Herbicidal compositions and methods of formulating and using same - Patents.com

Abstract

A herbicide composition for controlling weed plants is disclosed. The herbicide composition can include topramezone and dithiopyr. The herbicide composition can include topramezone, 2,4-D, and dicamba. The herbicide composition can include topramezone, 2,4-D, dicamba, and dithiopyr. Also disclosed are granules coated with the herbicide composition. A method for controlling weed plants includes spreading a plurality of granules coated with the herbicide composition on weed plants, or spraying a liquid herbicide composition on weed plants.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 925,535, filed October 24, 2019, which is hereby incorporated by reference in its entirety into this specification.

[0002] Technical Field

[0002] This disclosure relates generally to herbicidal compositions and methods of making and using same. [Background technology]

[0003] Granular weed control products utilized in the consumer turf industry typically contain systemic herbicides such as 2,4-D, MCPP-p and dicamba for post-emergence foliar application of broadleaf weeds. The active ingredient is generally applied to a granular inert carrier or fertilizer granules as a tack-on powder or in liquid form. Typically, the resulting granular material is then applied to moist broadleaf weed plants using a broadcast spreader to spread the granules on the leaf surface. The particles adhere to the moist leaves and solubilize the active ingredient, thus allowing the active ingredient to enter the weed cells and kill the weed plants. It would be desirable to provide a herbicidal composition with improved herbicide uptake in weed plants under suboptimal conditions (e.g., dry) and with more consistent weed control. Summary of the Invention

[0004] According to one embodiment, the herbicidal composition comprises topramezone and dithiopyr.

[0005] According to one embodiment, the herbicide composition comprises topramezone, 2,4-D and dicamba.

[0005]

[0006] According to one embodiment, the herbicide composition comprises topramezone, 2,4-D, dicamba and dithiopyr.

[0007] According to another embodiment, the herbicide composition is granular. The granular herbicide may include a granular carrier coated with the herbicide composition. The granular carrier may include a fertilizer granule or a non-fertilizer granule.

[0006]

[0008] According to another embodiment, the herbicide composition is applied in liquid form.

[0009] According to another embodiment, a method of making a granule includes coating the granule with a herbicide composition described herein.

[0007]

[0010] According to another embodiment, a method for controlling weed plants includes a step of spreading a granular herbicide on dry weed plants.

[0011] Representative embodiments are illustrated in the reference figures of the drawings. It is intended that the embodiments and figures disclosed herein be considered illustrative and not restrictive. [Brief description of the drawings]

[0008] [Figure 1]

[0012] 4 shows a photograph of the lawn 7 days after application of the comparative composition. [Diagram 2]

[0013] 1 shows a photograph of a lawn 7 days after application of a composition according to one embodiment. [Diagram 3]

[0014] 1 is a graph comparing crabgrass control results obtained from a comparative composition and compositions according to various embodiments. [Figure 4]

[0015] 1 is a graph comparing crabgrass density over time in areas treated with a comparative composition and compositions according to various embodiments. [Diagram 5]

[0016] Photographs of lawns are shown three weeks after treatment with various comparative compositions. [Figure 6] Photographs of lawns are shown three weeks after treatment with various comparative compositions. [Figure 7] Photographs of lawns are shown three weeks after treatment with various comparative compositions. [Figure 8]

[0017] 4 shows photographs of lawns 3 weeks after treatment with compositions according to various embodiments. [Figure 9] 4 shows a photograph of a lawn three weeks after treatment with compositions according to various embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009]

[0018] Described herein are compositions and methods for making herbicide compositions. The herbicide compositions can be useful for pre-emergent and post-emergent weed control. Also described herein are fertilizer or carrier granules coated with a coating of herbicide compositions. The herbicide compositions are effective even when applied to plants under suboptimal conditions (e.g., dry leaf conditions). The compositions and methods reduce the likelihood of consumer application errors and improve ease of use to liquid application products without sophisticated equipment while providing similar herbicide effectiveness.

[0010]

[0019] The herbicide composition may include a phenylpyrazolyl ketone herbicide-topramezone-and an auxin mimetic herbicide, a pyridine herbicide, or a combination thereof. In certain embodiments, the herbicide composition may include topramezone at an application rate within the range of about 0.01 lb.ai / A to about 45.36 g (0.1 lb.)ai / A, 4.536 g (0.01 lb.)ai / A to about 22.68 g (0.05 lb.)ai / A, or about 9.072 g (0.02 lb.)ai / A to about 18.14 g (0.04 lb.)ai / A. In various embodiments, the herbicide composition may include topramezone at an application rate of about 4.536 g (0.01 lb.) ai / A, about .03 g (0.05 lb.) ai / A, about .22.68 g (0.05 lb.) ai / A, or about .45.36 g (0.1 lb.) ai / A. In certain embodiments, the herbicide composition may include topramezone in a range of about 0.005 wt% to about 0.04 wt%, about 0.01 wt% to about 0.035 wt%, about 0.015 wt% to about 0.03 wt%, about 0.02 wt% to about 0.0275 wt%, or about 0.023 wt% to about 0.025 wt%. In some embodiments, the herbicide composition may include topramezone at about 0.02 wt%, 0.024 wt%, or 0.0241 wt%.

[0011]

[0020] In certain embodiments, the herbicide composition may include topramezone and an auxin-mimetic herbicide. The auxin-mimetic herbicide may include, for example, one or more of 2,4-dichlorophenoxyacetic acid (2,4-D), (2R)-2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP-p), 3,6-dichloro-2-methoxybenzoic acid (dicamba), and mixtures thereof. In various embodiments, the herbicide composition may include the auxin-mimetic herbicide at an application rate within the range of about 1 pound of active ingredient per acre (lb.ai / A) to about 2 lb.ai / A, about 1.5 lb.ai / A to about 2 lb.ai / A, or about 1.25 lb.ai / A to about 1.75 lb.ai / A. In certain embodiments, the herbicide composition may include an auxin mimetic herbicide at an application rate of about 1.5 lb.ai / A, about 1.6 lb.ai / A, or about 1.7 lb.ai / A. In some embodiments, the herbicide composition may include an auxin mimetic herbicide, which may include an auxin mimetic herbicide mixture, in a range of about 0.05 wt% to about 1.5 wt%, about 0.08 wt% to about 1.3 wt%, about 1 wt% to about 1.3 wt%, about 1 wt% to about 1.3 wt%, or about 1.2 wt% to about 1.3 wt%. In certain embodiments, the herbicide composition may include an auxin mimetic herbicide, which may include an auxin mimetic herbicide mixture, in a range of about 0.08 wt%, about 1.2 wt%, or about 1.285 wt%. In various embodiments, the herbicide composition may include 2,4-D in the range of about 1 wt% to about 1.5 wt%, about 1.1 wt% to about 1.3 wt%, or about 1.15 wt% to about 1.25 wt%, or about 1.2 wt% or about 1.205 wt%. In various embodiments, the herbicide composition may include dicamba in the range of about 0.01 wt% to about 0.2 wt%, about 0.05 wt% to about 0.1 wt%, or about 0.07 wt% to about 0.09 wt%, or about 0.08 wt%. As discussed further in the Examples below, combinations of topramezone with broadleaf herbicides (e.g., 2,4-D) have shown surprising, enhanced injury and control of dandelion and clover. The herbicidal compositions provide increased weed damage symptom development, more complete weed control, and more consistent weed control.Dry foliage application of the herbicidal composition can unexpectedly provide an acceptable level of weed control.

[0012]

[0021] In certain embodiments, the herbicide composition may also include topramezone, a pyridine herbicide, and dithiopyr, which is active against pre-emergent weeds. The herbicide composition including topramezone and dithiopyr may be used to provide late-stage grassy weed control. As further discussed in the examples below, the combination of dithiopyr and topramezone may act synergistically to provide granular post-emergent weed control. In certain embodiments, the herbicide composition may include dithiopyr at an application rate within the range of about 0.1 lb.ai / A to about 1 lb.ai / A, about 0.1 lb.ai / A to about 0.5 lb.ai / A, about 0.1 lb.ai / A to about 0.5 lb.ai / A, or about 0.2 lb.ai / A to about 0.5 lb.ai / A, or about 0.4 lb.ai / A to about 0.6 lb.ai / A. In some embodiments, the herbicide composition may include dithiopyr at an application rate of about 0.25 lb.ai / A, or about 0.5 lb.ai / A. In various embodiments, the herbicide composition may include dithiopyr in the range of about 0.01 wt% to about 0.5 wt%, about 0.1 wt% to about 0.3 wt%, about 0.15 wt% to about 0.25 wt%, or about 0.18 wt% to about 0.22 wt%, or 0.20 wt%. In some embodiments, the ratio of dithiopyr to topramezone is in the range of 8:0.9 to 9:1.1, or about 8.3:1.

