WO2013061165A2

WO2013061165A2 - Water dispersible granules

Info

Publication number: WO2013061165A2
Application number: PCT/IB2012/002914
Authority: WO
Inventors: Charles Omotayo KEROBO; Simone Renee BRIGHT; Katherine Lynne ADLER
Original assignee: Basf Se
Priority date: 2011-10-27
Filing date: 2012-10-25
Publication date: 2013-05-02
Also published as: WO2013061165A3

Abstract

A water dispersible granule includes an active component present in an amount ranging from 70 to 99 wt.% of the granule, a copolymer present in an amount ranging from 1 to 10 wt.% of the granule, a block-copolymer present in the amount ranging from 0.1 to 5 wt.% of the granule, and a wetting agent present in the amount ranging from 0.1 to 10 wt.% of the granule. The copolymer includes at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit. The block copolymer includes at least one ethylene-oxide unit and at least one propylene-oxide unit. The granule optionally includes a disintegrant agent. A method of producing the water dispersible granule is also provided.

Description

WATER DISPERSIBLE GRANULES

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application No. 61/552,232, filed on October 27, 2011, the disclosure of which is incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a water dispersible granule. More specifically, the present invention relates to a water dispersible granule including an active component, a copolymer, a block copolymer, and a wetting agent. The present invention also relates to a method of producing the water dispersible granule.

BACKGROUND OF THE INVENTION

[0003] Throughout the world, a considerable portion of agricultural production is destroyed each year by nuisance organisms which affect a target agricultural product. Such organisms can lead to production failure on a large scale, which threatens human alimentation and can impair agriculturally productive land.

[0004] There are many different types of nuisance organisms which affect agricultural products, including, but not limited to, insects, nematodes, snails, microbes, fungi, bacteria, viruses, viroids, and weeds. Higher animals, such as vertebrates and mammals, can also be considered to be nuisance organisms in the broadest sense. Elimination of these nuisance organisms remains an obstacle in modern agriculture. One method for eliminating nuisance organisms involves application of various active components.

[0005] The active component is commonly known in the art as an "active ingredient." Typically, active components are dissolved, emulsified or dispersed in an aqueous medium to obtain an aqueous spray mixture described as "tank mix." The tank mix is applied to the target agricultural product, such as crops.

[0006] Active components provided in a liquid form exhibit a number of disadvantages, such as a risk of water contamination due to possible runoff into the soil. Storage and transportation of liquid active components are more expensive since a solvent has to be transported and stored. The stability of liquid active components with regard to heat, cold and shear forces is low and requires expensive emulsifying and stabilizing additives. Thus, active components based on water dispersible granules offer considerable advantages in comparison with active components in liquid form.

[0007] Although granules offer many advantages over liquid active components, conventional granules can have poor suspensibility and dispersibility, and typically settle to the bottom of applicator tanks. Other granules may exhibit poor levels of suspensibility when dispersed in water, and do not mix properly. Thus, there remains an opportunity to form an improved granule. There also remains an opportunity to develop a method to form such granules.

SUMMARY OF THE INVENTION AND ADVANTAGES

[0008] The present invention provides a water dispersible granule. The water dispersible granule includes an active component present in an amount ranging from 70 to 99 wt.% by weight of the granule. The water dispersible granule also includes a copolymer present in an amount ranging from 1 to 10 wt.% by weight of the granule. The copolymer includes at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit. Further, the granule includes a block-copolymer present in an amount ranging from 0.1 to 5 wt.% by weight of the granule. The block-copolymer includes at least one ethylene-oxide unit and at least one propylene-oxide unit. Still further, the granule includes a wetting agent present in the amount ranging from 0.1 to 10 wt.% by weight of the granule. The present invention also provides a method of producing a water dispersible granule.

[0009] The granule described herein typically exhibits excellent performance. Without being limited by theory, it is believed that the copolymer and the block- copolymer synergistically act to provide a granule having excellent suspensibility, dispersibility, and disintegration time. These properties allow the granule to disperse throughout a solution with minimal settling at a tank bottom and minimal floating at a tank top and ensure quick mixing in the applicator tank and greater efficacy upon application DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention provides a water dispersible granule, hereafter simply referred to as a "granule," and a method of forming the granule, described in greater detail below.

