GB2049427A - Emulsifiable concentrate formulations compatible with water and liquid fertilizers - Google Patents

Abstract

The disclosure herein relates to stable emulsifiable concentrate formulations comprising as the biologically- active ingredient thereof at least one compound selected from the group consisting of substituted acetanilides, carbamates and anilines and an emulsifier system comprising an amino and a phosphated ethoxylated aliphatic alcohol or phosphated ethoxylated alkyl phenol. The formulations herein are physically compatible with both water and liquid fertilizers.

Description

SPECIFICATION Emulsifiable concentrate formulations compatible with water and liquid fertilizers BACKGROUND OF THE INVENTION Field of the invention The invention herein pertains to the field of emulsifiable concentrate formulations having biological activity, e.g., as herbicides, and having as the active ingredient thereof at least one compound selected from the group consisting of substituted acetanilides, carbamates and anilines.

Description ofthe PriorArt The prior art relative to emulsifiable concentrate (EC) formulations includes a wide variety of active ingredients and emulsifier/surfactant systems therefor. Such EC's are suitable for a variety of biological and agricultural utilities, both plant and animal, e.g., on soil or plants as herbicides, herbicidal antidotes, plant growth regulators, nematocides, bactericides, fungicides, insecticides, soil fumigants, etc.

In practice, the EC containing the biologically-active ingredient is diluted in water and/or liquid fertilizer before application to the target area. In some situations, the user of the biological formulation may be satisfied to use just an aqueous emulsion of the E.C., for any of the above-mentioned utilities, including herbicidal formulations. Alternatively, and of growing practice, the user of a biological formulation may desire to apply a liquid fertilizer simultaneously with and from the same container holding a herbicide, etc.

However, a distinct limitation upon the use of various EC's is that whereas an EC may be suitably compatible with water, it is incompatible with liquid fertilizers and vice-versa; said incompatibility being manifested by phase separation of components usually within a short period of time. Even when a herbicidal EC is specifically designed for compatibility with a liquid fertilizer, such compatibility can be short-lived. For example, in U.S.Pat. 3,236,626, the biocidal toxicant fertilizer composition designed for prolonged stability only had a useful life "... for periods of the order of at least hours." The instability of the herbicide-fertilizer mixture and phase separation results in non-uniform distribution of herbicide and fertilizer, hence erratic and incomplete weed control and crop feeding, in addition to apparatus and equipment problems and failures. It then requires continuous agitation of the herbicide-fertilizer mixture to keep the components in a homogeneous state, a practice both cumbersome, expensive and not always practicable.

In further attempts to obtain stable compositions of biologically active components, with or without fertilizer materials, various workers in the prior art have resorted to emulsifier-surfactant systems based upon a balancing of the hydrophilic and lipophilic (i.e., "HLB" balance) components of the system; see e.g., U.S. Patent Nos. 3,236,626,3,986,862 and 4,080,191.

A further problem associated with many prior art EC's is the necessity to use a stabilizer for various components therein. As an example, heretofore it has been necessary to use a stabilizer, or combination of stabilizers to stabilize herbicidal formulations of such acetanilides as alachlor, i.e., 2', 6'-diethyl-N (methoxymethyl)-2-chloroacetanilide.

Yet another problem in the use of prior art formulations mixed with fertilizers is the corrosion problem.

Containers used by farmers to tank mix herbicides and fertilizers are commonly made of mild steel, zinc or aluminum or alloys containing these elements. These containers are subject to corrosion from water and acidic components of the fertilizer and aqueous herbicidal formulations.

It is, therefore, the primary object of this invention to provide EC's of biologically-active formulations which are physically compatible with both water and liquid fertilizers.

Another object of this invention is to provide an emulsifier system for biologically-active EC's which simultaneously provides emulsification, stabilization and anti-corrosion properties.

A particular object and advantage of this invention is the provision of an EC of herbicidally-active compounds which can be used equally well in either aqueous systems or liquid fertilizer systems which are physically and homogeneously stable for a period of weeks, as opposed to hours as presently known.

Yet another object of this invention is the provision of a stabilized EC which is not dependent upon any particular HLB characteristic or parameter. Thus, for a fixed ratio of surfactants, the EC's of this invention are stable and compatible with all waters (i.e., soft, WHO and hard) and with fluid fertilizers, whereas prior art EC's using conventional anionic and nonionic surfactants must be present in matched pairs to balance performance in each water and fluid fertilizer system.

These and other objects will become apparent from the description below.

Summary of the Invention This invention relates in its broader aspect to an emulsifiable concentrate comprising (A) At least one biologically-active compound selected from the group consisting of substituted acetanilides, carbamates and anilines; (B) An emulsifier system comprising (1) one of more primary and/or secondary phosphate esters of ethoxylated mono, di- and trialkyl phenols or ethoxylated C820 aliphatic alcohols, and (2) an amine selected from the group consisting of (a) fatty tertiary amines of the formula R1N(R)2, where R is a C15 alkyl radical and R' is a Cub.18 aliphatic hydrocarbon radical; (b) fatty amine oxides of the formula

(c) beta-amines of the formula H2CCH(NH2)R1;; (d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2, and (e) ethoxylated tertiary amines of the formulae (i) R1-N(CH2CH2OH)2, and (ii) (HOCH2CH2)NR (CH2)3N(CH2CH2OH)2 and (f) polypropoxylated low molecular weight tertiary amines, and (C) A solvent when necessary or desired.

Particularly preferred herbicidal emulsifiable concentrates are those wherein component (A) is present in an amount within the range of about 5.0 - 98.0%, preferably within the range of about 10.0 - 30.0% by weight, component (B) is present in an amount within the range of about 2.0 - 50.0% by weight, preferably from 3.0 to 15.0%, and the balance component (C). The weight ratio of components (B)(1 ) to (B)(2) will vary somewhat in EC's having different component (A) members, but in general will be within the range of about 1:1 to 10:1, preferably from about 4:1 to 6:1.

The solvent component (C) may be either a straight solvent or mixed solvent, no criticality being placed thereon.

In another aspect, this invention relates to EC's of the above description wherein the biologically-active component is effective under appropriate conditions and concentrations as a herbicide, a non-phytoxic plant growth regulant, herbicidal antidote, insecticide, nematocide, fungicide, bactericide, or other biologicallyeffective utility. Although of very broad purview and contemplation, the presently-preferred biologicallyactive compounds are substituted 2-haloacetanilides, carbamates and anilines.Of particular interest as representative compounds of these classes are specifically mentioned in their embodiments as herbicidal compounds alachlor, butachlor, acetochlor, metolachlor, trial late, trifluralin, EPTC and butylate, with and without an antidote, e.g., N,N-diallyl-2, 2-dichloroacetamide, and homologs, isomers, analogs and other structurally related compounds having herbicidal activity.