[0013]

[0022] In certain embodiments, the herbicide composition may include 2,4-D, dicamba, dithiopyr, and topramezone. In various embodiments, the herbicide composition may consist essentially of 2,4-D, dicamba, dithiopyr, and topramezone. In certain embodiments, the herbicide composition may consist of 2,4-D, dicamba, dithiopyr, and topramezone. In some embodiments, the herbicide composition may include herbicides consisting of 2,4-D, dicamba, dithiopyr, and topramezone. In some embodiments, the ratio of 2,4-D to dicamba to dithiopyr to topramezone is within the range of 48:3:8:0.9 to 52:4:9:1.1, or about 50:3.3:8.3:1.

[0014]

[0023] The herbicide composition can be applied in liquid or granular form. Granular formulations may include the herbicide composition coated on fertilizer granules or on fertilizer-free granules, for example, on inert granules. Examples of fertilizer granules suitable for use herein are generally described in U.S. Pat. No. 9,663,412, the disclosure of which is incorporated herein in its entirety. In one example, the fertilizer granule may include a mixture of urea-containing fertilizer and rice husk. Typical carriers for such granular formulations described in U.S. Pat. No. 5,006,158, the disclosure of which is incorporated herein in its entirety, include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, corn cob, peanut husk, rice husk, and other organic or inorganic materials that can absorb or be coated with the herbicide composition. The granulated formulation can be made by mixing the herbicide composition and the granular carrier together and granulating the mixture to form a granulated herbicide composition. The carrier granules can be sprayed with the herbicide composition or immersed in the herbicide composition to coat the granules with the herbicide composition. In one embodiment, the carrier granules can be uniformly coated with the herbicide composition. The example weight percentage ranges and values ​​given above for the various components in the herbicide composition can be the weight percentage ranges and values ​​of these components relative to the total weight of the granular herbicide in various embodiments.

[0015]

[0024] In certain embodiments, the composition may comprise a herbicide composition comprising 2,4-D, dicamba, dithiopyr and topramezone coated on a fertilizer granule. In certain embodiments, the composition may consist essentially of a herbicide composition comprising 2,4-D, dicamba, dithiopyr and topramezone coated on a fertilizer granule. In certain embodiments, the composition may consist of a herbicide composition comprising 2,4-D, dicamba, dithiopyr and topramezone coated on a fertilizer granule comprising a mixture of urea-containing fertilizer and rice husk.

[0016]

[0025] In certain embodiments, the herbicide composition includes a solvent, modifier, or surfactant. For example, a viscosity modifier, such as dipropylene glycol (DPG), may be added to the herbicide composition. The viscosity modifier allows for lower processing temperatures, which reduces the possibility that the herbicide will decompose during the mixing process. In addition, the viscosity modifier may improve the distribution of the active ingredient (ai) on the surface of the granule. The herbicide composition may contain from greater than 0% to about 30% by weight of the viscosity modifier. In some embodiments, the herbicide may be combined with a solvent (e.g., water, DPG, etc.) before being applied to the granular carrier. When the composition is in granular form, in some embodiments, the granular herbicide may include a solvent in the range of about 0.5 wt% to about 5 wt%.

[0017]

[0026] In use, the herbicide-coated granules are applied to wet or dry weed leaves, and the herbicide disperses. The synergistic properties of topramezone and auxin mimetic herbicides (see Table 8 below) help increase the percentage of active ingredient dispersing from the coated granules, even when the weed leaves are dry. The higher degree of active ingredient translocation results in a greater percentage of weeds killed when applied to dry broadleaf weed leaves, compared to herbicides formulated without topramezone. In addition, topramezone and dithiopyr work synergistically to provide post-emergence grassy weed control of the granules (see Example 7).

[0018]

[0027] The present invention may be further understood by reference to the examples that follow the Summary and Detailed Description thereof, which are provided by way of illustration and are not meant to be limiting.

[0019] Example 1

[0028] Experiments were conducted in Ohio and Oregon to evaluate the efficacy of topramezone, an herbicide that inhibits 4-hydroxyphenylpyruvate dioxygenase (HPPD), in combination with other broadleaf herbicides. Experiments were conducted on common dandelion (Taraxacum officinale), white clover (Trifolium repens) and ragweed (Hypochaeris radicata). All treatments were applied to moist turf. The new herbicide was compared to a commercial granular composition (Comparative Example 1 or CE1) and a commercial spray composition (Comparative Example 2 or CE2).

[0020]

[0029] Treatments were applied with a shaker jar and spreader box. Each plot was 3' x 3' and surrounded by a 2' buffer strip. Granular treatments were applied either by dew to wet leaves or by hand sprayer. CE2 was applied at 1.5 gal / 1000 ft to dry leaves. 2 For the experiments in this example, the application rate of Inventive Example 1 (IE1) and CE1 was 2.856 lb / 1000 ft. 2 and the application rate of CE2 is 4 pints per acre (pt / A) of formulated product.

[0021]

[0030] Table 1 shows the formulations and application rates. IE1 and CE1 were applied at the same fertilizer base (0.8 lb.N / 1000 ft 2 ) which has an NPK ratio of 28-0-3. CE2 is a spray-applied product that does not contain a fertilizer base.

[0022] [Table 1]

[0023]

[0031] The experiment was designed using a randomized complete block design with four replications per treatment. Weed damage and weed control were tested. Weed damage included bleaching, distortion and stunting. Data on visual signs of weed damage were collected on a 0-10 rating scale (see Table 2 below) to quantify symptom development. Physiological signs included chlorosis (yellowing), necrosis (browning), bleaching (whitening), red / purple, leaf spotting, stunting, epistasis (twisting / malformation), etc.

[0024] [Table 2]

[0025]

[0032] Weed control estimates were made by comparing the appearance (e.g., size, vigor, physical condition, density) of individual weed species in the treated plots with the same species in the surrounding untreated buffer area. If the weed density in the plot appears the same as the weed density in the surrounding buffer zone, the "% weed control" is recorded as 0%. The difference in treated weeds compared to untreated weeds is assessed based on the severity of herbicidal symptoms and the progression of herbicidal action at the time of observation. Assessments are recorded as percentages, with a maximum of 100% resulting in complete weed removal from the plot. Percentage control data were analyzed using balanced ANOVA to determine if there was an interaction between location and treatment. When sets of data were statistically similar for a particular rating date, the data were combined and analyzed using one-way ANOVA. When there were statistical differences in the data, they were analyzed and reported separately. Treatment means were separated using Fisher's protected least significant difference test (P=0.05).

[0026] Effect of treatments on common dandelion (Ohio)

[0033] Dandelion trials in Ohio began in the spring when plants were at peak flowering. Dandelion damage (0-10) was assessed 7, 14, and 21 days after application (days after application, DAA, Table 3).

[0027] [Table 3]

[0028]

[0034] At the 7-day evaluation, treatment IE1, which contained topramezone, caused as much damage to dandelions as did liquid-applied CE2. All other granular products had statistically similar levels of herbicide symptomology, and all were significantly inferior to IE1 and CE2. At the 14-day rating, injury symptoms had progressed, but the statistical breakout was very similar to the previous rating, except that the topramezone treatment was beginning to show more injury than CE2. At the 22nd day, all dandelions in the topramezone plot had died, showing how this HPPD-inhibiting herbicide can accelerate the rate of efficacy when combined with CE1.

[0029]

[0035] Ratings of weed control do not generally begin until week 4 in conventional testing. However, because topramezone accelerated the reduction in weed density, it was determined that these ratings should be taken one week earlier. Table 4 shows the percent dandelion control (0-100) assessed between weeks 3 and 10.

[0030] [Table 4]

[0031]

[0036] At the 3 week rating, treatment IE1 with topramezone was rated as having 100% dandelion control. CE1 had statistically poorer control at 3 weeks. Although starting at 4 weeks, resprouting began to occur in many of the treatments, some worse than others. Although IE1 had resprouted plants, the control at the final 10 week rating was still considered fully acceptable. CE2 gave the most consistent results throughout the trial. CE1 gave slightly acceptable results early on, but by 10 weeks, dandelion control had dropped to unacceptable levels, thus illustrating the value of the topramezone addition. Of the treatments containing 2,4-D, this was the only treatment that did not result in acceptable weed control at 10 weeks.

[0032] Effect of treatments on burdock (Oregon)

[0037] In Oregon brambleweed control trials, brambleweed control rates (0-100) were evaluated 6-10 weeks after application (see Table 5 below).

[0033] [Table 5]

[0034]

[0038] Topramezone gave acceptable results beginning at week 6 (possibly earlier but no data taken prior to week 4) and maintained those results through the 10 week rating. In comparison, CE2 did not provide acceptable weed control at any of the ratings.

[0035] Treatment Effects on White Clover (Ohio)

[0039] The white clover trials in Ohio began when dandelions were still at peak flowering, a recognized trigger for consumer purchase and application of weed and feed type products in the northern U.S. White clover injury (0-10) was assessed 3, 10, 13 and 18 days after application (see Table 6 below).