[0011] The granule includes an active component, a copolymer, a block copolymer, and a wetting agent. Without intending to be bound by any particular theory, it is believed that the copolymer and the block-copolymer synergistically act, at least in part, to provide the granule with excellent suspensibility and dispersibility performance, and an effective disintegration time.

[0012] The granule can be applied in a variety of applications to a variety of target agricultural products. The granule can be applied to soil, crops, plants, organisms, and other targets of agricultural interest, which have an effect on the target agricultural product.

[0013] The active component may be defined as any substance or mixture of substances that can be used for the specific control of nuisance organisms. Exemplary active components include, but are not limited to, pesticides, insecticides, fungicides, and herbicides. An active component may also be defined as any substance or mixture of substances which has the purpose or effect of preventing infection of a plant or other target agricultural product by any nuisance organism, or of repelling, deterring or destroying the nuisance organism, or of reducing the damage caused by any nuisance organism.

[0014] The terminology "pesticide," as used herein, is well known in the art and is described at least by the Environmental Protection Agency (EPA), in the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), in the Insecticides and Environmental Pesticide Control Subchapter (7 U.S.C. §136(u)), in the Code of Federal Regulations (CFR) relating to the "Protection of Environment," and in the Regulations of the EPA in 40 CFR §152.3. A pesticide is typically recognized in the art as a substance that is used for preventing, destroying, repelling, regulating, and/or mitigating any pest. A pest is an organism that is deleterious to man or the environment but does not include any internal parasite of living man or other living animal or any fungus, bacterium, virus, or other microorganism on or in living man or other living animals. Said differently, the terminology "pest" does not typically include any organism that infects or sickens humans or animals. However, mosquito control and control of External Pests (such as stable flies) may be included herein. In addition, the terminology "pesticide," as used herein, does not typically include any human or animal drugs or pharmaceuticals, any article that is a "new animal drug" as defined in the art, any liquid sterilant applied to a device used in the human body, and/or any products intended for use against fungi, bacteria, viruses, or other microorganisms in or on living man or living animal. Moreover, the pesticide of this invention does not typically include drugs or pharmaceuticals used to control diseases of humans or animals (such as livestock and pets).

[0015] In a particular embodiment of the invention, the active component comprises a triazine herbicide. A triazine herbicide may include ametryn, atrazine, atraton, cyanazine, cyprazine, desmetryn, dipropetryn, isomethiozin, propazine, prometryn, prometon, sebuthylazine, secbumeton, simazine, terbutryn, terbumeton, terbuthylazine or trietazine. In another specific embodiment, the active component comprises atrazine.

[0016] It is also contemplated that the granule may comprise other active components well recognized by one of ordinary skill in the art. Accordingly, the disclosures of U.S. Patent Publication Nos. 2009/0170704 and 2010/0267790, including the specification, drawings and abstract, are incorporated herein by reference in their entirety.

[0017] The granule can also include various types of auxiliary substances that strengthen the desired effect of the active component. These auxiliary substances may simplify the handling, increase the shelf life, or otherwise improve the properties of the granule.

[0018] The granule includes the active component present in the amount ranging from 70 to 99 wt. by weight of the granule. Alternatively, the granule may include the active component in the amount ranging from 75 to 95 wt.%, or from 85 to 95 wt.% by weight of the granule.

[0019] The granule also includes a copolymer. The copolymer comprises at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit. Without being limited by theory, it is believed that the copolymer enhances the suspensibility and dispersibility of the granule. [0020] Alternatively, the copolymer may consist of, or consist essentially of, the at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit. It is also contemplated that the copolymer may consist of, or consist essentially of, the at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit, in addition to one or more polymer-forming monomer units which do not compromise the functionality or performance of the granules. In various embodiments where the copolymer consists essentially of the at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit, the copolymer is free of, or includes less than 5, 2.5, 1, 0.5, or 0.1 wt. % of, other monomer units. It is further contemplated that the aforementioned description of weight percents may apply to embodiments where the mixture consists essentially at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit. In other embodiments, the terminology "consisting essentially of describes the copolymer being free of compounds that materially affect the overall performance of the copolymer.