In its most preferred aspect, the present invention relates to herbicidal EC's of the above description wherein the herbicidally-active ingredient is alachlor and the preferred emulsifier system comprises as the phosphate ester a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and the preferred amine is an ethoxylated coconut oil amine.

Finally, the invention in practical application relates to physically stable emulsion of biologically-active, e.g., herbicidal, EC's as defined above in water and in liquid fertilizer compositions.

Detailed Description of the Invention As indicated in the Summary of the Invention, it has been discovered that broad spectrum performance with respect to stailization, spontaniety and corrosion inhibition in a wide variety of emulsifiable concentrates (EC's) has been achieved by means of a unique emulsification system which is equally effective in all waters and in liquid fertilizers.

The EC's herein comprise a complexed combination of the following components: (A) At least one biologically-active compound selected from the group consisting of substituted acetanilides, carbamates and anilines; (B) An emulsifier system comprising (1) one or more primary and/or secondary phosphate esters of ethoxylated mono, di- and trialkyl phenols or ethoxylated C820 aliphatic alcohols and (2) an amine selected from the group consisting of (a) fatty tertiary amines of the formula R1 N(R)2, where R is a C1.5 alkyl radical and R1 is a C818 aliphatic hydrocarbon radical; (b) fatty amine oxides ofthe formula

(c) beta-amines oftheformula H3CCH(NH2)R1; ; (d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2, where R is a C1.5 alkyl radical; (e) ethoxylated tertiary amines of the formulae (i) R2-N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1 (CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines; and (C) A solvent when necessary or desired.

With further respect to the above emulsification system, suitable phosphate esters of ethoxylated alcohols, both aromatic and aliphatic (component (B)(1)) are prepared by reacting P205 with a variety of non-ionic surface active agents as described in full detail in U.S. Patent 3,004,056, which is incorporated herein by reference. Representatives of such phosphate esters are commercially available, e.g., from GAF Corporation, under the GAFAC tradename series, e.g. GAFAC RE-610, GAFAC RM 510, GAFAC PE 510, etc.; these surfactants being defined as free acid of complex organic phosphate of aromatic or aliphatic hydrophobe base.

With further respect to the amine- components (B)(2), preferred members of the (a) subclass are those fatty tertiary amines where R1 is a C12H25 or C18H37 alkyl radical; a preferred subclass (b) member are fatty amine oxides wherein R1 is a C12H25 radical; preferred beta-amines of subclass (c) are those wherein R1 is an aliphatic C818 aliphatic hydrocarbon chain which may be saturated or unsaturated; preferred subclass (d) amido-bridged tertiary amines are those where R1 is a fatty radical (chiefly C12) derived from coconut oil or from castor oil (chiefly rincinoleic acid); preferred ethoxylated tertiary amines of subclass (2)(e)(i) above are those wherein R' is coconut oil or tallow, and for subclass (2)(e)(ii) R1 is tallow and preferred subclass (f) members are the commercially available (Witco) amines identified as OSA-75 and OSA-120.

It has been found that the above emulsifier system is suitable across a number of different classes of chemical compounds, thus suggesting broad spectrum applicability.

In preferred embodiments, the emulsifier system herein is useful in current commercial herbicides. Tests have shown that representative component (A) members include 2-haloacetanilides within the formula

wherein Xis chlorine, bromine or iodine; n is an integer from 0-5 and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkyalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocycyl radicals having up to 7 ring members, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and di-alkyl amino groups.The preferred R2 and R3 aliphatic members are those having up to 8 carbon atoms and preferred aromatic members having up to 10 carbon atoms. Of still more preferred interest are 2-haloacetanilides wherein R2 is an alkyl or alkoxyalkyl radical and R3 members are hydrogen, alkyl, alkoxy and/or alkoxyalkyl radicals, and, particularly, alkyl, alkoxy or alkoxyalkyl substitution in at least one, preferably both, ortho positions.Of primary importance are the specific members 2', 6'-diethyl-N (methoxymethyl)-2-chloro-acetanilide (common name "alachlor"); 2'6'-diethyl-N-(butoxy-methyl)-2chloroacetanilide (common name "butachlor"); 2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide (common name"acetochlor"); and 2'-ethyl-6'-methyl-N-(1-methoxyprop-2-yl)-2-chloroacetanilide (common name "metolachlor").

Another class of component (A) members are thio-carbamates having the formula

wherein R4 is a C1.4 alkyl or di- or trichloroallyl radical and R5 is a C1 4 alkyl, preferably n-or i-propyl and i-butyl. Preferred members within the above class are S-2,3,3-trichloroallyl diisopropylthiocarbamate (common name "triallate"), S-ethyl diisobutylthiocarbamate (common name "butylate") and S-ethyl di-n-propylthiocarbamate (common name "EPTC").

Yet another class of component (A) members in the above emulsification system are substituted 2,6-dinitro-4-trifluoromethylanilines of the formula

wherein R6 is C1 4 lower alkyl member, preferably, n-propyl. This class is represented by the compound 2,6-dinitro-4-trifluoromethylaniline (common name "trifluralin").

A solvent (component (C)) may be used to solubilize any component, esp. component (A), which is ' water-insoluble or normally insoluble at ambient temperatures. Exemplary solvents include aromatic, paraffinic or naphthenic hydrocarbon solvents or blends thereof, such as benzene, toluene, alkylated naphthalenes, cyclohexane, the xylenes and kerosene, halobenzenes, e.g., mono-chlorobenzene, halogen ated alkanes, etc. These and other organic solvents sold undertradenames, such as Tenneco T-400 or T-500-100, which are mixtures of aromatic hydrocarbons in the C8-C9 range, including the alkylbenzenes. The selection of a solvent is not critical to this invention, but is subject to normal considerations of safety, environmental impact considerations and physical and cost limitations.

In addition to the foregoing ingredients, other conventional additaments may be included, such as defoamers, e.g., silicone polymers, commercially available, e.g., as Mazu DF-100s, odorants and dyes, as will be understood by those skilled in the art.

