A glyphosate herbicide composition

Abstract

The application discloses a glyphosate herbicide composition, which comprises an active ingredient glyphosate, a phosphorus-containing additive, amino acids, an auxiliary agent and other substances. The herbicide composition has a synergistic effect compared with single glyphosate herbicide and glyphosate and phosphorus-containing additive combined herbicide.

Description

Technical Field

[0001] This invention belongs to the field of agrochemical herbicide formulations, and relates to a herbicide composition, specifically a herbicide composition containing glyphosate and glyphosate and its use in controlling harmful plants. Background Technology

[0002] Glyphosate is currently the most widely used and consumed herbicide of high quality. It is a systemic, slow-acting, broad-spectrum, non-selective herbicide. Glyphosate is absorbed through the green parts of the plant, such as stems and leaves, and translocated to all parts of the plant. It can control weeds in more than 40 families of plants, including monocots and dicots, annuals and perennials, herbs and shrubs. It is widely used for weed control in non-agricultural fields, orchards, roadsides, and forestry. Since its commercialization in the 1970s, it has been very popular, especially with the development of crop genetic engineering since the 1990s, making it the world's best-selling herbicide. However, due to the long-term, large-scale, and continuous use of glyphosate, weed resistance has become a prominent issue. Some weeds, such as goosegrass, have strong resistance to glyphosate, and glyphosate alone cannot effectively control them. Controlling these weeds is a problem that urgently needs to be solved. Plant growth and development are the coordinated and unified manifestation of many physiological and biochemical processes within the plant. Herbicides are substances used to kill or inhibit plant growth. When a herbicide interferes with a particular stage of plant growth, it disrupts the balance of the plant's physiological and biochemical processes, leading to inhibited growth and development or even death. Herbicides are classified into contact herbicides and systemic herbicides based on the mobility of their active ingredients within the plant. Based on their mechanism of action, herbicides can be categorized as those that inhibit weed photosynthesis, respiration, or protein synthesis, among others. Regardless of the mechanism, ensuring that weed-producing plants can effectively absorb more of the herbicide's active chemical components is a fundamental approach to improving weed control and reducing dosage. Another approach is to enhance overall weed control and reduce dosage by adding or combining auxiliary ingredients to create a synergistic effect, thereby increasing or introducing new interferences to the plant's normal physiological and biochemical processes.

[0003] In general, the mechanisms of action of herbicides are complex, and the mechanisms of action of many herbicides are still not fully understood. This is because their effectiveness is influenced not only by the target weeds but also by environmental conditions. The weed-killing effect of many herbicides is not limited to a single factor; sometimes several factors occur simultaneously, forming a complex process. Different weed species have varying sensitivities to different types and formulations of herbicides, even among the same species in different areas. Therefore, herbicide application requires selecting herbicides based on the sensitivities of weeds and crops. Furthermore, due to the increasingly complex nature of weed resistance, it is often necessary to mix several herbicides in production practice. Developing different herbicide formulations to address the sensitivities of different weeds and crops to different herbicide combinations is also an important research direction. Patents CN 115119851 A (a glyphosate-containing herbicide composition) and CN202011363830 (a glyphosate isopropylamine salt solution adjuvant) are specific examples of this approach.

[0004] Goosegrass is an annual herbaceous plant, but due to its well-developed and deep root system, strong drought resistance, high growth rate, adaptability, and tenacious vitality, it holds a leading position among various weeds. However, with the widespread use of non-selective herbicides such as paraquat and glyphosate, weed metabolism has changed, and through generations of selection, surviving offspring have developed increasingly significant herbicide resistance and stronger adaptability. Resistance also varies across different regions, making it a difficult-to-control and highly resistant weed. Furthermore, even after the above-ground stems and leaves wither in autumn, some plants retain their underground root systems, sprouting new above-ground stems and leaves the following spring for regrowth. Improving the control efficacy of goosegrass remains a challenging task.

[0005] Glyphosate, at low concentrations, is a plant growth inhibitor. It was the first commercially available sugarcane ripening agent in the United States, primarily used for increasing sugar content and ripening sugarcane and sugar beets, and for defoliating and ripening cotton. According to public reports, glyphosate also has herbicidal effects at certain high concentrations, and its herbicidal activity varies depending on the specific compound formulation. Some mixed formulations exist; however, overall, there are not many glyphosate formulations and products on the market, and its mechanism of action, efficacy research, and product manufacturing are not as widespread and well-understood as glyphosate. Its compound herbicidal effects warrant further investigation.