[0021] The co olymer may have the average formula (I):

In the above formula, and in one embodiment, the value of w ranges from 20 to 35, the value of x ranges from 17 to 27, the value of y ranges from 28 to 38, and the value of z ranges from 1 to 6. Alternatively, in the above formula, the value of w may range from 23 to 30, or from 25 to 28, the value of x may range from 20 to 26, or from 22 to 24, the value of y may range from 30 to 36, or from 32 to 36, and the value of z may range from 1.5 to 4, or from 2 to 3. Other ranges of w, x, y, and z are also contemplated.

[0022] In reference to the values of w, x, y, and z, they may be provided in various amounts relative to the other units. For example, in one embodiment, the ratio of w to x to y to z ranges from 20:17:28:1 to 35:27:38:6. In one specific embodiment, the ratio of w to x to y to z is about 26.9:23:34.2:2.7. However, other ratios are also contemplated.

[0023] As described above, the copolymer includes the at least one styrene unit. It is contemplated that the at least one styrene unit may be derived from a variety of compounds. The styrene units may have the followin general formula (II):

[0024] The copolymer also includes the at least one alpha-methyl-styrene unit. It is contemplated that the at least one alpha-methyl-styrene unit may be derived from a variety of compounds. The alpha-methyl-styrene unit may be derived from the radical emulsion polymerization of 4-chloro-alpha-methylene styrene or isopropyl benzene. The alpha-methyl-styrene unit may have the followin general formula (III):

[0025] The copolymer also includes the at least one acrylic acid unit. The acrylic acid unit may be derived from a variety of compounds, which include, but are not limited to, alkylacrylic acids, 3-alkylacrylic acids and 3-haloacrylic acids. Specific examples include crotonic acid, cinnamic acid, citraconic acid, sorbic acid, fumaric acid, methacrylic acid, ethacrylic acid, 3-methylacrylic acid, 3-chloroacrylic acid and 3-chloromethacrylic acid. In one embodiment, the acrylic acid unit may have the following general formula (IV):

[0026] The copolymer also includes the at least one ethoxyethoxyethyl acrylate unit. It is contemplated that the at least one ethoxyethoxyethyl acrylate unit may be derived from a variety of compounds. The ethoxyethoxyethyl acrylate unit may have the following general formula (V):

[0027] The copolymer has a weight average molecular weight (M_w) ranging from

5,000 to 50,000. Alternatively, the copolymer may have a weight average molecular weight (M_w) ranging from 5,000 to 15,000, or from 7,000 to 10,000.

[0028] The granule includes the copolymer in an amount ranging from 1 to 10 wt. by weight of the granule. Alternatively, the granule may include the copolymer in an amount ranging from 2 to 9 wt.%, or from 3 to 8 wt.% by weight of the granule.

Alternatively, it is also contemplated that the granule may include other amounts of copolymer, as will be appreciated by one or ordinary skill in the art.

[0029] The copolymer described above may have a variety of structures and configurations, as long as it includes the at least one styrene unit, the at least one alpha-methyl-styrene unit, the at least one acrylic acid unit, and the at least one ethoxyethoxyethyl acrylate unit. For example, the copolymer can be a linear copolymer, a cross-linked copolymer, a randomly branched copolymer, a block copolymer, a periodic copolymer, a graft copolymer, a star copolymer, a star block copolymer, a dendrimer or a combination of the above-listed structures.

[0030] The copolymer described above may be prepared by any method known in the art. For example, the copolymer can be prepared by radical polymerization of the at least one styrene unit, the at least one alpha-methyl-styrene unit, the at least one acrylic acid unit, and the at least one ethoxyethoxyethyl acrylate unit. The polymerization can be carried out by free radical polymerization or by controlled radical polymerization processes. The polymerization can utilize one or more initiators and can be carried out as solution polymerization, as emulsion polymerization, as suspension polymerization, or as bulk polymerization. The polymerization can be carried out batch-wise, semi- continuously or continuously.

[0031] The granule also includes a block-copolymer that comprises at least one ethylene-oxide unit and at least one propylene-oxide unit. Without being limited by theory, it is believed that the block copolymer enhances the suspensibility and dispersibility of the granule. The block-copolymer may include other monomer units besides the ethylene oxide and propylene oxide units. In one embodiment, the block- copolymer is a difunctional block copolymer terminating in primary hydroxyl groups.