In broad purview, the EC's of this invention contain biologically-active compounds (component (A) members) exemplified above and are suitable for use in any biological utility of which said compounds are effective. The primary aspect of this invention is the EC; the particular utility is secondary, being dictated by the properties and characteristics of actve ingredient(s) in the EC. Thus, EC's herein find utility in such biological areas as herbicides, herbicidal antidotes, plant growth regulators, insecticides, fungicides, nematocides, bactericides, soil fumigants, etc. However, of primary interest and application herein, the present EC's are equally compatible in all waters and fluid fertilizers making them highly desirable vehicles for plant and soil treatment, e.g., in herbicidal, herbicide/antidote and plant growth regulator formulations.

Of particular interest herein is the provision of herbicidal and herbicide/antidote EC's which are of broad commercial application and which contain as the active ingredient thereof the above preferred compounds identified by chemical nomenclature and common name. While particularly useful in many crop/weed regimes, the above herbicide formulations have particular limitations which are recognized. Thus, alachlor, if used alone is somewhat injurious to sorghum; butylate somewhat injurious to field corn and butachlor to some rice. Consequently, herbicidal antidotes or safeners have been developed to reduce crop injury by the herbicide. For example, it has been found that suitable antidotes for alachlor, butachlor, acetochlor or metolachlor in sorghum are ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate and benzyl-2-chloro-4trifluoromethyl-5-thiazolecarboxylate.An effective antidote for butachlor in rice is 3-(2'5'dimethoxyphenacyl)-phthalide or ethyl 5-(2,4-dichlorophenyl)-4-isoxazolecarboxylate. An effective antidote for metolachlor in corn is a-(cyanomethoxyamino)-benzacetonitrile and an effective antidote for EPTC and butylate in field corn is N,N-diallyl-2, 2-dichioro-acetamide.

The herbicidal EC's herein are very versatile in use. Thus, where it is desired to apply a herbicide either in straight water base or in a fluid fertilizer solution, the EC's herein are equally suitable; such EC's are unknown to the prior art. In current practice, distinct EC's must be provided for use in water-based formulations and in fluid fertilizer-based formulations, because neither formulation is compatible with or physically stable in the other base. Moreover, the prior art EC's generally require added stabilizers to retard degradation of the E.C.

The preferred EC's- herein are those wherein component (A) is present in a herbicidally effective amount within the range of about 5.0 - 98.0% by weight, preferably 5.0 - 50%, component (B) is present in an amount within the range of about 2.0 - 50.0% by weight, preferably from 3.0 to 15% by weight and the balance component (C); the weight ratio of components (B)(1) to (B)(2) is within the range of about 2:1 to 10.1. The preferred component (B)(1) member is a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and component (B)(2) is an ethoxylated tertiary amine of the formula R1 N(CH2CH2-OH)2 wherein R1 is a C818 aliphatic hydrocarbon radical, the weight ratio of components (B)(1) to (B)(2) being within the range of about 4.0:1.0 to 6.0:1.0.A more preferred component (B)(1) member is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and a preferred component (B)(2) member is an ethoxylated tertiary amine derived from coconut oil, soybean oil, cottonseed oil, palm oil or tallow, exemplified by commercially-available surfactants such as Ethomeen C/12, C/15, C/20, C/25, S/12, 5/15, S/20, T/1 2, T/1 3, T/20, etc. Preferred emulsifiable concentrates herein are those wherein component (A) is selected from the group consisting of alachlor, butachlor, acetochlor, metolachlor, triallate, trifluralin, EPTC and butylate.

Preferred EC's according to this invention are described in Examples 1-8 below.

Example 1 In this example, a 4 Ib/gal (0.48 kg/l) EC formulation of alachlor is described.

Ingredients Weight Percent Alachlor (91% assay) 49.63 GAFAC RE-610 4.125 Ethomeen C/12 0.875 MazuDF-100s 0.010 Methyl violet 0.017 Solvent (monochloro benzene and T-400) 45.343 100.00 Example 2 This example describes a 5 Ib/gal (0.6 kg/l) EC formulation of butachlor.

Ingredients Weight Percent Butachlor (89% assay) 65.46 GAFAC PM 510 4.125 Ethomeen C/12 0.875 Methyl violet 0.017 Mazu DF-100s 0.01 T500-100 29.513 100.00 Example 3 This example describes a 4 Ib/gal EC formulation of acetochlor.

Ingredients Weight Percent Acetochlor (93% assay) 51.59 GAFAC RE-610 8.25 Ethomeen C/12 1.75 T-500-100 38.41 100.00 Example 4 This example describes a 4 Ib/gal EC formulation of metolachlor.

Ingredients Weight Percent Metolachlor (93.77%) 48.19 GAFAC RE-610 2.00 GAFAC PE-510 2.00 Ethomeen C/12 1.00 Solvent (T400 and monochlorobenzene) 46.81 100.00 Example 5 A 4 Ib/gal EC formulation of trial late is described in this example.

Ingredients Weight Percent Triallate (91%) 43.27 GAFAC RE-610 1.80 GAFAC PE-510 2.70 Ethomeen C/12 0.50 Xylene 51.73 100.00 Example 6 This example describes a 7 lb/gal (0.84 kg/l) EC formulation of butylate.

Ingredients Weight Percent Butylate (100%) 90.00 GAFAC RE-610 3.60 GAFAC TE-51 0 5.40 Ethomeen C/12 1.00 100.00 Example 7 This example describes a 7 Ib/gal EC of butylate containing as an antidote the compound N,N-diallyl-2,2dichloro-acetamide.

Ingredients Weight Percent Butylate (100%) 85.83 Antidote 4.17 GAFAC RE-610 3.60 GAFAC TE-51 0 5.40 Ethomeen C/12 1.00 100.00 Example 8 This example illustrates a 4 Ib/gal EC formulation of trifluralin.

Ingredients Weight Percent Trifluralin (95%) 48.32 Flo MO6NP 4.25 Ethomeen C/12 0.75 Solvent (T 400) 46.68 100.00 In order to demonstrate the compatability and stability of the EC's of this invention in emulsions of water and fluid fertilizers, a series of tests were run using a variety of emulsification systems according to this invention. In these tests, the water used conformed to World Health Organization (WHO) standard water, defined as a combination hard water of 342 ppm hardness (0.304 g. CaCI2, an hydros or 0.4027 g.

CaC12.2H20, plus 0.139 g. MgCl2.6H2O plus distilled water to make 1 liter). The fertilizer solution used was a 28% nitrogen solution fertilizer made up by dissolving 496.4 g. of NH4NO3 and 396.8 g. of urea in 386.56 g.

distilled water to make a one liter solution.

In conducting the stability tests in the fluid fertilizer solution approximately 1.6 ml of the EC is added to 40 mis of fertilizer solution in a suitable container which is then stoppered and vigorously shaken. Volume percent separation is observed and determine after 15 minutes.