[0036] [Table 6]

[0037]

[0040] IE1 gave better results early (1-2 weeks) that appeared to be similar to those produced by CE2. Again, IE1 showed accelerated results compared to the other granular products, as observed with dandelion (Table 5). However, by week 3, all treatments caused very similar levels of weed damage.

[0038]

[0041] White clover control rates (0-100) were evaluated in Ohio between 3 and 8 weeks after application (see Table 7 below).

[0039] [Table 7]

[0040]

[0042] CE2 provided excellent clover control. However, IE1, a granular treatment containing topramezone, also provided outstanding clover control. CE1 provided marginally acceptable results, providing over 80% control throughout the six weeks.

[0041] Treatment Effects on White Clover (Oregon)

[0043] White clover control rates (0-100) were evaluated in Oregon between 4 and 10 weeks after application (see Table 8 below).

[0042] [Table 8]

[0043]

[0044] The results from this trial were drastically different from those found in Ohio. The consistency of control provided by the combination containing topramezone in the Ohio trial was not observed at this location. The treatments provided very short-term, high levels of control. CE1 did not provide acceptable clover control at any time point. CE2 spray provided acceptable control only at weeks 6 and 7.

[0044] conclusion

[0045] In most cases, topramezone resulted in accelerated injury and higher control rates of target weeds when compared to the herbicide combination without topramezone.

[0045]

[0046] The inclusion of topramezone in 2,4-D + dicamba accelerated the rate of activity against common dandelion and white clover in Ohio. The addition of topramezone tended to enhance the overall herbicide efficacy when compared to the combination without topramezone. This herbicide combination was the only treatment in Oregon that showed acceptable burdock control. Topramezone in combination with 2,4-D + dicamba (IE1) gave the granular formulation results much more similar to those of the sprayed standard CE2, which was an improvement over the granular standard CE1.

[0046] Example 2

[0047] Experiments were conducted to explore the potential of herbicidal compositions containing the active ingredient topramezone, where a pre-emergent herbicide and a post-emergent broadleaf herbicide were combined with a post-emergent crabgrass component. Experiments were conducted in spring and mid-summer in Ohio and Nebraska on Taraxacum officinale and Trifolium repens. In addition, compositions containing pendimethalin or dithiopyr were tested, as shown below in Table 9.

[0047]

[0048] All granular products are based on MLARS (0.8 lb.N / 1000ft 2) was utilized. Treatments were applied with shaker jars and spreader boxes. Plots were 3' x 3' in Ohio and 5' x 5' in Nebraska with a 2' buffer strip surrounding each plot. Granular treatments were applied either by dew to wet leaves or by hand sprayer. In Ohio, CE2 was applied at 1.5 gal / 1000 ft to dry leaves. 2 Spray application was performed using a consumer grade single nozzle applicator wand at a spray volume of 2.856 lb / 1000 ft. In Nebraska, CE2 was applied using a three nozzle boom equipped with an 8002vs nozzle and a CO2 backpack sprayer set at 30 PSI. For the experiments in this example, the application rate for all compositions except CE2 was 2.856 lb / 1000 ft. 2 The application rate of CE2 was 4pt / A.

[0048]

[0049] Table 9 shows the formulations and application methods. Inventive Examples 2 and 3 (IE2 and IE3) and Comparative Example 3 (CE3) were applied at the same fertilizer base (0.8 lb.N / 1000 ft ) as IE1 and CE1. 2 CE2 is a spray product with no fertilizer base.

[0049] [Table 9]

[0050] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1. Treatment Effects (Ohio)

[0051] Tests were conducted in the spring at the peak of dandelion flowering. Dandelion damage (0-10) was assessed 1 and 2 weeks after application in the spring (see Table 10 below).

[0051] [Table 10]

[0052] Treatments formulated with topramezone had the greatest activity of all granular treatments at 14 DAA. They caused the same amount of damage to dandelions as the sprayable gold standard, CE2. Non-topramezone granules (CE1) caused significantly less damage at 14 days.

[0053] Dandelion control (%) was taken at 4, 6, 8 and 10 weeks after application (see Table 11 below). Clover control (%) was taken at 4WAA and total weed control was taken at 8WAA.

[0054] [Table 11]

[0055] At 29 days, all herbicide treatments provided excellent dandelion control, but by 44 days, CE3 began to decline (Table 11). A relative lack of efficacy was observed in the % clover control and overall weed control scores. The two topramezone-based formulations provided excellent control through 72 days. Control was as good as that provided by the sprayable gold standard. CE1 had very desirable dandelion control, but the late season clover and overall weed control scores indicate less effectiveness than the treatments containing topramezone.

[0056] Dandelion damage (0-10) was assessed between weeks 1 and 3 in mid-summer (see Table 12 below).

[0057] [Table 12]

[0058] The treatment list for Ohio was changed to focus on treatments that work better for midsummer timing. CE3 was replaced with IE3. By 2WAA and 3WAA, it was clear that all treatments with topramezone caused much more damage to the dandelions than those without topramezone. Even liquid-applied CE2 had statistically poorer symptoms when compared to these treatments. This is likely due to the blackish-brown necrosis caused by these herbicides, which is much more severe and cosmetically impactful than the epiphytic growth associated with auxinic herbicides such as CE2. By 3WAA, plants treated with the combination of topramezone and auxin mimetic herbicide(s) were mostly dead.

[0059] Dandelion control (%) was evaluated in mid-summer between weeks 3 and 9 (see Table 13 below).

[0060] [Table 13]

[0061] At 19 DAA rating, dandelion control in many of the plots treated with the combination of topramezone and auxin mimetic herbicides showed advanced symptoms, warranting evaluation of % weed control, which is usually not done until 4 weeks. At 19 DAA, most topramezone-containing treatments had 90% or higher dandelion control, while the granular comparison without topramezone had only 77.5% control. Interestingly, sprayed CE2 had the poorest control of all herbicide combinations. At 4 weeks, a more conventional time frame for rating initial % dandelion control, CE2 caught up with the topramezone treatment, as happened with granular CE1. All treatments continued to provide excellent dandelion control through 51 DAA rating. By day 65, the control rates for all granular treatments began to decrease, but as CE2 showed, the duration of control was not diminished by the granular delivery of active ingredient, also indicating that topramezone and its more accelerated rate of dandelion control did not reduce overall long-term efficacy when compared to the conventional control methods CE1 and CE2.

[0062] Effect of treatments on common dandelion (Nebraska) Dandelion damage (0-10) was rated in the spring between 5 and 28 days after application (see Table 14 below).

[0063] [Table 14]

[0064] In many of the Ohio trials, the addition of topramezone significantly accelerated dandelion damage. In this Nebraska trial, all granular treatments, whether or not they contained topramezone, caused very similar levels of dandelion damage (Table 14). Interestingly, they all tended to have better initial damage than the sprayable CE2 gold standard. The CE4 fertilizer blank caused no weed damage at all.

[0065] Dandelion control (%) was evaluated in the spring between weeks 4 and 10 (see Table 15 below).

[0066] [Table 15]

[0067] As the dandelion control test reached the 28-day mark, the data began to show that CE3 did not work as well as the other granular formulations, which provided only minimally acceptable weed control rates at that time and then became unacceptable. These treatments, including the two-way combination of topramezone and 2,4-D + dicamba, provided fully acceptable dandelion control rates through 70 days, all of which were significantly better than the gold standard CE2.

[0068] Dandelion damage (0-10) was rated in mid-summer, 4-21 days after application (see Table 16 below).

[0069] [Table 16]

[0070] In many of the Ohio trials, the addition of topramezone significantly accelerated dandelion damage. In this Nebraska trial, which began in mid-summer, all granular treatments caused very similar levels of dandelion damage, whether or not they contained topramezone. Interestingly, they all tended to cause more weed damage than the sprayable CE2 gold standard. The CE4 fertilizer blank caused no weed damage at all.

[0071] Dandelion control (%) was evaluated in mid-summer between 4 and 10 weeks after application (see Table 17 below).

[0072] [Table 17]

[0073] Application of IE1 resulted in a clean plot at the 4-week weed control rating. The other granular formulations were not significantly different as they also provided acceptable dandelion control rates. Sprayable CE2 provided significantly lower weed control rates than all granular treatments at the 4-week rating. As time progressed to the 10-week rating, certain treatments dramatically reduced in weed control rates, especially IE2 and CE2. IE1, CE1 and CE3 also reduced control rates, but not to the levels of the treatments listed above.

[0074] Treatment Effects on White Clover (Ohio) Clover injury (0-10) was rated in the spring between 3 and 18 days after application (see Table 18 below).

[0075] [Table 18]

[0076] In Ohio, the CE2 spray tended to cause the most damage to clover at this peak season application. The one treatment that came closest to its efficacy during the first two weeks was IE1. However, by the 18th day, IE2 and CE1 were causing as much damage as CE2. CE3 had inferior results, which could not be explained.

[0077] Percentage clover control was evaluated in the spring between 3 and 10 weeks after application (see Table 19 below).