[0032] The block copolymer may have a cloud point in a 1 wt. aqueous solution ranging from 10 to 100°C, and a weight average molecular weight ranging from 1,000 to 12,000. The block copolymer may have the formula (VI):

Y[(EO)_p(A)_q(EO)_rH]_s

(VI)

wherein "Y" represents the nucleus of an active hydrogen-containing organic compound having a functionality of s and either from 2 to 6 carbon atoms and 2 to 4 reactive hydrogen atoms or, from 6 to 18 carbon atoms and 2 to 3 reactive hydrogen atoms in the above formula. "A" represents a lower alkylene oxide selected from the group consisting of propylene oxide, butylene oxide, tetrahydrofuran, or mixtures thereof wherein up to 25 percent by weight of "A" is reacted directly with "Y" and 75 percent by weight or more of EO is subsequently reacted to produce the block copolymer. Moreover, in the above formula, "p" ranges from 0 to 65, "q" ranges from 0 to 90, and "r" ranges from 0 to 65.

[0033] The granule includes the block-copolymer in an amount ranging from 0.1 to 5 wt. by weight of the granule. Alternatively, the granule may include the block- copolymer in an amount ranging from 0.5 to 1.5 wt.% by weight of the granule.

[0034] In addition, it is also contemplated that the granule can include other block-copolymers not described above. These block-copolymers can be provided as a liquid, a paste, or in flake form. The block copolymer may also comprise a blend of polyoxyalkylene and fatty alcohols having oxyethylate moieties.

[0035] In addition to the components described above, the granule includes a wetting agent in one or more embodiments. Without being limited by theory, it is believed that the wetting agent enhances the dispersibility of the granule. The wetting agent typically comprises alkylnaphthalene sulfonate. However, it is also contemplated that other wetting agents may be included in the granule as will be appreciated by one of ordinary skill in the art. The wetting agent may comprise anionic, amphoteric, or nonionic surfactants. It is also appreciated that the granule may include a combination of different wetting agents.

[0036] Suitable anionic surfactants for use as the wetting agent include, but are not limited to, carboxylates; alkali earth metals; sodium salts of fatty acids; acyl glutamates; sarcosinates; taurates; methylcelluloses; alkyl phosphates, e.g., monophosphoric acid alkyl esters and hypophosphoric acid alkyl esters; sulfates; monomeric sulfonates, in particular, alkyl- and alkylarylsulfonates, alkylbenzenesulfonic acids, such as, for example, phenolsulfonic acids, naphthalene- and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, or mono- or dialkylsuccinic acid ester sulfonates; protein hydrolysates and spent lignosulfite waste liquors.

[0037] Suitable nonionic surfactants for use as the wetting agent include, but are not limited to, glycerol esters, such as, for example, glycerol monostearate; sugar surfactants, in particular, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate) and esters of mono- or polyhydric alcohols, such as, for example, alkyl(poly)glycosides and N-alkylgluconamides; alkyl methyl sulfoxides; and alkyldimethylphosphine oxides, such as tetradecyldimethyl- phosphine oxide [0038] The amphoteric surfactants for use as the wetting agent include, but are not limited to, sulfobetaines, carboxybetaines, and alkyldimethylamine oxides, e.g., tetradecyldimethylamine oxide.

[0039] Alternatively (or in addition to the above), the wetting agent may comprise silicone surfactants; phospholipids, such as, e.g., lecithin or chemically modified lecithins; amino acid surfactants, e.g., N-lauroylglutamate, polyacrylic acids in the form of their salts, polyvinyl alcohol, polypropylene oxide, poly-ethylene oxide, maleic anhydride/isobutene copolymers and vinylpyrrolidone/vinyl acetate copolymers.

[0040] Furthermore, the wetting agent may comprise one or more of the following compositions: dioctyl sulfosuccinate (e.g., "Pelex OTP"), dialkylsulfonimide ("Leophen RBD"), diisobutylnaphthalene- sulfonate ("Nekal BX"), various alkylalkynols ("Surfynol," "Bisterfeld"), alkylarylphenol ether phosphate esters ("Phospholan PNP") and polyethylene glycol ("Pluriol"), and also combinations of the materials described.