In conducting the water tests, both for spontaniety ("bloom") and stability, a measured volume of the EC is poured into the water in a suitable container, e.g., a Nesslertube, via a funnel and observing the degree of spontaneous emulsification. After the emulsion cloud reaches the bottom of the tube, the tube is stoppered, inverted 15 times and observed after 15 minutes and/or one hour for any separation. This test is usually run at a dilution rate of 1:19, e.g., 5 ml of EC in 95 ml water.The criteria for judging spontaniety is as follows: "Perfect" - a thick emulsion cloud descending to the bottom of the tube without separation of any type; "Good" - thin "bloom" or cloud with no separation or thick cloud with minor separation such as emulsion trials at 1" (2.5 cm) or less from the bottom of the tube, "flowering", etc., and "Poor" - emulsion cloud containing oil droplets with oil separation from cloud above 1 " from bottom of the tube.The criteria for measuring stability is the formation of 2 ml or less cream and no oil in WHO water and 5 mi or less cream and no oil in soft and hard waters; "soft water" is defined as having 114 ppm hardness prepared by diluting 1 part WHO hard water (defined above) with 2 parts of distilled water, and "hard water" is defined as 1000 ppm all calcium (prepared by dissolving 1.4691 g. of 100% CaCl2.2H2O in distilled water and diluting to 1 liter) = 1000 ppm CaCO3. The volume separation in mls is converted by formula into volume percent separation.

In Table 1 data is presented for tests at 60"C of a plurality of emulsification systems for alachlor as the active ingredients (component (A)) in the above EC description. In these tests, the phosphate ester component ((B)(1) above) was a mixture of mono- and di-phosphate esters of ethoxylated nonylphenol and the amine component ((B)(1 )(a)-(f)) in the above EC description is identified as in Examples 9-20. All the surfactants used herein, both phosphate esters and amines are available from commercial surfactant suppliers.

TABLE 1 Surfactant Volume Percent Separation Wt.% (after 15 minutes) Example Phosphate Ester Amine (B)(1): WHO Fertilizer No. (B(1) Component) (B(2) Component) (B)(2) (2)Water Solution (28% N) 9 GAFAC RE-610 (a) H25C12N(CH3)2 90:10 Zero Zero 10 DO (a) H37C18N(CH3)2 85:15 Zero Zero O # 11 Do (b) H25C12N(CH2CH2OH)2 75:25 Zero Zero 12 Do (c) H21C10CH(NH2)CH3 70:30 Zero Zero 13 Do (c) H41C20CH(NH2)CH3 85:15 Zero Zero 14 Do (d) RCON(CH2)3N(CH3)2 80:20 Zero Zero (R = fatty radical derived from coconut oil; chiefly C12) 15 Do (d) RCO(CH2)3N(CH3)2 80:20 Zero Zero (R = fatty radical derived from castor oil; chiefly rincinoleic acid) 16 Do (e)(i) R-N(CH2CH2OH)2 82.5:17.5 Zero Zero (R = coconut oil) 17 Do (e)(i) R-N(CH2CH2OH)2 90:10 Zero Zero (R = tallow) 18 Do (e)(ii) (HOCH2CH2)NR- 90:10 Zero Zero (CH2)3N(CH2CH2OH)2 R = tallow) 19 GAFAC RE-610 (f) Polypropoxylated low 60:40 Zero Zero molecular weight tertiary amine OSA-75 (Witco) 20 Do (f) Do, but OSA-120 60:40 Zero Zero As will be apparent from the stability data in Table 1, the EC's according to this invention were all perfectly stable 15 minutes after emulsification. The significance of this stability data will be more appreciated by reference to the stability data for commercial EC's set forth in Table 2 below according to test procedures described above.

In Table 2, under the first column are listed various EC's; these EC's were tested in waters of various hardness ranging from soft through WHO to hard waters indicated under the second column and in liquid fertilizer solutions of 28% nitrogen ("LF" in second column). The properties of the tested EC's are shown under the columns entitled "Spontaniety" and "Stability"; the data for the invention EC's is listed side-by-side that for EC's now in commercial use. As stated earlier herein, since EC formulations of a particular composition which are stable in water are unstable in liquid fertilizers and vice-versa, the result is a necessity to resort to two distinct EC's differently formulated in order to obtain maximum stability in the different emulsion bases. Thus, in Table 2, Formulation A is a commercial "water-grade" EC containing alachlor as the active ingredient and Formulation B is a differently-formulated commercial alachlor EC for use in liquid fertilizers. Similarly, Formulation C is a water-grade butachlor EC and formulation D is a fertilizer-grade butachlor EC. The emulsification systems of the commercial EC's are proprietary to the manufacturers, but are of no significance for purposes of these tests other than to show the overall inferiority thereof relative to the unique emulsification system of this invention.

TABLE 2 Stability (Vol. % separation Spontaniety after 15 min.,; 60 C) Water Hardness Invention Commercial Invention Commercial E.C. (CaCO3Eq.) EC EC EC EC A 114 - Perfect - Zero (Water-grade 312 - " - " Alachlor) 1000 - " - " LF - Poor - 50-60 B 114 - Poor - 50-60 (Fertilizer-grade 312 - " - " Alachlor) 1000 - " - " LF - Good - Zero C 114 - Perfect - Zero (Water-grade 312 - " - Zero Butachlor) 1000 - " - Zero LF - Poor - 50-60 D 114 - Poor - 60 (Fertilizer-grade 312 - " - " Butachlor) 1000 - " - " LF - Good - Zero Alachlor 114 Perfect (See Formu- Zero (See Formulations (Example 1) 312 " lations A & B) " A and B) 1000 " " LF Good " Butachlor 114 Perfect (See Formula- Zero (See Formulations (Example 2) 312 " tions C & D) " C & D) 1000 " " LF " " TABLE 2 (Cont'd) Stability (Vol. % separation Spontaniety after 15 min.; 60 C) Water Hardness Invention Commercial Invention Commercial E.C. (CaCO3Eq.) EC EC EC EC Acetochlor 114 Perfect Perfect Zero (Example 3) 312 " - " 1000 " - " LF " - " Metychlor 114 Perfect Perfect Zero Zero (Example 4) 312 " " " " 1000 " " " " LF " " " 99 Triallate 114 Perfect Perfect Zero Zero (Example 5) 312 " " " " 1000 " " " " LF " " " 50 Butylate 114 Perfect Perfect Zero Zero (Example 6) 312 " " " " 1000 " " " " LF " " " 90 EPTC 114 Perfect Perfect Zero Zero (Example 7) 312 " " " " 1000 " " " " LF " " " 90 Trifluralin 114 Perfect Perfect Zero Zero (Example 8) 312 " " " " 1000 " " " " LF " " " 98 Analysis of the data in Table 2 immediately points up the overall outstanding superiority of the invention EC's both on an absolute basis and as compared to typical EC's of leading commercial herbicides.In more particular, it will be noted that the invention EC's: (1) generally rate "Perfect" in spontaniety in all waters and in liquid fertilizers; (2) maintain 100% stability (i.e., zero % separation) after 15 minutes with all active ingredients tested in both waters and liquid fertilizers and (3) as a corollary to (2), utilizes a single emulsification system for both waters of all hardnesses and for liquid fertilizers.In contrast, the prior art commercial EC's are shown to exhibit such deficiencies as: (1) lack of uniform spontaniety and stability in both water and fluid fertilizers; while generally exhibiting good stability in water, the commercial EC's are uniformly unstable in liquid fertilizers, except as in the case of Formulations B and D where (2) distinct formulations are required to obtained a modicum of stability and (3) when resort is had to different formulations, spontaniety suffers with respect to the other base, whether water or liquid fertilizer. That is, e.g., while spontaniety of water-grade Formulations A and C is "Perfect" in water, it is "Poor" or no better than "Good" in liquid fertilizers. Similarly, although spontaniety of fertilizer grade EC's B and D is "Good" in liquid fertilizer, it is "Poor" in all waters.Concomitantly, when changing formulations to accommodate different base systems, it is commonly required to add nsnionic and anionic surfactants to balance the hydrophilic and lipophilic properties of the system ("HLB"). The present invention eliminates any need for consideration and cost of additional surfactants to achieve any required HLB criteria.