[0078] [Table 19]

[0079] Throughout the 70 day test, CE2 provided excellent clover control, but was not significantly different from the two topramezone-based treatments. CE1 had significantly lower clover control, indicating the benefit of adding topramezone in IE1. CE3 performed the poorest.

[0080] Clover damage (0-10) was rated in mid-summer, 1 and 2 weeks after application (see Table 20 below).

[0081] [Table 20]

[0082] Midsummer applications of topramezone produced early and severe visual symptomology on dandelions in the trials, but this effect was less pronounced on clover when compared with non-topramezone treatments. All treatments imparted very similar clover injury intensity during the first two weeks of the trial.

[0083] Percentage clover and dandelion control was evaluated in mid-summer between weeks 3 and 8 (see Table 21 below).

[0084] [Table 21]

[0085] At 3 weeks, all topramezone treatments and CE2 provided 90%+ clover control. Granular CE1 was somewhat slower in its ability to control clover, but by the 4 week rating it was not statistically different from all other treatments. All treatments provided excellent clover control throughout the remainder of the test. As there was a significant population of dandelion within the study site, this weed was also scored 3 and 4 weeks after application. All treatments provided fully acceptable dandelion control supporting the findings in the dandelion test reported earlier.

[0086] Effect of treatments on white clover (Nebraska) Clover injury (0-10) was rated in the spring between 5 and 28 days after application (see Table 22 below).

[0087] [Table 22]

[0088] These herbicides worked on clover as well as they did on dandelions, in that all of the granular formulations were very similar to each other in their rate of activity, and they were all significantly faster in activity than the liquid-applied CE2. In this test, the CE4 fertilizer blank caused a small amount of damage to the clover, which then recovered completely.

[0089] Percentage white clover control was evaluated in the spring between 4 and 10 weeks after application (see Table 23 below).

[0090] [Table 23]

[0091] This test tended to show the benefit of topramezone in that IE1 and IE2 were the only treatments that provided acceptable control of clover. Granular treatments lacking topramezone and sprayed CE2 did not provide acceptable results (80% or greater) on any of the scoring dates. As seen in other parameters in these spring broadleaf tests in Nebraska, CE2 tended to weaken in its ability to control clover. This lack of efficacy by the gold standard could not be explained.

[0092] Clover damage (0-10) was rated in mid-summer between 4 and 21 days after application (see Table 24 below).

[0093] [Table 24]

[0094] The damage caused to clover by the granular and liquid products applied in midsummer was very similar over the test period. At no time point did topramezone significantly increase clover damage above that caused by granular CE1 and CE3. All granular treatments were very similar to sprayed CE2.

[0095] Percent white clover control was evaluated in mid-summer between 4 and 10 weeks after application (see Table 25 below).

[0096] [Table 25]

[0097] Clover was highly susceptible to all treatments at this midsummer application timing in Nebraska. Excellent clover control was maintained throughout the 10 week rating period.

[0098] conclusion In most cases, the addition of topramezone resulted in accelerated visual signs of weed damage and improved control rates of dandelion and clover when compared to the herbicide combination without topramezone. Sometimes the effect of this addition outpaced the efficacy of CE2, the gold standard treatment sprayed. The accelerated activity provided by topramezone did not reduce the long-term efficacy of any weed species, as can happen when perennial weeds are "killed" by triggering too rapid regrowth. Weed control rates tended to be just as effective in the spring peak period as they were in the midsummer test. In addition, the efficacy of weed control of CE3 was not inferior when compared to CE1. Thus, the addition of pendimethalin does not overturn the final results.

[0099] Example 3

[0084] An experiment was conducted to explore the potential of topramezone for its ability to enhance the effectiveness of controlling two key broadleaf weeds. The experiment was conducted in Ohio in early summer on common dandelion (Taraxacum officinale) and white clover (Trifolium repens). Since the study site had good populations of both dandelion and white clover, both were evaluated and assessed together for the overall weed control rate.

[0100] Treatments were applied with a shaker jar. Plots were 3' x 6' with a 2' buffer strip. Granular treatments were applied to moist turf with a hand sprayer. CE2 was applied at 1.5 gal / 1000 ft. 2 The spray volume was applied using a consumer grade single nozzle applicator wand.

[0101] Table 26 shows the formulations and application methods. IE2, CE1, CE2, Comparative Example 5 (CE5) and Comparative Example 6 (CE6) are granular products and were applied to wet foliage. CE2 is a liquid product with no fertilizer base and was sprayed onto dry foliage. CE5 is a liquid product with the same fertilizer base (0.8 lb.N / 1000 ft) as described above and was sprayed onto dry foliage. 2 , NPK ratio of 28-0-3) was used. CE6 was formulated in a physical mixture of the same fertilizer base and clay.

[0102] [Table 26]

[0103] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1. The application rate for CE2 is 4 pt / A and the application rate for CE6 is 5.0 lb / 1000 ft 2 All other compositions had an application rate of 2.856 lb / 1000 ft 2 It was decided.

[0104] Overall weed control (%) was determined between 2 and 10 weeks after application (see Table 27 below).

[0105] [Table 27]

[0106] One of the key observations of this test was the mechanical weed damage associated with the topramezone treatment (IE2) observed as early as 2 weeks after application. Weed control was scored at about 2 weeks, too early for the conventional treatments, since this was when dandelion and clover had so much damage / density reduction. At the 2 week score, it is clear that IE2 with topramezone had significantly higher control when compared to the other treatments, including the gold standard CE2, which was sprayed. By 4 weeks, all other treatments had caught up to the level of control provided by IE2.

[0107] As the test progressed through the 10-week scoring, the sprayed gold standard CE2 had the best overall weed control score, but was not significantly different from the two other formulations, CE1 and IE2, which contained 2,4-D plus dicamba. All other treatments were statistically inferior and did not provide the desired minimum level (80%) of broadleaf weed control. These included CE5 and CE6, both of which contained 2,4-D plus MCPP-p.

[0108] conclusion The addition of topramezone accelerated injury to dandelion and clover when compared to the herbicide combination without topramezone. At times, the visual effect of topramezone outpaced that of CE2, the sprayed gold standard treatment.

[0109] IE2 and CE1 provided the best overall weed control results over the longest period. Both of these treatments contained the active ingredients 2,4-D plus dicamba. Of these two treatments, only one provided acceptable weed control as early as two weeks after application, which was IE2. This accelerated activity was provided by topramezone. Early results improved even when compared to the sprayed gold standard CE2.

[0110] Example 4 Experiments were conducted in Ohio and Nebraska in June to evaluate the overall contribution of topramezone (no PRE herbicide) in combination with either dithiopyr or pendimethalin (PRE herbicide) for postemergence (3-5 leaf) crabgrass control when formulated on fertilizer granules. Experiments were conducted on large crabgrass (Digitaria sanguinalis) in Ohio and northern crabgrass (Digitaria ischaemum) in Nebraska.

[0111] At both study sites, crabgrass pressure was promoted by scalping the turf weekly to promote crabgrass germination and development. At both locations, tests were conducted in crabgrass stands where the majority of the population was at the 3-5 leaf stage. Mowing was withheld for 48 hours prior to application to ensure sufficient weed area was present for uptake. The experimental units for the turfgrass postemergence weed control tests were individual plots measuring 3' x 3' in Ohio and 5' x 5' in Nebraska. The study areas for the turfgrass postemergence weed control tests contained crabgrass in sufficient quantity and uniformity to allow product performance to be accurately and consistently evaluated. The plots were separated on each side by a 2 ft untreated buffer strip. The products were premeasured and hand applied to each plot via a shaker jar. In Ohio, a spreader box was also used to aid in uniform distribution of the granules. All treatments were applied to moist leaves and allowed to sit on the leaf surface for 24-48 hours before watering. Following application, mowing did not occur until the treatments were watered.

[0112] Table 28 shows the formulations. IE4, IE5 and Comparative Examples 7-9 (CE7, CE8 and CE9) were prepared using the same fertilizer base (0.8 lb.N / 1000 ft 2 ) which has an NPK ratio of 28-0-3. A commercially available granular composition (Comparative Example 10, CE10) was used for comparison and has a fertilizer base with an NPK ratio of 16-0-1. In the experiments in this example, the application rate for all compositions except CE10 was 2.856 lb / 1000 ft2 The application rate of CE10 was 5.0 lb / 1000 ft 2 It was decided.

[0113] [Table 28-1]

[0114] [Table 28-2]

[0115] Crabgrass weed injury following application of treatments in deep dive to crabgrass control rates in Nebraska (0-10) (see Table 29 below).

[0116] [Table 29]

[0117] Crabgrass damage was first observed 3 DAA, and all treatments containing topramezone (IE1, IE3-IE5) showed more damage than treatments without topramezone. By 7 DAA, signs of damage from treatments containing topramezone continued to progress in the range of 5.5-6.5, while no other treatments had damage scores above 1.5. At 9 DAA, these trends remained true. Interestingly, at 14 DAA, treatments containing both topramezone and dithiopyr (IE3 and IE5) had the highest means, but were not statistically greater than IE4. Regardless of rate, dithiopyr alone, CE8, and CE9 caused more crabgrass damage than pendimethalin alone, CE7, whose damage was between 5.8 and 6.5. Thus, the results showed that the inclusion of topramezone generally caused crabgrass damage symptoms sooner and more symptomology than treatments that did not contain topramezone.