[0041] The granule includes the wetting agent in the amount ranging from 0.1 to 10 wt. by weight of the granule. Alternatively, the granule may include the wetting agent in the amount ranging from 0.1 to 8 wt.%, or from 2 to 4 wt.% by weight of the granule. Alternatively, it is also contemplated that the granule may include other amounts of wetting agent.

[0042] In one or more additional embodiments, the granule optionally comprises a disintegrant agent. Without being limited by theory, it is believed that the disintegrant agent lowers the disintegration time of the granule. If present, the disintegrant agent may comprise polyvinylpyrrilodone. In one embodiment, the disintegrant agent has the following general formula (VII):

[0043] If the disintegrant agent is present, the granule typically includes the disintegrant agent in the amount ranging from 0.1 to 5 wt.% by weight of the granule. It is also contemplated that the disintegrant agent may be present in the amount ranging from 0 to 5 wt.%, or from 0 to 4 wt.%, or from 0 to 2 wt.% by weight of the granule. The disintegrant agent ensures that the granule exhibits optimal disintegration time.

[0044] The above described active component, copolymer, block-copolymer, wetting agent, and disintegrant agent may be contained in suspensions and pre- concentrates, or in some alternative form, prior to forming the granule. These forms may aid in forming a granule having the desired physical and chemical properties.

[0045] The granule may also include auxiliary components, such as antifoaming agents, additional suspension agents, retention agents, pH buffers and drift retardants, wherein each category may comprise a multitude of suitable substances. These auxiliary components may include, but are not limited to, anti-dusting agents, supporting substances, polymers for improving the structure of the granule, coating agents or polymeric flow improvers. Such auxiliary components may be selected by a person skilled in the art. Hydrophilic pyrogenic silicas, such as the Aerosil brands (Degussa), can also function as auxiliary agents and/or antiblocking agents.

[0046] The granule may be essentially anhydrous. Therefore, the granule may have a water content of less than 5 wt.% or less than 2 wt.% by weight of the granule. Alternatively still, the granule may include up to 10 wt.% or, up to 15 wt.% of water by weight of the granule.

[0047] The granule may optionally include various mineral and water-soluble powders, which may act as fillers. Examples of mineral powders that may be used in the present invention include diatomaceous earth, talc, clay, bentonite, and calcium carbonate. Examples of water-soluble powders that may be used in the present invention include saccharides, urea and various types of salts. Saccharides include lactose, fructose, and glucose. Salts include alkali metal salts and sodium salts of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid or carbonic acid. These powders may be used singularly or in combination in the granule formulation.

[0048] The granules formed may exhibit several desirable properties. The suspensibility of the inventive granules may range from 60 to 95%, or from 70 to 95%, or from 85 to 95% when tested according to CIPAC MT 168. The dispersibility of the inventive granules ranges from 5 to 30 inversions, or from 5 to 25 inversions, or from 5 to 20 inversions. The disintegration time of the inventive granules ranges from 5 to 300 seconds, or from 10 to 200 seconds, or from 10 to 100 seconds. [0049] The invention also provides a method of producing a granule is described. The method includes the step of providing the active component, copolymer, block- copolymer, and wetting agent (step a). The disintegrant agent may optionally be provided. The method also includes the step of mixing the active component, copolymer, block-copolymer, and wetting agent (step b). The method also includes the step of forming the mixture of step (b) into water dispersible granules (step c).

[0050] During the step of mixing, the active component, copolymer, block- copolymer, and wetting agent may be combined with an appropriate amount of water as determined by one having ordinary skill in the art. It is contemplated that the above components may be added in any order. In addition, any of the above components may be pre-dissolved in water or other solvent to aid in the mixing step, provided that the ultimate solubility in water is not significantly affected. Optional components may also be added at various points throughout the method of producing a granule.

[0051] In one embodiment, the mixing step may be accomplished with a wet milling machine, such as a ball mill. Alternatively, the mixing step may be accomplished with a masticating extruder, such as a kneader. Alternatively still, it is also contemplated that the mixing of the above components may be accomplished with other mixer types, such as various blending mixers, as will be appreciated by one of ordinary skill in the art. Depending on the mixing step used, a dough or slurry is created. The dough or slurry can be formed into the granules through additional steps described below.