[0006] Hydroxymethylphosphonic acid is a compound with a phosphonic carboxyl group structure, and its application in the field of herbicide enhancement has been rarely reported.

[0007] Amino acids are the basic building blocks of proteins and play a vital role in biology. They are not only the building blocks of proteins but also function as biocatalysts, signaling molecules, acid-base balance regulators, nutrients, and drugs. Common small-molecule amino acids include serine, proline, glycine, glutamic acid, aspartic acid, arginine, proline, lysine, histidine, and threonine. With advancements in science and technology, chemists have brought amino acids into the agricultural arena. For example, various amino acids can be used to prevent and treat various crop diseases or promote growth. Japanese scientists sprayed a 0.04% proline solution on corn, increasing yield by 20%. Indian scientist Singh sprayed low concentrations of methionine on rice to prevent damage from rice root rot fungi. Some scientists have found that spraying tryptophan, cysteine, and alanine on crops can resist and eliminate crop pathogens. Patent IT2000FE000003 describes a herbicide containing amino acids or peptides. Compared to conventional formulations with the same active ingredient, the combination of glyphosate and / or glufosinate with amino acids, low-chain peptides, or protein fragments increases herbicidal activity and shortens the time it takes for the herbicide to take effect, thereby reducing the weeding time. However, there are few reports on the enhancement of weed control efficacy of herbicides containing substances such as amino acid molecules, especially for specific resistant and difficult-to-control weeds (such as goosegrass). The synergistic effect of single glycine or peptide additives on the herbicide combination has certain limitations. New experimental studies have found that the combination of amino acids as an effective synergistic component and new substances can further improve the synergistic effect. Summary of the Invention

[0008] This invention discloses a herbicidal composition comprising the active ingredient glyphosate or simultaneously containing glyphosate and glyphosate-phosphonate, and further comprising amino acids and hydroxymethylphosphonic acid, specifically a compound of glyphosate, glyphosate, small molecule amino acids, and hydroxymethylphosphonic acid. The purpose of this invention is to develop a glyphosate compound formulation to improve the weed control efficacy of glyphosate-only herbicides or simple glyphosate-phosphonate mixtures, thereby enhancing the weed control effect of a single application.

[0009] This herbicidal composition has the advantages of good weed control and good control of goosegrass in citrus fields in western Hubei, providing a new optimization idea for enhancing the efficacy of glyphosate herbicides and controlling goosegrass in citrus fields.

[0010] A glyphosate herbicide composition, wherein the herbicide composition contains the herbicidal active substance glyphosate, amino acids, and hydroxymethylphosphonic acid;

[0011] The mass ratio of glyphosate, amino acids, and hydroxymethylphosphonic acid is 100:(0.01-10):(0.01-5).

[0012] The herbicide composition also contains glyphosate, and the mass ratio of glyphosate to glyphosate is (1-50):(20-70).

[0013] The amino acid is any one of an amino acid or its carboxylate, and the carboxylate includes sodium salt, potassium salt, or ammonium salt.

[0014] Preferably, the amino acid is glutamic acid, lysine, arginine, threonine, glycine, or alanine.

[0015] Preferably, the formulation also contains ammonium hydrogen phosphate.

[0016] A herbicide comprising a pesticide-acceptable adjuvant to the glyphosate herbicide composition.

[0017] The formulation of the herbicide is selected from any one of wettable powder, soluble powder, soluble granules, water-dispersible granules, pellets, suspension concentrates, dry suspension concentrates, soluble concentrates, dispersible oil suspensions, or water emulsions.

[0018] Beneficial Effects: Under certain formulation and application conditions, the addition of small-molecule amino acids and hydroxymethylphosphonic acid according to this formula promotes the transport of the herbicide within the plant to the roots and other tillers and other parts, thus enhancing its efficacy. Furthermore, the presence of hydroxymethylphosphonic acid and amino acid molecules improves the storage stability of glyphosate formulations. Under the influence of amino acid molecules, the microscopic distribution of glyphosate and glyphosate molecules in the formulation is more uniform. Small-molecule amino acids and hydroxymethylphosphonic acid have physicochemical effects; through their physiological activity applied to plant leaves, they can improve the wettability and permeability of the glyphosate herbicide after application, increasing the absorption channels and utilization rate of herbicidal active molecules such as glyphosate and glyphosate. The presence of glyphosate and hydroxymethylphosphonic acid may, through interactions including but not limited to hydrogen bonding, promote this physiological activity of amino acids. In summary, the mixed composition of the present invention exhibits superior herbicidal activity compared to existing formulations. Under the combined effects described above, it demonstrates a synergistic herbicidal effect. Compared to glyphosate alone or glyphosate-glyphosate mixtures, using the same pesticide adjuvants, the composition or herbicide of the present invention shows higher herbicidal efficacy and lower regreening rate. Furthermore, while maintaining the same efficacy, the amount of glyphosate herbicide used can be reduced accordingly.