[0118] Crabgrass weed injury following application of treatments in Marysville at deep dive to crabgrass control rate (0-10) (see Table 30 below).

[0119] [Table 30]

[0120] Crabgrass damage in Ohio was first observed at 7 DAA, when treatments containing topramezone were the only treatments that showed crabgrass damage. Damage was observed as leaf chlorosis. It was also observed at this time that treatments with both topramezone and dithiopyr (IE3 and IE5) showed less severe leaf chlorosis compared to treatments containing topramezone but no dithiopyr (IE1 and IE4) (Figures 1 and 2). Note the reduced leaf chlorosis in Figure 2 and how the crabgrass plants appear stunted compared to the plants treated with the pendimethalin-based formulation in Figure 1.

[0121]

[0101] Percent weed control of crabgrass following application of the treatments in Nebraska and Ohio was evaluated (see Table 31 below).

[0122] [Table 31]

[0123] Initial crabgrass control scores were taken at both locations at 28 DAA and the results were statistically different and therefore could not be combined. However, in both Nebraska and Ohio, the three treatments provided excellent control of crabgrass, with IE3, IE5 and CE9 all providing control rates above 90%. Dithiopyr alone, CE8 and CE9 provided fair control rates (72-97%) at both locations. There was a significant rate response with low control rates at CE8, with the lower dithiopyr rate. However, this rate response was only statistically significant in Ohio. CE9 provided consistently excellent control rates, but dithiopyr 0.25 lb paired with topramezone (IE3) improved the level of control rates beyond CE8, dithiopyr 0.25 lb alone, providing near complete crabgrass control rates. When topramezone was paired with pendimethalin (IE4) or applied without a preemergence herbicide (IE1), control rates were generally low, ranging from 48 to 78%. As expected, pendimethalin alone (CE7) provided only marginal levels of control.

[0124] At 42 DAA, the results from the two locations were again statistically different and could not be combined. Control from 28-42 DAA declined for all treatments, with some treatments recovering more than others. Again, IE3, IE5, and CE9 were the best performing treatments. Those treatments containing 0.5 lbs of dithiopyr (IE5 and CE9) provided crabgrass control of over 94%. IE3 still had an acceptable level of control, with 95% control in Nebraska and 85% control in Ohio. Control provided by 0.25 lbs of dithiopyr alone (CE8) declined to 76% control in Nebraska and 67% control in Ohio. As with 8 DAA, at both locations, treatments without dithiopyr generally had poor control (i.e., less than 67% control).

[0125]

[0104] The data between locations were statistically similar for 56DAA and 70DAA, so they were pooled across locations. Control rates were maintained for the treatments, never dropping below 86% for IE3, IE5, and CE9. Crabgrass control rates were significantly worse for all other treatments than 56DAA, with no other treatments having control rates above 38%. Given that only dithiopyr 0.25 lb alone (CE8) had a 65% control rate at 70DAA, and only topramezone without a pre-emergence herbicide resulted in a 25% control rate at 70DAA, the results show that none of the herbicides alone is a good choice for post-emergence control of crabgrass when applied as a granule. However, when combined, these herbicides work together to provide improved results.

[0126] Despite the differences in crabgrass species and locations tested, the statistical similarity between these data at 56 and 70 DAA indicates that treatment performance was repeatable across locations and crabgrass species, making these results more robust. IE3, IE5 and CE9 provide good post-control rates when applied to crabgrass at the 3-5 leaf stage, with effective season-long suppression. IE3, containing topramezone and dithiopyr 113.4 g (0.25), provided acceptable results, while CE8 (dithiopyr 0.25 alone) was not as effective. Topramezone resulted in poor levels of postemergence crabgrass control (i.e., less than 37% control at 70 DAA) when formulated without a preemergence herbicide (IE1) or with pendimethalin (IE4), indicating that topramezone provides little or no control as a granular treatment for postemergence crabgrass control when dithiopyr is not present. In addition, the combination of dithiopyr and topramezone reduces the leaf blanch and visual effects caused by topramezone without dithiopyr, providing a more acceptable consumer experience.

[0127] Example 5 A research trial was conducted in Ohio to evaluate compositions for post-emergence crabgrass control. The trial evaluates compositions for post-emergence crabgrass control at the 6+ tiller (mature) growth stage. The experimental unit for the turfgrass post-emergence weed control trial was 3' x 3'. The plots were separated by 2 ft of untreated buffer strips on each side.

[0128]

[0107] Before the start of the trials, crabgrass pressure was encouraged in the early spring by scalping the turf weekly to encourage crabgrass germination and development. When crabgrass emerged and became evident in the turf canopy, the mowing height was increased back to the original 3" mowing height to replicate a more realistic scenario. Mowing was withheld for 48 hours prior to treatment application to ensure sufficient weed leaf area was present for herbicide absorption. The study areas contained crabgrass in sufficient quantity and uniformity to allow product performance to be accurately and consistently evaluated.

[0129] Granular products were pre-measured and hand applied to each plot via a shaker jar and spreader box to aid in uniform distribution of the granules. Granular formulations were applied to natural dew in the early morning. Following application, no cutting occurred until the treatments were watered within 48 hours of application. Plots were irrigated 2 days after application to water the produce. For the experiments in this example, the application rate for granular products IE1-IE3 and CE11 was 2.85 lb / M, and the application rate for CE12 was 1.5 fl.oz. / A.

[0130] The compositions and application rates are shown below in Table 32. Comparative Example 11 (CE11) was prepared using the same fertilizer base (0.8 lb.N / 1000 ft) as described above. 2 It is a granular product utilizing a 28-0-3 NPK ratio. The treatments were compared to an industry standard for Pylex crabgrass control mixed with a crop oil concentrate (COC) (Comparative Example 12, CE12) and an untreated control. CE12 is a spray product with no fertilizer base.

[0131] [Table 32]

[0132]

[0110] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1. Crabgrass damage (0-10) was measured between 3 and 21 days after application (see Table 33 below).

[0133] [Table 33]

[0134] At the first crabgrass damage rating 3 DAA, no significant damage was observed. At 8 DAA, damage from all treatments was observed. Pylex (CE12) and topramezone alone (CE11) were in the highest statistical performance groups, each with a damage rating of 5.5. Damage from topramezone appeared to be slightly lower in damage when paired with 2,4-D and dicamba, but the numerical differences between damage ratings were small and not always statistically significant. The treatment with the lowest damage rating score was IE3, which contained 2,4-D, dicamba, dithiopyr, and topramezone. It was noted that crabgrass grew less quickly and had significantly less whitening of the leaves than the other treatments with higher damage ratings.

[0135] By 13 days after application, sprayed Pylex (CE12) separated itself from the experimental treatments with the greatest amount of weed damage, with a rating of 8. Experimental formulations containing topramezone alone (CE11) and 2,4-D + dicamba + topramezone (IE1) were in the second best performing statistical category, with injury ratings of 5.0 and 4.3, respectively. The treatment containing both dithiopyr and topramezone (IE3) again had the lowest injury rating of all treatments.

[0136] Final injury scores 21 days after application showed that leaf chlorosis from most of the granular topramezone treatments had disappeared, except for IE3, which contained dithiopyr and topramezone and showed increased crabgrass injury. Leaf necrosis, root crazing, and general stunting and decline of plants were observed.

[0137] Granular treatments containing topramezone often showed good initial results, but crabgrass often recovered. The only exception was 2,4-D + dicamba + dithiopyr + topramezone (IE3), which had the highest injury score at the last day of injury rating among the compositions other than Pylex (CE12). There is a large performance gap between sprayed Pylex and topramezone in granular form, but that is also to be expected given the difference in coverage between the two products.

[0138] Percent crabgrass control was determined between weeks 3 and 8 (see Table 34 below).

[0139] [Table 34]

[0140] On the first day of crabgrass control rating, 21 days after application, CE12 provided the highest level of control with a 93% control. The combination of dithiopyr + topramezone at IE3 continued to develop damage and had a control rating of 74% control. No other treatment had a control rate of more than 43% through 43DAA. Dithiopyr + topramezone (IE3) continued to increase in control, with 81% and 86% control at 28DAA and 42DAA. The stunted crabgrass plants were eventually overwhelmed by the thriving grass canopy and were no longer visible over time. It is theorized that some of the plants were removed by the lawnmower due to the lack of a proper root system to provide a foothold for the plants. By 56 days after application, overall crabgrass health and vigor had declined significantly as fall approached. The ratings were extremely difficult and should be interpreted with caution as the untreated control was given a control rating of 18%.