[0052] The step of forming the mixture of step (b) into granules may be further defined as including the steps of granulating the mixture into wet granules and drying the wet granules to form the water dispersible granules. Alternatively, the step of forming the mixture of step (b) into granules may comprise utilizing a spray dryer or fluidized bed to form the granules that are dried through the granulating process.

[0053] Furthermore, the step of granulating the mixture of step (b) into wet granules described above may comprise radially extruding the mixture into wet granules. Alternatively, the step of granulating the mixture of step (b) may comprise pan-granulating the mixture into wet granules.

[0054] The step of drying of the wet granules may be performed with one or more ovens, air dry systems, or alternative drying systems, as will be appreciated by one of ordinary skill in the art. [0055] If a spray dryer is used to perform the step of drying the wet granules, the hot-air inlet temperature of the spray dryer is typically set to a temperature lower than, or equal to, the melting point of the active component used in the granule. Alternatively, the hot-air inlet temperature of the spray dryer may be set to a temperature which is 20 °C less than the melting point of the active component.

[0056] The granules may be sieved in order to yield granules of relatively uniform size. In this context, the granules have a particle size ranging from 5 to 100 mesh, or from 10 to 40 mesh.

EXAMPLES

[0057] Without being limited, one suitable method to form the granule described herein is provided below. In this example, atrazine, the copolymer, the block copolymer and alkylnapthalene sulfonate, and polyvinylpyrrolidone homopolymer are mixed in a Waring commercial blender for 10 min. Deionized water is then sprayed onto the mixture to form a wet cake. The wet cake is transferred to a radial extruder set at a speed of 25 r/min to begin granulation. After granulation, the wet granules are dried in an oven at 50 °C for at least 2 hours to reduce the moisture level from 10-15 wt. to less than 1.5 wt. . Finally, the granules are sieved to yield a free-flowing, non-dusting granule having a particle size between 10 and 40 mesh (0.425 mm to 2.0 mm).

[0058] As used herein, hard water refers to water which is made with calcium chloride dihydrate and magnesium hexahydrate at a 4:1 Ca/Mg ratio with a final concentration of 342 ppm.

[0059] The granules described herein exhibit excellent suspensibility levels. In other words, the granules described herein minimally settle when prepared in an aqueous dispersion (suspension) within foreseeable periods and minimally separate at the surface ("creaming"). One measure for this characteristic is the suspensibility as defined in CIPAC MT 168. In this measurement, a suspension of known concentration of hard water is added to a measuring cylinder at a constant temperature, and allowed to remain undisturbed for the specified time. The top 9/10ths of the hard water by volume are drawn off and the content of active ingredient in the bottom 1/lOth by volume determined. Based on the concentration on the bottom 1/lOth, the concentration of the top 9/10ths can be determined. Table 1 provided below sets forth the measured suspensibility of several embodiments. [0060] The granules described herein are dispersible in water. The granules have the ability to break-up under agitation and be distributed in a liquid. In this measurement, 2 grams of granules are added to a 98 ml of the 342 PPM hard water in a 100 mL graduated cylinder and mixed by manual inversion. The dispersibility is determined when there are no longer unbroken granules in the cylinder. Table 1 provided below sets forth the dispersibility of several embodiments of the present invention.

[0061] In addition to having excellent suspensibility and dispersibility, the inventive granules also demonstrate excellent disintegration times. As described herein, the disintegration time refers to the time it takes for the granule to fall below the surface of the water and break-up, as determined visually. In this measurement, 2 grams of granules are added to 98 mL of the 342 PPM hard water in a 100 mL graduated cylinder and a timer is started. The disintegration time result is determined when 95 to 98% of the granules fall below the surface of the hard water.

TABLE 1: Example Compositions

[0062] It is to be understood that the appended claims are not limited to express any particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments that fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and/or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[0063] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims and are understood to describe and contemplate all ranges, including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.

[0064] In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

The invention has been described in an illustrative manner and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings and the invention may be practiced otherwise than as specifically described.