[0019] The herbicide composition screened and formulated using this invention was used in a citrus field in western Hubei Province to control the resistant weed *Eleusine indica*. The results showed a significant improvement in control efficacy under this scheme, and a slight improvement in the overall control efficacy against weeds in the citrus field. The 12-day control efficacy against weeds in the experimental field was approximately 3% higher than the control group (from approximately 90% to approximately 93%). In particular, the 14-day control efficacy against *Eleusine indica*, a difficult-to-control weed in the experimental citrus field in western Hubei Province, was approximately 6% higher (from approximately 76% to approximately 82%). The proportion of *Eleusine indica* plants with all tillers dying out of the total number of controlled weeds was also higher. The 30-day greening rate was lower than the control group, indicating a significant reduction in resistance, thus improving control efficacy and reducing herbicide usage. Detailed Implementation

[0020] The present invention will be further described in detail below with reference to specific embodiments, but the present invention is not limited to the following specific embodiments, nor is it limited thereto:

[0021] Examples 1-7

[0022] 1000g of a 70% glyphosate-ammonia soluble concentrate mixture was prepared according to the method in Example 1 of patented technology CN 115119851 A, wherein the mass ratio of glyphosate to glyphosate was 20:50, and the glyphosate content was 20% and the glyphosate content was 50%. Seven parallel samples (numbered A1-7#) were taken at 100g each. 1.1g of glutamic acid, lysine, arginine, threonine, glycine, and alanine were added to samples A1-6# in sequence, and 0.3g of hydroxymethylphosphonic acid was added to each sample. A7# was a blank control (no hydroxymethylphosphonic acid was added). Ammonia gas was slowly introduced to adjust the pH value to 6, and water was added to dilute to 125ml. The mixture was thoroughly mixed. A weed control test was conducted on a non-cultivated land in a citrus field in Yichang, Hubei Province. The glyphosate ammonium salt solution was diluted and mixed at a ratio of 2ml / 220g water and sprayed on a 10-square-meter plot for efficacy testing. In the A1-A7# sample test plots, weeds began to show yellowing leaves from the third day. After 12 days, the overall control efficacy was 91% in the A7# sample test plot, and 72% for *Eleusine indica* after 14 days. The overall control efficacy was 92% in the A1 and A5# sample test plots, and 93% in the A6 and A2-A4# sample test plots. The 14-day control efficacy for *Eleusine indica* was 80% in the A1-6# sample test plots. After 30 days, the regreening rate of weeds was 18% in the A7# sample test plot, and below 12% in all the A1-A6# sample test plots.

[0023] Examples 8-14: Prepare 40% glyphosate·glyphosate-enhancing aqueous solution according to the following method:

[0024] Formula (by weight): Add 600g water, 500g 95% glyphosate ammonium salt technical grade, 100g 90% glyphosate ammonium salt technical grade, and 80g synergist A. Stir thoroughly to obtain 1280g of 40% glyphosate·glyphosate soluble powder, with a glyphosate to glyphosate mass ratio of 33:7. Take 7 parallel samples (100g each, labeled B1-8#). Add 1.5g of glutamic acid, 1.5g of lysine, 1.5g of arginine, 1.5g of threonine, 1.5g of glycine, and 1.5g of alanine to samples B1-6# in sequence. Add 0.3g of hydroxymethylphosphonic acid to samples B1-7#. Add 1.5g of glutamic acid, 0.3g of hydroxymethylphosphonic acid, and 1.0g of ammonium hydrogen phosphite to sample B7#. B8# is a blank control (no amino acids or hydroxymethylphosphonic acid added). Dilute B1-8# with water to 110ml each, mix thoroughly, and then dilute the glyphosate ammonium salt solution at a ratio of 2ml / 220g water, mix thoroughly, and spray on a 10m² plot for efficacy testing. In the B1-B7# sample plots, weeds began to show yellowing leaves from the third day. After 12 days of efficacy testing, the overall control efficacy of the B8# sample plot was 91%, and the control efficacy against goosegrass after 14 days was 76%; the overall control efficacy of the B1-B6# sample plots was all above 92%, and the control efficacy against goosegrass after 14 days was 81%; the overall control efficacy of the B7# sample plot was all above 96%, and the control efficacy against goosegrass after 14 days was 93%. After 30 days, the regreening rate of weeds was 16% in the B7# sample plot, 8-11% in the A1-A6# sample plots, and below 6% in the A7# sample plot.

