P/00/01I Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Invention Title: High-strength, low-temperature stable herbicidal formulations of 2,4-dichlorophenoxy acetic acid salts The following statement is a full description of this invention, including the best method of performing it known to us: 800499824 HIGH-STRENGTH, LOW-TEMPERATURE STABLE HERBICIDAL FORMULATIONS OF 2,4-DICHLOROPHENOXY ACETIC ACID SALTS The present invention relates to herbicidal formulations of 2,4 5 dichlorophenoxy acetic acid (2,4-D). More particularly, the present invention concerns high-strength formulations of mixed 2,4-D salts that remain liquid at low temperature. 2,4-D is a known, effective herbicide. Various formulations are currently marketed, many of which are aqueous solutions that can be used as is or diluted 10 prior to use. Typically the 2,4-D is provided as a salt, which exhibits sufficiently high solubility in water to provide a high-strength aqueous herbicidal formulation. A high-strength formulation is desirable for a variety of economic and environmental reasons. For example, it is desirable to provide a high-strength formulation to reduce shipping and handling costs and to reduce the amount of 15 packaging material that must be disposed. The high-strength formulations should be stable and retain potency during storage and shipping. Furthermore, the high strength formulation should be a clear, homogeneous liquid that is stable at ambient temperatures and should not exhibit any precipitation at temperatures as low as 0*C. 20 A major limitation of the dimethylamine (DMA) salt of 2,4-D is limited stability at low temperature and high concentration. For example, an aqueous formulation containing 625 grams acid equivalent per liter (gae/L) of the DMA salt of 2,4-D crystallizes at 0*C. The present invention seeks to address these needs and provides a wide variety of benefits and advantages. 25 Surprisingly, it has now been found that the low temperature solubility of a high-strength 2,4-D DMA solution can be improved by adding the dimethylethanolamine (DMEA) or diethylethanolamine (DEEA) salt of 2,4-D to the solution. 2 800499824 The present invention provides a herbicidal formulation comprising a mixture of DMA salt of 2,4-D with a DMEA salt or a DEEA salt of 2,4-D or a mixture thereof in a relative ratio of 2,4-D DMA salt to 2,4-D DMEA or DEEEA salt of between about 55 : 45 to about 40 : 60. 5 More particularly, the present invention provides a stable, high-strength herbicidal formulation, which remains a clear, homogeneous liquid at temperatures as low as 0*C, comprising a mixture of a dimethylamine (DMA) salt of 2,4-dichlorophenoxy acetic acid (2,4-D) with a dimethylethanolamine (DMEA) salt or a diethylethanolamine (DEEA) salt of 2,4-D or a mixture thereof in a 10 relative ratio of 2,4-D DMA salt to 2,4-D DMEA or DEEA salt of between about 55 : 45 to about 40 : 60, wherein the formulation contains at least about 625 gram acid equivalents per liter (gae/L) to about 740 gae/L based upon the 2,4-D acid equivalent of the 2,4-D salt mixture. In still yet another form, the present invention provides a method of 15 treating plants with a herbicidal formulation. The formulation can be provided as described above. The formulation can be applied as a highly concentrated solution or alternatively diluted prior to application to the plants. In general the present invention is directed to a high-strength herbicidal formulations containing 2,4-D salt mixtures. The 2,4-D salt mixture comprises a 20 combination of cations selected from dimethylethanolamine (DMEA) and/or diethylethanolamine (DEEA) cations in admixture with dimethylamine (DMA) cations. The relative amounts of the DMEA and/or DEEA to DMA salts are selected to be between about 45 and about 60 weight percent (wt %) DMEA and/or DEEA salt of 2,4-D and between about 40 and about 55 wt % DMA salt of 25 2,4-D. The herbicidal formulation includes the 2,4-D salt mixture in an amount sufficient to provide the high-strength formulation. The high-strength herbicidal formulation includes at least about 625 gram acid equivalents per liter (gae/L) to about 740 gae/L based upon the 2,4-D acid equivalent of the 2,4-D salt mixture; 30 more preferably, the high-strength herhicidal formulation includes at least about 710 gae/L to about 725 gae/L based upon the 2,4-D acid equivalent of the 2,4-D salt mixture. 3 800499824 Furthermore, the herbicidal formulation also does not exhibit separation or precipitation (or crystallization) of any of the components at low temperatures. For example, the high-strength formulation remains a clear solution at temperatures below about I 0C, more preferably at temperatures about 0*C. 5 The formulations described herein can be applied to plants in an amount sufficient to induce a herbicidal effect. For example, a formulation prepared according to the present invention can be applied as an aqueous solution to plants including the plants' leaves, stems, branches, flower and/or fruit. The herbicidal formulation can be applied in a herbicidally effective amount sufficient to inhibit 10 plant growth or kill individual plants. The agricultural composition prepared according to the present invention are highly effective as a herbicide composition against a variety of weeds and can be used to control weeds in 2,4-D tolerant crops. The formulations of the present invention can be used as is or combined with other components including other 15 agriculturally acceptable adjuvants commonly used in formulated agricultural products, such as antifoam agents and/or sequestering agents. The concentrated agricultural formulations are typically diluted in water and then applied by conventional means well known to those in the art. Reference to any prior art in the specification is not, and should not be 20 taken as, an acknowledgment, or any form of suggestion, that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art. As used herein, except where the context requires otherwise, the term 25 "comprise" and variations of the term, such as "comprising", "comprises" and comprised", are not intended to exclude other additives, components, integers or steps. For the purposes of promoting further understanding and appreciation of the present invention and its advantages, the following Examples are provided. It 30 will be understood, however, that these Examples are illustrative and not limiting in any fashion. 4 800499824 Example 1: Preparation of High-Strength 2,4-D Mixed Salt Formulations A high-strength 2,4-D formulation was prepared containing 728 gram acid equivalent (gae) of 2,4-D per liter (L) in the form of a mixture of 45% DMA / 55% DMEA by dissolving 2,4-D technical (58.8 wt%), dimethylamine (5.5 wt%) and 5 dimethylethanolamine (13 wt%) with stirring in water (22.7 wt%) at room temperature. Example 2: Storage Stability of High-Strength 2,4-D Mixed Salt Formulations 4a High-strength 2,4-D formulations were prepared containing 720 gae of 2,4 D per L according to the general procedure described in Example 1. The formulations contained varying amounts of DMA salt and DMEA salt. Storage 5 stability results at room temperature and at 0*C are summarized in Table I. Table 1 Percentages: Storage: DMA DMEA pH ("as is") 0 0 C RT 100 0 7.03 X C 70 30 7.46 X C 60 40 7.51 X C 55 45 7.65 C C 50 50 7.74 C C 45 55 7.83 C C 40 60 7.90 C C 30 70 7.99 X C 0 100 8.18 X not tested 10 X crystallized C clear The results in Table 1 clearly demonstrate the synergistic effect of the mixed 2,4-D salt solution on the cold temperature stability. Whereas the straight 15 2,4-D DMA salt crystallizes at 0*C and the straight 2,4-D DMEA salt crystallizes even at room temperature, the mixed 2,4-D DMA / DMEA salt solution at certain ratios provides a clear solution at 0*C free from any crystals. 5