec 2018
9. The aqueous suspension concentrate composition of any one of the previous claims wherein the first surfactant component is present in the suspension composition in an amount of 35 g/L to 45 g/L
10. The aqueous suspension concentrate of any one of the previous claims wherein the second surfactant component is present in an amount of from 5g/L to 80 g/L.
11. The aqueous suspension concentrate of any one of the previous claims wherein the second surfactant is selected from the group consisting of alcohol ethoxylates, polyarylether phosphates or sulfates and salts thereof and mixtures thereof.
12. The aqueous suspension concentrate of any one of the previous claims wherein the first surfactant is selected from the group consisting of naphthalene sulfonate-formaldehyde condensates that may optionally be alkylsubstituted and salts thereof and mixtures thereof, the second surfactant is selected from the group consisting of sulfates of polyarylphenol ethoxylates in their acid forms or as salts, and wherein the second surfactant further comprises a polycarboxylate including a polycarboxylate having a molecular weight in the range 600 to 12,000.
13. The aqueous suspension concentrate according to claim 12 wherein the first surfactant is present in an amout of 20 g/L to 80 g/L, and the second surfactant comprises the sulfates of polyarylphenol ethoxylates in their acid forms or as salts present in the range 30 g/L to 60 g/L of the suspension concentrate and polycarboxylates present in the range 3g/L to 25 g/L of the suspension concentrate.
14. The aqueous suspension concentrate composition of any one of the previous claims wherein the second surfactant comprises one or more selected from the group consisting of:

(a) sulphates and phosphates of polyarylphenol ethoxylates in their acid forms, or as salts in an amount of 20 g/L to 50 g/L of concentrate;

(b) polycarboxylates including polycarboxylates having a molecular weight in the range of about 600 to about 12,000;

2018282387 20 Dec 2018 (c) a C9-C11 alcohol ethoxylate, with 4-10 moles EO in an amount in the range 5 g/L to 25 g/L; and (d) comb graft copolymers comprising (meth)acrylic acid, (meth)acrylate or methyl (meth)acrylate polymers which have chains of a polyether such as polyethylene glycol, extending from the (meth)acrylate polymer backbone in an amount of 3 g/L to 30 g/L.
15. The aqueous suspension concentrate composition of any one of the previous claims comprising one or more anti-freeze agents selected from the group ethylene glycol, propylene glycol, urea and glycerine in a total amount of no more than from 2% w/w to 20% w/w of the composition.
16. The aqueous suspension concentrate of any one of the previous claims, comprising glycerol anti-freeze in the range 50 g/L to 80 g/L.
17. The aqueous suspension concentrate of any one of the previous claims, comprising an inorganic thickening agent in the range 3 g/L to 30 g/L.
18. The aqueous suspension concentrate of any one of the previous claims, comprising an organic thickening agent in the range 0.5 g/L to 5 g/L.
19. The aqueous suspension concentrate of any one of the previous claims comprising:

particulate clofentezine and abamectin in a total amount of 100 g/L to 300 g/L and weight ratio of clofentezine to abamectin of 5:1 to 20:1;

a first surfactant component comprising 15 g/L to 70 g/L of the concentrate of at least one one of naphthalene sulfonate-formaldehyde condensate and alkylnaphthalene sulfonate-formaldehyde condensate in an amount 15 g/L to 70 g/L;

a second surfactant comprising 20 g/L to 60g/L of the concentrate of sulphates of polyarylphenol ethoxylates;

optionally a polycarboxylate surfactant in an amount of from 5g/L to 25 g/L;

optionally a viscosity modifier or modifiers in an amount of 0.5 g/L to 10 g/L; and optionally an antifreeze in an amount of 20 g/L to 100 g/L.

2018282387 20 Dec 2018
20. The aqueous suspension concentrate of any one of the previous claims, wherein the first surfactant comprises at least one of a salt of naphthalene sulfonic acid-formaldehyde condensates or alkylnaphthalene sulfonic acidformaldehyde condensates in an amount of 20 g/L to 60 g/L and the second surfactant comprises (a) sulphates of polyarylphenol ethoxylates in their acid forms or as salts in 20 g/L to 60 g/L and (b) polycaboxylates in an amount of 5g/L to 15 g/L.
21. The aqueous suspension concentrate of any one of the previous claims, wherein the particle size distribution of the suspension concentrate has a Dv 0.9 less than 40 microns.
22. A process for preparation of the suspension concentrate according to any one of the previous claims comprising combining particulate abamectin and particulate clofentezine with an aqueous mixture comprising the first surfactant component and the second surfactant component and milling the composition to reduce the particle size of abamectin and clofentezine to provide an aqueous suspension concentrate comprising suspended particles of clofentezine and suspended particles of abamectin.
23. The process of claim 22 comprises adding 30% to 70% water prior to milling, and adding the reminder of the water with stirring following milling.
24. A process of claim 22 or claim 23 wherein at least 20% of the anti-freeze agent is added in the following milling.
25. The process of any one of claims 22 to 24, wherein at least 50% of the organic thickener is dispersed in the portion of the anti-freeze agent that is added following milling.
26. A method for controlling pests comprising applying to the pests or locus of the pests the suspension concentrate according to any one of claims 1 to 21.
27. The method of claim 26, wherein the composition is applied to plants to control insect and aracnid/mite pests.
28. The method of claim 27, wherein the plants are selected from lawn, turf and fruit trees.