Claims

CLAIMS What is claimed is:

1. A water dispersible granule comprising:

a. an active component present in an amount ranging from 70 to 99 wt.% by weight of said granule;

b. a copolymer present in an amount ranging from 1 to 10 wt.% by weight of said granule and comprising at least one styrene unit, at least one alpha- methyl- styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit;

c. a block-copolymer present in an amount ranging from 0.1 to 5 wt.% by weight of said granule and comprising at least one ethylene-oxide unit and at least one propylene-oxide unit; and

d. a wetting agent present in an amount ranging from 0.1 to 10 wt.% by weight of said granule.

2. A water dispersible granule as set forth in claim 1, wherein said copolymer has the following average formula:

wherein w ranges from 20 to 35, x ranges from 17 to 27, y ranges from 28 to 38, and z ranges from 1 to 6.

3. The water dispersible granule as set forth in claim 2, wherein a ratio of w to x to y to z ranges from 20:17:28:1 to 35:27:38:6.

4. The water dispersible granule as set forth in any preceding claim, wherein said wetting agent comprises alkylnaphthalene sulfonate.

5. The water dispersible granule as set forth in any preceding claim, further comprising a disintegrant agent present in an amount ranging from 0.1 to 5 wt. by weight of said granule, wherein said disintegrant agent comprises polyvinylpyrrolidone.

6. The water dispersible granule as set forth in any preceding claim, wherein the suspensibility of said granule ranges from 60 to 95% when tested according to CIPAC MT 168, and wherein the disintegration time of said granule ranges from 5 to 300 seconds when 2 grams of said granule are added to 98 mL of 342 ppm hard water.

7. The water dispersible granule as set forth in any preceding claim, wherein the dispersibility of said granule ranges from 5 to 30 inversions when 2 grams of said granule are added to 98 mL of 342 ppm hard water.

8. The water dispersible granule composition as set forth in any preceding claim, wherein said copolymer has a weight average molecular weight (M_w) ranging from 5,000 to 50,000.

9. A water dispersible granule as set forth in any preceding claim, wherein:

said copolymer is present in an amount ranging from 2 to 9 wt.% by weight of said granule; said block-copolymer is present is an amount ranging from 0.5 to 1.5 wt.% by weight of said granule; and

said wetting agent is present in an amount ranging from 2 to 4 wt.% by weight of said granule.

10. The water dispersible granule as set forth in any preceding claim, wherein said copolymer consists essentially of said at least one styrene unit, said at least one alpha-methyl-styrene unit, said at least one acrylic acid unit, and said at least one ethoxyethoxyethyl acrylate unit.

11. A method of forming water dispersible granules, said method comprising:

a. providing: an active component in an amount ranging from 70 to 99 wt.% by weight of the granules, a copolymer in an amount ranging from 1 to 10 wt.% by weight of the granules, a block-copolymer present in an amount ranging from 0.1 to 5 wt.% by weight of the granules, and a wetting agent present in an amount ranging from 0.1 to 10 wt.% by weight of the granules,

wherein the copolymer comprises at least one styrene unit, at least one alpha-methyl-styrene unit, at least one acrylic acid unit, and at least one ethoxyethoxyethyl acrylate unit, and

wherein the block-copolymer comprises at least one ethylene-oxide unit and at least one propylene-oxide unit;

b. mixing the active component, the copolymer, the block- copolymer, and the wetting agent to form a mixture; and

c. forming the mixture of step (b) into water dispersible granules.

12. The method of producing water dispersible granules as set forth in claim 11, wherein step (c) is further defined as:

granulating the mixture of step (b) into wet granules; and drying the wet granules to form the water dispersible granules.

13. The method of producing water dispersible granules as set forth in claim 11 or 12, wherein the step of granulating the mixture of step (b) into wet granules comprises radially extruding the mixture into wet granules.

14. The method of producing water dispersible granules as set forth in claims 11-13, wherein the copolymer has the following average formula:

15. The method of producing water dispersible granules as set forth in claims 11-14, wherein the copolymer consists essentially of the at least one styrene unit, the at least one alpha-methyl-styrene unit, the at least one acrylic acid unit, and the at least one ethoxyethoxyethyl acrylate unit.