[0025] Examples 15-21

[0026] Glyphosate isopropylamine salt solution was prepared according to the method described in Example 3 of patented technology CN 112471170 B. A 46% glyphosate isopropylamine salt was prepared and mixed with adjuvants at a mass ratio of 8:2 to obtain the glyphosate isopropylamine salt solution. In this example, the mass ratio of glyphosate to glyphosate was 27.3:0. Seven parallel samples (C1-7#) were taken, each weighing 100g. 1.1g of glutamic acid, lysine, arginine, threonine, glycine, and alanine were added sequentially to samples C1-6#, along with 0.3g of hydroxymethylphosphonic acid. C7# served as a blank control (without added amino acids or hydroxymethylphosphonic acid). The mixture was diluted with water to 108ml and thoroughly mixed. A non-cultivated land weed control experiment was conducted in a citrus field in Yichang, Hubei Province. The glyphosate ammonium salt solution was diluted and mixed thoroughly with 2ml / 220g water and sprayed on a 10-square-meter plot for efficacy testing. In the C1-C7# sample test plots, weeds began to show yellowing leaves from the third day. After 12 days, the overall control efficacy was 91% for the C7# sample test plot, and 75% for *Eleusine indica* after 14 days. The overall control efficacy was 90% for the C6# sample test plot, and 92% for the C1-C5# sample test plots. The 14-day control efficacy for *Eleusine indica* in the C1-C6# sample test plots was above 79%. After 30 days, the regreening rate of weeds was 14% for the C7# sample test plot, and below 12% for all C1-C6# sample test plots.

[0027] Comparative Examples 22-28:

[0028] The adjuvant was prepared according to the method described in Example 3 of patented technology CN 112471170 B. A 33% glyphosate ammonium salt solution, 90% glyphosate ammonium salt technical grade, and the prepared adjuvant were mixed at a mass ratio of 8:1:2 to obtain a glyphosate and glyphosate compound mixture with a glyphosate to glyphosate mass ratio of 22:8. Seven parallel samples (numbered D1-7#) were taken at 100g each. 0.2g of glutamic acid, 0.8g of lysine, 0.9g of arginine, 1.1g of threonine, 1.2g of glycine, and 1.6g of alanine were added sequentially to samples D1-6#, along with 0.3g of hydroxymethylphosphonic acid. D7# served as a blank control (without amino acids or hydroxymethylphosphonic acid). The mixture was diluted with water to 120ml and thoroughly mixed. The glyphosate ammonium salt solution was then diluted and mixed thoroughly with water at a ratio of 2.5ml / 220g water and sprayed onto a 10-square-meter plot for efficacy testing. In the D1-D7# sample test plots, weeds began to show yellowing leaves from the third day. After 12 days, the overall control efficacy was 90% in the D7# sample test plot, and 76% for *Eleusine indica* after 14 days. In the D1-D6# sample test plots, the overall control efficacy was above 92%, and 82% for *Eleusine indica* after 14 days. After 30 days, the regreening rate of weeds was 15% in the D7# sample test plot, below 14% in the D1# sample test plots, below 11% in the D2 and D4# sample test plots, and below 9% in the D3, D5, and D6# sample test plots.

[0029] Comparative Example 29:

[0030] A commercially available 41% glyphosate isopropylamine salt solution (single agent) was purchased as a reference and diluted in the same proportion (2ml / 220g water). The solution was sprayed on a 10-square-meter plot in the experimental field to conduct an efficacy test. The overall weed control efficacy was 89% after 12 days, and the control efficacy of goosegrass was 62% after 14 days.

Claims

1. A glyphosate herbicide composition, characterized in that, The herbicide composition contains the herbicidal active substances glyphosate, amino acids, and hydroxymethylphosphonic acid; the mass ratio of glyphosate, amino acids, and hydroxymethylphosphonic acid is 100:(0.01-10):(0.01-5). The herbicide composition also contains glyphosate, and the mass ratio of glyphosate to glyphosate is (1-50):(20-70). The amino acids are glutamic acid, lysine, arginine, threonine, glycine, or alanine.

2. A herbicide comprising the glyphosate herbicide composition of claim 1 and a pesticide-acceptable adjuvant.

3. The herbicide according to claim 2, characterized in that, The formulation of the herbicide is selected from any one of wettable powder, soluble powder, soluble granules, water-dispersible granules, pellets, suspension concentrates, dry suspension concentrates, soluble concentrates, dispersible oil suspensions, or water emulsions.