[0141] Dithiopyr appears to add an ingredient to crabgrass control, whereas pendimethalin does not. Given that dithiopyr as a spray is labeled for postemergence (pre-tillering) crabgrass control, one would expect some effect on late stage crabgrass. However, the accelerated and sustained stunting and necrosis of crabgrass with dithiopyr + topramezone indicates that these two active ingredients are synergistic.

[0142] As shown in Figure 3, IE2, and topramezone alone, CE11, performed poorly. However, IE3 resulted in excellent control, indistinguishable from the industry standard Pylex (CE12). This indicates that dithiopyr and topramezone combine together synergistically to create this surprisingly high level of control as a granule.

[0143] IE3 worked very well for crabgrass control at 6+ tillers. Granularly formulated topramezone either with pendimethalin or without a preemergence herbicide caused early injury / control that disappeared.

[0144] Example 6

[0121] An experiment was conducted in Ohio in November to evaluate how different compositions performed when applied to dry leaves compared to when applied to wet leaves. The experiment was conducted on common dandelion (Taraxacum officinale).

[0145]

[0122] Individual plots measured 3' x 3' in Ohio and were separated on each side by a 2 ft untreated buffer strip. The product was pre-measured and hand applied to each plot via a shaker jar and spreader box.

[0146] Table 35 shows the formulations. IE3 and CE1 are based on the same fertilizer base (0.8 lb.N / 1000 ft 2 ) which has an NPK ratio of 28-0-3. Both IE3 and CE1 were applied to wet leaves (from dew) and dry leaves. A commercial liquid composition (Comparative Example 13 or CE13) was used for comparison and had no fertilizer base. CE13 was applied to dry leaves at 0.68 gal / 1000 ft at 36 psi. 2 In the experiments in this example, IE3 and CE1 were applied using a CO2 power boom equipped with two TeeJet 8002-VS nozzles calibrated to deliver 2.85 lb / 1000 ft. 2 and CE13 was applied at a rate of 3.25 pints / A.

[0147] [Table 35]

[0148]

[0124] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1.

[0125] Weed damage (0-10) was measured between 1 and 5 weeks after application (see Table 36 below).

[0149] [Table 36]

[0150] As early as one week after application, it was apparent that IE3 applied to the wet leaves had better activity (weed damage) than all other treatments due to the combined effect of topramezone, the auxin mimetic herbicide, and dithiopyr. By two weeks, the dry leaf IE3 treatments began to separate from both the wet leaf CE1 treatments and the dry leaf CE1 treatments. This effect was maintained through the five week weed damage rating, when CE1 treated weeds (wet and dry) had stopped developing symptoms of damage, while IE3 treated weeds continued to decline.

[0151] During cool fall conditions, the effectiveness of CE13 on dandelions slowed considerably, but here both IE3 treatments continued to kill the weeds. These granular formulations often appear to be more effective than the sprayed industry standard CE13. Sprayed CE13 performed very similarly to CE1 (applied to moist foliage).

[0152] Percent weed control was determined 6 and 8 weeks after application (see Table 37 below).

[0153] [Table 37]

[0154] IE3 accelerates the herbicidal effect of the granule application composition when compared with its conventional counterpart CE1. IE3 produced significantly more effective results than CE1 and CE13 for both wet and dry leaf application. IE3 even produces acceptable results when applied to dry leaves of dandelion, especially when compared with CE1. The combination of topramezone, auxin mimetic herbicide and dithiopyr in IE3 enhances the activity of this granular composition, so that it overcomes the limitations of dry leaf conditions. IE3 improves the consistency of granule application broadleaf herbicides, especially when climatic conditions are not ideal for the performance of conventional combined herbicides-fertilizers.

[0155] Example 7

[0130] A study was conducted in Ohio in July and August to evaluate the synergy between the granular forms of dithiopyr and topramezone. The study was conducted on northern crabgrass (Digitaria ischaemum).

[0156] Treatments were applied with a shaker jar and spreader box. Each plot was 3' x 3' surrounded by a 2' buffer strip. Granular treatments were applied either to moist leaves, by dew, or by hand sprayer. Plot areas were selected for grassy weed populations with the goal of achieving an evaluation of control rate by assessing reduction in weed populations when compared to untreated buffer areas around each plot.

[0157] Table 38 shows the formulations and application rates. All of the formulations were applied at the same fertilizer base (0.8 lb.N / 1000 ft 2 ) which has an NPK ratio of 28-0-3, except for IE7, which utilizes the inert carrier BioDac. The application rate in these experiments was 2.86 lb / 1000 ft 2 It was decided.

[0158] [Table 38]

[0159]

[0133] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1. These experiments were conducted during late summer for post-emergence control rates of late crabgrass. The crabgrass growth stages for each application were as follows: Run 1 was applied on July 19 (2-3 tillers and highly visible on the turf canopy), Run 2 was applied on July 24 (3-5 tillers), and Run 3 was applied on August 2 (5-7 tillers and beginning to produce plants that set seed after flowering). These were repeated three times to ensure that the effects observed were consistent and reproducible. Due to the rapid nature of crabgrass growing and maturing during summer growing conditions, the trials were repeated in rapid succession. Run 1 Crabgrass damage (0-10) was rated 3, 7 and 12 days after application (see Table 39 below).

[0160] [Table 39]

[0161]

[0136] Additionally, visual crabgrass control (0-100) was assessed 21, 28, 35 and 42 days after application (see Table 40 below).

[0162] [Table 40]

[0163] Run 2 Crabgrass damage (0-10) was rated 7 and 14 days after application (see Table 41 below).

[0164] [Table 41]

[0165]

[0138] Additionally, visual crabgrass control (0-100) was assessed 22, 28 and 35 days after application (see Table 42 below).

[0166] [Table 42]

[0167]

[0139] Figures 5-7 show photographs of the lawn 3 weeks after treatment with CE4, CE8 and CE11 respectively. Figures 8 and 9 show photographs of the lawn 3 weeks after treatment with IE6 and IE7 respectively. Run 3 Crabgrass damage (0-10) was rated 7, 14 and 21 days after application (see Table 43 below).

[0168] [Table 43]

[0169]

[0141] Additionally, visual crabgrass control (0-100) was assessed 28 days after application (see Table 44 below).

[0170] [Table 44]

[0171] result Early results from these three trials showed that crabgrass injury was significantly greater with topramezone alone (CE11) compared to dithiopyr alone (CE8) (see Tables 39-44). The initial injury in crabgrass was always apparently greater than that with dithiopyr, as topramezone caused highly visible leaf chlorosis, which appeared to simply inhibit crabgrass growth. The chlorosis effect of topramezone was somewhat attenuated when it was combined with auxinic herbicides (i.e., 2,4-D and dicamba in IE3). The combination of dithiopyr and topramezone in an inert carrier (i.e., BioDac(IE7)) showed very low crabgrass injury because the higher density rounded particles of the BioDac carrier caused poor adhesion to crabgrass leaves and therefore poor transfer of the active ingredient from the particles to the crabgrass leaves compared to the fertilizer carrier. In addition to these physical properties, many of the fertilizer particles are readily soluble on contact with water, thereby releasing their active ingredients. BioDac does not readily dissolve on contact with water. Treatments containing fertilizer particles alone caused no injury to crabgrass.

[0172] Visual crabgrass control ratings were made by comparing crabgrass density within a plot to that in an adjacent 2-foot untreated buffer strip to determine visual estimated percent control. In all three tests, the combination of dithiopyr and topramezone on the fertilizer carrier (IE6) tended to provide the best and most consistent crabgrass control of any treatment. As seen in the injury ratings, the addition of an auxinic herbicide to this combination consistently caused a reduction in control, but the differences were rarely statistically significant. Dithiopyr and topramezone, each on the fertilizer carrier, also provided varying degrees of visual crabgrass control, but not to the level provided by the combination of dithiopyr and topramezone (all using the fertilizer base). When these active ingredients were placed on the BioDac carrier, crabgrass control was significantly reduced compared to the same active ingredients placed on the fertilizer base. As noted above, this was believed to be due to differences in the physical properties of the two carriers and their ability to adhere to the narrow needle-like leaves of crabgrass.

[0173] The crabgrass control profile of these formulations was analyzed using visually estimated crabgrass density ratings (see FIG. 4, Run 1 below), comparing the initial density with the density in subsequent weekly ratings. To determine percent control, these density estimates were then calculated using the Henderson-Tilton equation:

[0174]

number

[0175] [In the formula, W.D. C is the percent weed density (crabgrass) in the control plot, and WD T is the percent weed density (crabgrass) in the treated plot. This equation fits the control results by accounting for pest populations which are variable and can shift during the test. In the case of crabgrass, which continues to grow in size over the course of the test, this equation was appropriate.