In additional comparative tests, the EC of Example 1 was tested with and without added stabilizer; it is known that EC B in Table 2 requires and contains an added stabilizer. These test results showed that zero separation (100% stability) occurred after 15 minutes at 60"C according to standard test methods. It is thus shown that the unique emulsification system of this invention has the important added advantage of eliminating the necessity to use and cost of added stabilizers in commercial EC's.

An even more profound demonstration of the outstanding advantages of the EC's of this invention is shown in long-term stability tests. The EC's of Examples 1-3 were further tested according to the above test protocol in WHO water and 28% liquid fertilizer solution; samples of the EC of Example 1 included material both with and without added stabilizer. The data from these tests showed that there was zero percent phase separation and no decomposition or deterioration of active ingredient even after aging for a month at 60"C.

The benefits of long-term stability in such emusions is manifest, e.g., with respect to shelf-life, warehousing, transporting and use of product. These stability data are to be contrasted with prior art and current commercial liquid fertilizer emulsions which are physically stable in terms of only a few hours.

An incidental, but important, additional advantage accruing from the discovery of the EC's herein is the elimination of analytical test procedures designed to determine the "redispersability" properties of emulsions made from known and experimental EC's. Due to the instability of such emulsions, phase separation occurs when the EC is diluted in mix tanks and allowed to sit. The formulation must then be agitated, stirred or shaken to redisperse the ingredients. Hence, analytical tests have been developed to determined the re-dispersability property of the emulsions. EC's of the present invention render such redispersion tests obsolete; by itself a marked advance in the art.

Yet another important contribution to the EC art, the present EC's provide markedly enhanced corrosion inhibition vis-a-vis other known fertilizer grade formulations of the prior art, both "dry" and in the presence of water. As an illustration of the increased corrosion inhibition, the EC of Example 1 was compared with the commercial fertilizer-grade EC of Formulation B in Table 2; both of these EC's contain alachlor as the active ingredient. The comparative data is shown in Tables 3 and 4. In Table 3 is summarized the corrosion rates of the compared EC's on mild steel, in the dry state and containing various amounts of added water; data based on accelerated static corrosion tests for 3 days at 600C. In Table 4 is summarised the corrosion rates of steel, aluminum and zinc, again with and without added water. Test conditions were static partial immersion for 3 days at 490C.

TABLE 3 Corrosion in Mils Per Year Water Added (%) Formulation "Dry" 0.5 1.0 2.0 B 2.0 10.0 46.4 52.9 Example 1 Nil 4.0 29.2 38.1 Analysis of the data in Table 3 shows that the EC of Example 1 is unexpectedly superior to EC B from the stand-point of corrosion inhibition. In terms of percentages the EC of Example 1 is 200%, 60%, 37% and 28%, respectively, less corrosive than EC B in the dry state and with 0.5%, 1.0% and 2.0%, respectively, water added.

TABLE 4 Corrosion Rate in Mils Per Year Formulation Steel Aluminum Zinc B-"Dry" 2.0 0.4 180.0 Ex.1-"Dry" Nil Nil 7.7 B - 2% H2O 52.9 14.2 245.0 Ex. 1 - 2% H2O 38.1 Nil 6.6 Analysis of the data in Table 4 shows that the anti-corrosion properties of the EC of Example 1 is significantly superior to those of EC B with respect to the three metals tested. In particular, it is noted that the EC of Example 1 is non-corrosive in the dry state in steel and aluminum and in aluminum even when containing 2% water. An out-standing improvement in corrosion resistance in zinc is shown by the EC of Example 1 vis-a-vis that of EC B in both dry and wet states; notable improvement is also shown in the EC of Example 1 over EC B when each contains 2% water in aluminum.

The particular significance for comparative tests of the respective EC's in steel, aluminum and zinc is that these are the primary metals used in the containers when the EC's are transported, shelved, warehoused and/or mixed by formulators, distributors and farmers.

Emulsifiable concentrates according to this invention have been widely tested as herbicides in the field in numerous crops and weeds. It has been found that there are no significant differences in crop safety or yield or in weed control between the EC's of this invention and analogous ones of the prior art not containing the unique emulsification system of this invention. Typical of such field tests are illustrated in Examples 21-36 in Tables 5-7. The data in these tables represents a composite summary of tests conducted in many different states across America. These tests involved applying herbicidal formulations of Formulations A and B (Table 2) and Example 1 to corn, soybeans and snapbeans under identical conditions.In Tables 5-7 are shown in the columns from left to right, the example number, particular formulation, carrier volume in gallons/acre (liters/hectare), application rate of active ingredient (alachlor) in pounds/acre (kg/hectare), application mode, i.e., whether pre-emergence ("Pre") or preplant incorporated ("PPI"); "DAT" represents the number of days after treatment of the plants that observations were made and recorded, the crop and weeds (a dash indicates species not in test) and the percent injury to the plants in terms of stand reduction and the states in which the tests were conducted.The letter symbols "a....1" represent weeds according to the following legend: a - Yellow nutsedge g-- Barnyard grass b- Lambsquarter h - Common purslane c- Green foxtail i- Seedlingjohnsongrass d - Velvetleaf j - Pennsylvania Smartweed e- Giantfoxtail k- Redroot pigweed f- Large crabgrass I - Yellow foxtail TABLE 5 Applica Carrier Vol. tion Rate Applica- Percent Injury (Stand Reduction) Ex. Gal/A. (lb/A) tion No. E.C. (L/H) (Kg/H) Mode DAT Corn a b c d e f g h i j k l State 21 A 20(187) 2.5(2.8) Pre 25 0 - - - 80 - - - 97 - - - - - Neb.

Ex. 1 " " " " 0 - - - 68 - - 90 - - - - 22 A 25(233.8) 2.5(2.8) " 27 0 - 97 - - - - - - - 95 - B " " " " 0 - 98 - - - - - - - 98 - - Ohio Ex.1 " " " " 0 - 100 - - - - - - - 100 - 23 A 20(187) 2.5(2.8) " 34 0 - - - 96 97 - - - - - - B " " " " 0 - - - 96 96 - - - - - - - Ind.

Ex.1 " " " " 0 - - - 96 96 - - - - - - 24 A 30(280.5) 3.0(3.4) PPI 35 0 - - - - - - - - - - - 100 Id.

Ex.1 " " " " 0 - - - - - - - - - - - 100 25 A 30(280.5) 3.0(3.4) PPI 39 0 - - 81 - - - - - - - - Ex.1 " " " " 0 - - 77 - - - - - - - - - Id.

26 A 20(187) 3.0(3.4) Pre 43 0 - - 99 - - - - - - 99 99 - ND EX.1 " " " " 0 - - 99 - - - - - - 99 99 27 A 25(233.8) 3.5(3.9) Pre 34 0 - - 99 99 - - - - - - - B " " " " 0 - - 99 99 - - - - - - - - Ia.

Ex.1 " " " " 0 - - 99 99 - - - - - - - 28 A 20(187) 3.5)3.9= PPI 56 0 - - - 50 95 - - - - - - B " " " " 0 - - - 50 98 - - - - - - - III.

Ex.1 " " " " 0 - - - 40 98 - - - - - - 29 A 20(187) 3.5(3.9) Pre 30 0 - 88 88 - - - - - - - - Ex.1 " " " " 0 - 100 100 - - - - - - - - - Minn.

30 A 18(168.3) 40.0(4.48) Pre 26 0 - - - - - 80 - - - - 93 Ex.1 " " " " 0 - - - - - 85 - - - - 93 - Col.

TABLE 6 Applica- Percent injury (Stand Reduction) Carrier Vol. tion Rate Applica Ex. Gal/A. (lb/A) tion Soy No. E.C. (L/H) (Kg/H) Mode DAT beans a b c d e f g h i j k l State 31 A 20 (187) 2.5 (2.8) Pre 0 - - - - - - - - - - 93 Ex.1 " " " 0 - - - - - - - - - - 93 - Okla.

32 B 20 (187) 2.5 (2.8) Pre 43 4 - - - - - 99 95 - - - - Ex. 1 " " " " 14 - - - - - 70 80 - - - - - Tenn.

33 A 21 (196.4) 3.5 (3.9) Pre 21 0 - - - - - - - - 65 - - Ex. 1 " " 2 " 0 - - - - - - - - 40 - - - La.

34 A 21 (196.4) 3.5 (3.9) Pre 22 0 - - - - - - - - 20 - - Ex. 1 " " " " 0 - - - - - - - - 35 - - - La.

35 A 20 (187) 3.0 (3.4) Pre 32 0 - - 96 - - - - 86 - - - B " " " " 0 - - 94 - - - - 91 - - - - Neb.

Ex. 1 " " " " 0 - - 97 - - - - 98 - - - - TABLE 7 Applica- Percent Injury (Stand Reduction) Carrier Vol. tion Rate Applica Ex. Gal/A. (lb/A) tion Snap No. E.C. (L/H) (Kg/H) Mode DAT beans a b c d e f g h i j k l State 36 A 29 (271.2) 3.0 (3.4) PPI 36 6 91 - - - - - - - - - - Ex. 1 " " " " 5 84 - - - - - - - - - - - Calif.

Analysis of the data in Tables 5-7 leads to a conclusion that the herbicidal alachlor EC of Example 1, representative of this invention, and the current water-grade alachlor formulation (EC A) and fertilizer-grade alachlor formulation (EC B) perform essentially identically under comparable test conditions and locations, with an exception or two which under replication would undoubtedly level out.

It will, therefore, be manifestly apparent that the broad spectrum performance of the EC's of this invention is unique in this field. Thus, in summary, the outstanding advantages and improvements of the EC's of the present invention over prior art EC's are as follows: 1. A single, homogeneous EC which is compatible with and physically stable in both water (of all normal degrees of hardness, including WHO) and in fluid fertilizers,.

2. Long-term stability; some EC's of the invention have survived aging for at least one month.

3. Corrosion inhibition improvement shown by orders of magnitude in some cases.

4. Elimination ofthefollowing (a) Added stabilizers; (b) Anionic and nonionic surfactants previously required for "butting" and HLB balancing, and (c) Analytical test procedures for redispersability.

5. A unitary container; it is no longer necessary to provide separate containers of different materials having differing anti-corrosion properties for water grade and fertilizer-grade EC's and 6. The improved EC's of this invention exhibit the same herbicidal properties as prior art herbicides having the same active ingredient with respect to crop safety and weed control.

The general parameters ofthe EC's and dispersions thereof have been outlined above. However, it may be pointed out that in the experience of the assignee herein, the preferred active ingredients herein are 2-haloacetanilides wherein the a-halogen is chlorine or bromine; the anilide ring is substituted with hydrogen, C1.6 alkyl, alkoxy or alkoxyalkyl radicals, preferably one or both ortho positions relative to the anilide nitrogen being occupied with alkyl and/or alkoxy radicals and, occasionally a further addition of one or two alkyl and/or alkoxy ring substitutions notably in the meta positions. The preferred R2 members are hydrogen, C1.4 alkyl radicals or an alkoxy-alkyl radical having up to 12 carbon atoms, up to 8 of which may be in the alkoxy moiety and up to 4 of which may be in the alkyl moiety.