[0176] The percent control values ​​for dithiopyr alone and topramezone alone were subjected to the Colby equation to generate an expected control (E) to aid in determining synergy between the two herbicides. The Colby equation is:

[0177]

number

[0178] where x is the efficacy (percent control) of "Herbicide A" applied alone, y is the efficacy (percent control) of "Herbicide B" applied alone, and E is the expected control rate of the combination of "Herbicide A" and "Herbicide B". The expected control rate is then compared to the field-produced percentage of control provided by the two herbicides applied in combination. If the expected control rate (E) is lower than that measured in the field, synergy exists according to the Colby test. Tables 45-47 show the percent control and expected control rates (for IE6) for runs 1-3, respectively.

[0179] [Table 45]

[0180] [Table 46]

[0181] [Table 47]

[0182] It is apparent that the incidence of synergy between dithiopyr and topramezone is consistent and highly reproducible. Thus, treatments containing the combination of dithiopyr and topramezone in fertilizer granules provided acceptable postemergence control of crabgrass (+80%) at most application times. In addition, the grassy weed herbicides dithiopyr and topramezone acted synergistically at three stages of late season crabgrass. Another noteworthy observation is that there is a consistent decrease in crabgrass efficacy whenever 2,4-D and dicamba are included with the dithiopyr and topramezone combination (IE3). While in most cases this decrease in crabgrass control is not significant, it does indicate possible antagonism between the auxinic herbicides and the dithiopyr and topramezone combination. Also note the possible decrease in efficacy when the dithiopyr and topramezone combination is loaded onto BioDac (IE7) compared to when it is loaded onto fertilizer granules. As expected, the fertilizer carrier alone (CE4) did not control crabgrass and tended to stimulate crabgrass growth compared to the untreated control.

[0183] Example 8

[0148] Experiments were conducted in Ohio in the fall (after flowering) and spring (peak flowering) to evaluate the synergy between two auxinic herbicides, 2,4-D and dicamba, and topramezone. The experiments were conducted in common dandelion (Taraxacum officinale).

[0184] Treatments were applied with shaker jars and spreader boxes. Each plot was 3' x 3' surrounded by a 2' buffer strip. Granular treatments were applied either to moist leaves, by dew, or by hand sprayer. Plot areas were selected for broadleaf weed populations with the goal of achieving an evaluation of control rate by assessing reduction in weed populations when compared to untreated buffer areas around each plot.

[0185] Table 48 shows the formulations and application rates. All of the formulations were applied at the same fertilizer base (0.8 lb.N / 1000 ft 2) which has an NPK ratio of 28-0-3, except for IE8, which utilizes the inert carrier BioDac. The application rate for these experiments was 2.86 lb / 1000 ft 2 It was decided.

[0186] [Table 48]

[0187]

[0151] These experiments were designed in the same manner as discussed above for Example 1. The results were similarly collected and analyzed in the same manner as discussed above for Example 1. Postemergence control rate of dandelions during autumn Dandelion damage (0-10) was assessed 5, 8, 14, 27 and 35 days after treatment (see Table 49 below).

[0188] [Table 49]

[0189] Symptoms of dandelion injury began to show for most of the treatments at the 5 and 8 day ratings, but it was not until the 27 day rating that separation began to appear in the treatments. Treatments containing 2,4-D, dicamba and topramezone on the fertilizer carrier (IE1 and IE3) exhibited significantly more weed damage than all other treatments. Topramezone alone and the combination of 2,4-D and dicamba alone had less effect on dandelions, suggesting an enhanced effect when these herbicides were combined. Interestingly, when these three herbicides were applied using BioDac, the effect obtained was significantly reduced compared to the combination in the fertilizer granules. These trends continued at the 35 day rating.

[0190]

[0154] Additionally, visual dandelion control (%) was assessed 8 weeks after treatment (see Table 50 below).

[0191] [Table 50]

[0192] At 8 weeks, visual dandelion control results revealed nearly complete control with all of the treatments containing 2,4-D and dicamba on the fertilizer carrier. The addition of topramezone appeared to be necessary to provide early results, but the combination of 2,4-D with dicamba alone eventually caught up and was similarly effective. The combination of 2,4-D with dicamba and topramezone on BioDac (IE8) gave very poor control, as did topramezone alone (CE11).

[0193]

[0156] This study also showed that the addition of dithiopyr to the herbicide mix (IE3) did not reverse the synergistic effect of topramezone in combination with 2,4-D and dicamba when compared to the no treatment (IE1).

[0194] Post-emergence control rate of dandelions during spring Dandelion damage (0-10) was assessed 5, 8, 14, 27 and 35 days after treatment (see Table 51 below).

[0195] [Table 51]

[0196] This test showed results very similar to those obtained in the autumn test (Tables 49 and 50). One notable difference is that in this test, the formulations containing 2,4-D, dicamba and topramezone on the fertilizer carriers (IE1 and IE3) did not cause significantly more damage than the combination of 2,4-D and dicamba on the fertilizer carrier (CE1). The addition of topramezone did not increase the herbicidal effect as seen in the autumn test. This could not be explained. The formulation using the BioDac carrier (IE8) again gave significantly inferior results compared to the control treatment that contained fertilizer particles as carrier (IE1). Topramezone alone (CE11) caused slight and short-lived leaf decolorization, but most had little activity on spring dandelions.

[0197]

[0159] Additionally, visual dandelion control (%) was assessed 8 weeks after treatment (see Table 52 below).

[0198] [Table 52]

[0199] Visual dandelion control, scored 4 and 8 weeks after treatment, revealed that formulations containing 2,4-D and dicamba on fertilizer carriers (IE1, IE3, and CE1) provided statistically similar dandelion control. However, it should be noted that among these treatments, only those containing topramezone (IE1 and IE3) provided commercially acceptable control of 85% or greater. This same set of active ingredients on a BioDac carrier (IE8) again provided poor dandelion control.

[0200] result The dandelion control aspect of these formulations was further analyzed using visual estimated dandelion density ratings, and percent control was determined as discussed in Example 7. The Henderson-Tilton data transformation fits the control results by accounting for pest populations that may be variable or shift during testing. As also discussed in Example 7, expected control was determined for topramezone alone and for the combination of 2,4-D and dicamba, and then compared to the percent control produced in the field by the combination of 2,4-D, dicamba, and topramezone applied. Synergy exists according to the Colby test when the expected control (E) is lower than that measured in the field. Tables 53 and 54 show the percent control and expected control (for IE1) for the fall and spring tests, respectively.

[0201] [Table 53]

[0202] [Table 54]

[0203] It is clear that the rate of synergy between topramezone and the combination of 2,4-D and dicamba is consistent and highly reproducible in common dandelion whether tested in fall or spring. Thus, these tests successfully documented the postemergence herbicidal synergy of 2,4-D, dicamba and topramezone in common dandelion. Furthermore, the formulation containing 2,4-D, dicamba and topramezone on the fertilizer carrier provided exceptional postemergence dandelion control (+85%) at both application times. The addition of dithiopyr to the combination of 2,4-D, dicamba and topramezone did not appear to affect efficacy on broadleaf weeds.

[0204]

[0163] These results showed a noticeable decrease in efficacy of 2,4-D, dicamba and topramezone when loaded onto BioDac compared to when loaded onto the fertilizer granules. The combination of particle shape, density and chemical makeup gives the fertilizer carrier a clear and measurable advantage over BioDac. As expected, the nitrogen-based fertilizer carrier alone did nothing to control dandelions.

[0205]

[0164] As used herein, all percentages (%) are weight percent of the total composition and may also be expressed as weight / weight %, %(w / w), w / w, w / w%, or simply %, unless otherwise specified.

[0206]

[0165] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​quoted. Instead, unless otherwise specified, each such dimension is intended to mean both the quoted value and a functionally equivalent range surrounding that value.

[0207]

[0166] It is to be understood that every maximum numerical limit given throughout this specification includes every lower numerical limit, as if such lower numerical limits were expressly written herein. It is to be understood that every minimum numerical limit given throughout this specification will include every higher numerical limit, as if such higher numerical limits were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that is subsumed within such broader numerical range, as if such narrower numerical ranges were expressly written herein.

[0208] All documents cited herein, including any cross-references or related patents or applications, are hereby incorporated by reference in their entirety, unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, or that it alone or in combination with any other reference, or that it refers to, teaches, suggests or discloses any such invention. Furthermore, to the extent that any meaning or definition of a term in this document is inconsistent with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall control.