Representative straight or branched alkyls (the term embraces primary, secondary and tertiary alkyls) include methyl, ethyl, propyl, the butyls, pentyls, hexyls, heptyls, octyls, nonyls, decyls, undecyls and dodecyls.

Representative alkenyl members include vinyl, allyl, crotyl, methallyl and ethylenically unsaturated analogs of the above alkyls.

Representative alkynyls include ethynyl, the propynyls, butynyls and acetylenically unsaturated analogs of the above alkyls.

Representative alkoxy radicals include methoxy, ethoxy, propoxy, butoxy, etc., and the isomeric alkoxys thereof.

Representative alkoxyalkyls include methoxymethyl, ethoxymethyi, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl, the isomeric amyloxymethyls, hexyloxymethyls, etc., and the corresponding alkoxyethyls, alkoxypropyls and alkoxybutyls, all of which may be substituted with non-interfering groups, e.g., lower alkyl, etc., aliphatic members of which contain up to 4 carbons.

Representative heterocycles and heterocyclylalkyls include furanyl, furfuryl, tetrahydrofuryl, tetrahydrofurfuryl, pyranyl, tetrahydropyranyl, thienyl, pyrrolyl, pyrazolyl, thiazole, oxazinyl, triazinyl, etc.

Representative cycloalkyl and cycloalkylalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclobutylmethyl, etc.

Representative aryl, aralkyl and alkaryl radicals include phenyl, benzyl, tolyl, xylyl, naphthyl, methylphenyl, ethylphenyl, etc.

While the various components of the EC's herein have been generally disclosed and particularly described in specific working embodiments, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit and scope of this invention. Illustrative of such modifications are the combination of one or more biologically-active ingredients that complement one another, e.g., the combination of different herbicides that effectively control different weeds such as alachlor pius atrazine, linuron, metribuzin, etc. Also, it is within the purview of this invention to combine various phosphate esters and/or amines of the present emulsification system to achieve the same or modified emulsification effects. In like manner, various solvents may be mixed to effect cost or performance optima.

The fluid fertilizers herein include water-soluble or suspensions of nitrogen, potassium and/or phosphate salts ranging from 3-18-18 and a 10-34-0 analysis to 32% nitrogen solution, e.g., derived from urea and ammonium nitrate.

The foregoing description is understood to be exemplary and not exhaustive of the scope of the invention which otherwise is defined by the claims herein.

Claims (48)

1. An emulsifiable concentrate comprising (A) At least one biologically-active compound selected from the group consisting of substituted acetanilides, carbamates and anilines; (B) An emulsifier system comprising (1) one or more primary and/or secondary phosphate esters of ethoxylated mono, di and trialkyl phenols or ethoxylated C820 aliphatic alcohols and (2) one or more amines selected from the group consisting of (a) fatty tertiary amines of the formula R1N(R)2, where R is a C18 alkyl radical and P1 is a C818 aliphatic hydrocarbon radical; (b) fatty amine oxides of the formula

(c) beta-amines of theformula H3CCH(NH2)R1;; (d) amido-bridged tertiary amines of the formula R1CON(CH2)3N(R)2, where R is a C1-5 alkyl radical; (e) ethoxylated tertiary amines of the formulae (i) R1-N(CH2CH2OH)2 and (ii) (HOCH2CH2)NR1 (CH2)3N(CH2CH2OH)2; and (f) polypropoxylated low molecular weight tertiary amines; and (C) A solvent when necessary or desired.

2. Emulsifiable concentrate according to Claim 1 wherein component (A) is present in a herbicidally effective amount within the range of about 5.0 - 98.0% by weight, component (B) is present in a amount within the range of about 2.0 - 50.0% by weight and the balance component (C).

3. Emulsifiable concentrate according to Claim 2 wherein the weight ratio of components (B)(1) to (B)(2) is within the range of about 1:1 to 10:1.

4. Emulsifiable concentrate according to Claim 3 wherein component (B)(1) is a mixture of mono- and diphosphate esters of ethoxylated nonylphenol and component (B)(2) is an ethoxylated tertiary amine of the formula P1 N(CH2CH2OH)2 wherein R' is a C818 aliphatic hydrocarbon radical, the weight ratio of components (B)(1 ) to (B)(2) being within the range of about 4.0:1.0 to 6.0:1.0.

5. Emulsifiable concentrate according to Claim 4 wherein component (B)(1) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (B)(2) is Ethomeen C/12.

6. Emulsifiable concentrate according to Claim 5 wherein component (A) is a 2-haloacetanilide having the formula

wherein Xis chlorine, bromine or iodine; n is an integer from 0-5 inclusive and R2 and R3 represent hydrogen, halogen, alkyl, alkenyl, alkynyl, akoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkyalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and di-alkyl amino groups.

7. Emulsifiable concentrate according to Claim 5 wherein Xis chlorine or bromine; n is an integer from 0-3 inclusive, R2 is hydrogen, C1 4 alkyl or a Cm 12 alkoxyalkyl radical having up to 8 carbons in the alkoxy moiety and up to 4 carbons in the alkyl moiety and R3 is hydrogen or C1.8 alkyl, alkoxy or alkoxyalkyl radical.

8. Emulsifiable concentrate according to Claim 7 wherein component (A) is alachlor.

9. Emulsifiable concentrate according to claim 7 wherein component (A) is butachlor.

10. Emulsifiable concentrate according to Claim 7 wherein component (A) is acetochior.

11. Emulsifiable concentrate according to Claim 7 wherein component (A) is metolachlor.

12. Emulsifiable concentrate according to Claim 5 wherein component (A) is a thiocarbamate having the formula

wherein R4 is a C1.4 alkyl or di- ortrichloroallyl radical and R5 is a C1.4 alkyl radical.

13. Emulsifiable concentrate according to Claim 12 wherein said thiocarbamate is triallate.

14. Emulsifiable concentrate according to Claim 12 wherein said thiocarbamate is buty!ate.

15. Emulsifiable concentrate according to Claim 12 wherein said thiocarbamate is EPTC.

16. Emulsifiable concentrate according to Claim 5 wherein component (A) is a compound having the formula

wherein R6 is a C1 4 alkyl radical.

17. Emulsifiable concentrate according to Claim 16 wherein said compound is trifluralin.

18. Emulsifiable concentrate according to any of Claims 6-16 or 17 wherein a defoamer, odorant and/or dye is present.

19. Emulsifiable concentrate according to any of claims 6-17 or 18 which further contains an antidote for component (A).

20. Emulsifiable concentrate according to Claim 19 wherein said antidote is ethyl 2-chloro-4trifluoromethyl-5-thiazolecarboxylate or benzyl-2-chloro-4-trifluoromethyl-5-thiazolecarboxylate when component (A) is alachlor, butachlor, acetochlor or metolachlor.