[0209]

[0168] The foregoing description of the embodiments and examples has been presented for purposes of illustration. It is not intended to be exhaustive or limited to the forms described. Numerous variations are possible in light of the above teachings. Some of these variations have been contemplated, and others will be understood by those skilled in the art. The embodiments were chosen and described to illustrate various embodiments. The scope is, of course, not limited to the examples or embodiments described herein, but may be utilized in any number of applications and equivalent papers by those skilled in the art. Rather, it is hereby intended that the scope be defined by the "claims" appended hereto. Aspects of the invention [Aspect 1] Topramezone, Dithiopyr and 1. A herbicide composition comprising: [Aspect 2] The herbicide composition according to aspect 1, wherein topramezone is present in the range of about 0.01 wt% to about 0.035 wt%, and dithiopyr is present in the range of about 0.1 wt% to 0.3 wt%. [Aspect 3] The herbicide composition of Aspect 1, wherein topramezone is present in the range of about 0.023 wt% to about 0.025 wt% and dithiopyr is present in the range of about 0.18 wt% to 0.22 wt%. [Aspect 4] The herbicide composition of Aspect 1 or 2, further comprising an auxin-mimetic herbicide, the auxin-mimetic herbicide comprising at least one of 2,4-dichlorophenoxyacetic acid (2,4-D), (2R)-2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP-p), or 3,6-dichloro-2-methoxybenzoic acid (dicamba). [Aspect 5] The herbicide composition according to any one of aspects 1 to 4, comprising an auxin-mimetic herbicide, the auxin-mimetic herbicide comprising 2,4-D and dicamba. [Aspect 6] The herbicide composition of Aspect 5, wherein 2,4-D is present in the range of about 1 wt% to about 1.5 wt% and dicamba is present in the range of about 0.01 wt% to about 0.2 wt%. [Aspect 7] The herbicide composition according to any one of Aspects 1 to 6, further comprising a viscosity modifier. [Aspect 8] The herbicide composition of Aspect 7, wherein the viscosity modifier is dipropylene glycol. [Aspect 9] The herbicide composition according to any one of Aspects 1 to 8, consisting of topramezone, 2,4-D, dicamba, dithiopyr, and optionally a viscosity modifier. [Aspect 10] The herbicide composition according to any one of Aspects 1 to 9, comprising herbicides consisting of topramezone, 2,4-D, dicamba and dithiopyr. [Aspect 11] The herbicide composition of Aspect 1, wherein topramezone is present in the range of about 0.023 wt% to about 0.025 wt%, 2,4-D is present in the range of about 1.15 wt% to 1.25 wt%, dicamba is present in the range of about 0.07 wt% to about 0.09 wt%, and dithiopyr is present in the range of about 0.18 wt% to about 0.22 wt%. [Aspect 12] A granular herbicide comprising a granular carrier coated with the herbicide composition according to any one of aspects 1 to 11. [Aspect 13] The granular herbicide according to Aspect 12, wherein the granular carrier comprises a fertilizer granule. [Aspect 14] The granular herbicide according to aspect 13, wherein the fertilizer granule comprises a mixture of a urea-containing fertilizer and rice husk. [Aspect 15] The granular herbicide according to Aspect 12, wherein the granular carrier comprises a non-fertilizer granule. [Aspect 16] A granular herbicide according to any one of Aspects 12 to 15, wherein topramezone is present in a range of about 0.01 wt% to about 0.035 wt%, and dithiopyr is present in a range of about 0.1 wt% to 0.3 wt%. [Aspect 17] A granular herbicide according to any one of Aspects 12 to 15, wherein topramezone is present in a range of about 0.023 wt% to about 0.025 wt%, and dithiopyr is present in a range of about 0.18 wt% to 0.22 wt%. [Aspect 18] A granular herbicide according to any one of aspects 12 to 15, wherein 2,4-D is present in a range of about 1 wt% to about 1.5 wt% and dicamba is present in a range of about 0.01 wt% to about 0.2 wt%. [Aspect 19] A granular herbicide according to any one of Aspects 12 to 15, wherein topramezone is present in the range of about 0.023 wt% to about 0.025 wt%, 2,4-D is present in the range of about 1.15 wt% to 1.25 wt%, dicamba is present in the range of about 0.07 wt% to about 0.09 wt%, and dithiopyr is present in the range of about 0.18 wt% to about 0.22 wt%. [Aspect 20] A method for making a granular herbicide, comprising the step of coating a granular carrier with the herbicide composition according to any one of aspects 1 to 11. [Aspect 21] A method for controlling weed plants, comprising the step of applying a granular herbicide according to any one of aspects 12 to 19 or a herbicide composition according to any one of aspects 1 to 11 onto a weed plant. [Aspect 22] The method according to aspect 21, further comprising a step of killing weed plants. [Aspect 23] The method of aspect 21, wherein the applying step comprises applying topramezone at a rate of 0.03 lb. / A, 2,4-D at a rate of 1.5 lb. / A, dicamba at a rate of 0.1 lb. / A, and dithiopyr at a rate of 0.25 lb. / A. [Aspect 24] Topramezone, 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6-dichloro-2-methoxybenzoic acid (dicamba) and Including, topramezone is present in the range of about 0.023 wt% to about 0.025 wt%, 2,4-D is present in the range of about 1.15 wt% to 1.25 wt%, and dicamba is present in the range of about 0.07 wt% to about 0.09 wt%; A herbicidal composition for controlling broadleaf vegetation. [Aspect 25] The herbicide composition according to aspect 24, further comprising a granular carrier.

Claims

1. Topramaison and Dithiopyr and Auxin mimetic herbicides including 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (dicamba); 1. A herbicide composition comprising:

2. 2. The herbicidal composition of claim 1, wherein topramezone is present in the range of 0.01 wt % to 0.035 wt % and dithiopyr is present in the range of 0.1 wt % to 0.3 wt %.

3. 2. The herbicidal composition of claim 1, wherein topramezone is present in the range of 0.023 wt % to 0.025 wt % and dithiopyr is present in the range of 0.18 wt % to 0.22 wt %.

4. The herbicide composition of claim 1, wherein the auxin mimetic herbicide further comprises (2R)-2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP-p).

5. 2. The herbicidal composition of claim 1, wherein 2,4-D is present in the range of 1 wt % to 1.5 wt % and dicamba is present in the range of 0.01 wt % to 0.2 wt %.

6. 6. The herbicidal composition of claim 1, further comprising a viscosity modifier.

7. 7. The herbicidal composition of claim 6, wherein the viscosity modifier is dipropylene glycol.

8. 8. The herbicidal composition of any one of claims 1 to 7, consisting of topramezone, 2,4-D, dicamba, dithiopyr, and optionally a viscosity modifier.

9. 9. The herbicidal composition according to any one of claims 1 to 8, comprising the herbicides topramezone, 2,4-D, dicamba and dithiopyr.

10. 2. The herbicidal composition of claim 1, wherein topramezone is present in the range of 0.023 wt % to 0.025 wt %, 2,4-D is present in the range of 1.15 wt % to 1.25 wt %, dicamba is present in the range of 0.07 wt % to 0.09 wt %, and dithiopyr is present in the range of 0.18 wt % to 0.22 wt %.

11. A granular herbicide comprising a granular carrier coated with the herbicide composition of any one of claims 1 to 10.

12. 12. The granular herbicide of claim 11, wherein the granular carrier comprises a fertilizer granule.

13. 13. The granular herbicide of claim 12, wherein the fertilizer granule comprises a mixture of urea-containing fertilizer and rice husk.

14. 12. The granular herbicide of claim 11, wherein the granular carrier comprises a non-fertilizer granule.

15. 15. A granular herbicide according to any one of claims 11 to 14, wherein topramezone is present in the range of 0.01 wt % to 0.035 wt % and dithiopyr is present in the range of 0.1 wt % to 0.3 wt %.

16. 15. A granular herbicide according to any one of claims 11 to 14, wherein topramezone is present in the range of 0.023 wt% to 0.025 wt% and dithiopyr is present in the range of 0.18 wt% to 0.22 wt%.

17. 15. A granular herbicide according to any one of claims 11 to 14, wherein 2,4-D is present in the range of 1 wt % to 1.5 wt % and dicamba is present in the range of 0.01 wt % to 0.2 wt %.

18. 15. A granular herbicide according to any one of claims 11 to 14, wherein topramezone is present in the range of 0.023 wt % to 0.025 wt %, 2,4-D is present in the range of 1.15 wt % to 1.25 wt %, dicamba is present in the range of 0.07 wt % to 0.09 wt %, and dithiopyr is present in the range of 0.18 wt % to 0.22 wt %.

19. 11. A method of making a granular herbicide comprising the step of coating a granular carrier with the herbicide composition of any one of claims 1 to 10.

20. 20. A method for controlling weed plants, comprising the step of applying a granular herbicide according to any one of claims 11 to 18 or a herbicide composition according to any one of claims 1 to 10 onto the weed plants.

21. 21. The method of claim 20, further comprising the step of killing weed plants.

22. 21. The method of claim 20, wherein the applying steps include applying topramezone at a rate of 0.03 lb. / A, 2,4-D at a rate of 1.5 lb. / A, dicamba at a rate of 0.1 lb. / A, and dithiopyr at a rate of 0.25 lb. / A.

23. Topramaison and 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6-dichloro-2-methoxybenzoic acid (dicamba), Dithiopyr and Including, topramezone is present in the range of 0.023 wt % to 0.025 wt %, 2,4-D is present in the range of 1.15 wt % to 1.25 wt %, and dicamba is present in the range of 0.07 wt % to 0.09 wt %; A herbicidal composition for controlling broadleaf vegetation.

24. 24. The herbicidal composition of claim 23 further comprising a granular carrier.

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