21. Emulsifiable concentrate according to Claim 19 wherein said antidote is 3-(2'5'dimethoxyphenacyl)phthalide or ethyl 5-(2,4-dichlorophenyl)-4-isoxazolecarboxylate when component (A) is butachlor.

22. Emulsifiable concentrate according to Claim 19 wherein said antidote is a-(cyanomethoxyamino)benzacetonitrile when component (A) is metolachlor.

23. Emulsifiable concentrate according to Claim 19 wherein said antidote is N,N-diallyl-2, 2- dichloroacetamide when component (A) is EPTC or butylate.

24. A physically stable emulsion comprising (I) Water as the dispersion medium or (II) A liquid fertilizer comprising solutions or suspensions of nitrogen, potassium and/or phosphate salts ranging from 3-18-18 and a 10-34-0 analysis to 32% nitrogen solution as the dispersion medium;; (III) At least one biologically-active compound selected from the group consisting of substituted 2-haloacetanilides, carbamates and anilines and (IV) An emulsifier system comprising (A) one or more primary and/or secondary phosphate esters of ethoxylated mono-, di- and trialkyl phenols or ethoxylated C80 aliphatic alcohols and (B) one or more amines selected from the group consisting of (1) fatty tertiary amines of the formula R' N(R)2, where R is a C1 5 alkyl radical and R1 is a C818 aliphatic hydrocarbon radical; (2) fatty amine oxides of the formula 0 P1N(CH2CH2OH)2; (3) beta-amines oftheformula H3CCH(NH2)R';; (4) amido-bridged tertiary amines of the formula R'CON(CH2)3N(R)2, where R is a C1 5 alkyl radical; (5) ethoxylated tertiary amines of the formula (a) R1-N(CH2CH2OH)2 and (b) (HOCH2CH2)NR1 (CH2)3N(CH2CH2OH)2; and (6) polypropoxylated low molecular weight tertiary amines and (C) A solvent when necessary or desired.

25. Emulsion according to Claim 24 wherein said dispersion medium is component (I) of soft, hard or WHO hardness.

26. Emulsion according to Claim 24 wherein said dispersion medium is component (II).

27. Emulsion according to claims 25 or 26 wherein said emulsifier system comprises (a) a mixture of mono and diphosphate esters of ethoxylated mono- and dinonyl phenols and (b) an ethoxylated tertiary amine of the formula P1 N(CH2CH2OH)2 wherein P1 is an aliphatic hydrocarbon radical derived from coconut oil, castor oil or tallow, the weight ratio of components (a) to (b) being within the range of about 1.0:1.0 to 10:1.0.

28. Emulsion according to Claim 27 wherein component (a) is a free acid of a complex organic phosphate ester of aromatic or aliphatic hydrophobe base and component (b) is Ethomeen C/12, the weight ratio of (a) to (b) being within the range of about 4.0:1.0 to 6.0:1.0.

29. Emulsion according to Claim 28 wherein component (III) is a 2-haloacetanilide having the formula

wherein X is chlorine, bromine or iodine; n is an integer from 0-5 inclusive and R2 and R3 represent hydrogen, halogen, alkyl, akenyl, akynyl, alkoxyalkyl or polyalkoxyalkyl groups having up to 18 carbon atoms, cycloalkyl, cycloalkyloxy or cycloalkylalkyl groups having up to 10 carbon atoms, aralkyl or alkaryl groups having up to 18 carbon atoms or O, S or N heterocyclyl or heterocyclylalkyl radicals having up to 7 ring members, and up to 3 carbons in the alkyl moiety, or said R2 and R3 members substituted with alkyl, alkenyl, alkynyl, halo, nitro, cyano, hydroxy, CF3, amino, mono- and di-alkyl amino groups.

30. Emulsion according to Claim 29 wherein Xis chlorine or bromine; n is an integer from 0-3 inclusive, R2 is hydrogen, C1 4 alkyl or a C1-12 alkoxyalkyl radical having up to 8 carbons in the alkoxy moiety and up to 4 carbons in the alkyl moiety and R3 is hydrogen or Cur 8 alkyl, alkoxy or alkoxyalkyl radical.

31. Emulsion according to Claim 30 wherein component (III) is alachlor.

32. Emulsion according to Claim 30 wherein component (Ill) is butachlor.

33. Emulsion according to Claim 30 wherein component (III) is acetochlor.

34. Emulsion according to Claim 30 wherein component (III) is metolachlor.

35. Emulsion according to Claim 28 wherein component (Ill) is a thiocarbamate having the formula

wherein R4 is a Cur 4 alkyl or di- ortrichloroallyl radical and R5 is a C1 4 alkyl radical.

36. Emulsion according to claim 35 wherein said thiocarbamate is trial late.

37. Emulsion according to Claim 35 wherein said thiocarbamate is butylate.

38. Emulsion according to Claim 35 wherein said thiocarbamate is EPTC.

39. Emulsion according to Claim 28 wherein component (III) is a compound having the formula

wherein R6 is a C1 4 alkyl radical.

40. Emulsion according to Claim 39 wherein said compound is trifluralin.

41. Emulsion according to any of claims 29-39 or 40 wherein a defoamer, dye and/or odorant is present.

42. Emulsion according to any of Claims 29-40 or 41 which further contains an antidote for component (111).

43. Emulsion according to Claim 42 wherein said antidote is ethyl 2-chloro-4-trifluoromethyl-5thiazolecarboxylate or benzyl-2-chloro-4-trifluoromethyi-5-thiazolecarboxylate when component (ill) is alachlor, butachlor, acetochlor or metolachlor.

44. Emulsion according to Claim 42 wherein said antidote is 3-(2'5'-dimethoxyphenacyl)phthalide or ethyl 5-(2,4-dichlorophenyl)-4-isoxazolecarboxylate when component (III) is butachlor.

45. Emulsion according to Claim 42 wherein said antidote is a-(cyanomethoxyamino)-benzaceto-nitrile when component (III) is metolachlor.

46. Emulsion according to Claim 42 wherein said antidote is N,N-diallyl-2,2-dichloroacetamide when component (Ill) is EPTC or butylate.

47. Emulsion according to Claim 26 wherein component (II) is a nitrogen solution derived from urea and ammonium nitrate having up to 32% nitrogen.

48. Emulsifiable concentrate according to Claim 2 wherein component (B) is present in an amount within the range of about 3.0 to 15.0%.