KR920003974B1 - Improved glyphosate formulations - Google Patents

Abstract

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Description

Glyphosate Formulation with Enhanced Herbicides

1 is a comparison between the addition of ammonium sulfate to Formulation No. 1 and Formulation No. 1 of the present invention and the herbicidal ability of wheat by control solutions 1 and 3,

FIG. 2 shows the results after 14 days of spraying a spray solution containing C2 as a surfactant to blackgrass.

3 shows the result of 14 days after spraying black spray with a spray solution containing C8 as a surfactant,

Figure 4 is obtained after 14 days of treatment with a formulation containing monoisopropyl amine glyphosate (1 and 10), ammonium glyphosate (20 and 26) and potassium potassium glyphosate (19 and 25). Represents the result,

FIG. 5 shows the result of spraying native wheat flour with the addition of ammonium sulfate to Formulation No. 1 at an amount equivalent to 0.27 Kg glyphosate acid (aicd equivalent: a.e.) / Hectare,

Figure 6 shows the herbicidal effect of glyphosate preparations on annual broad leaf tobacco,

7 and 8 show the herbicidal effect of Formulation No. 1 on perennial green grass and clover,

9 shows the herbicidal effect of the formulations of the present invention on couch,

10 shows the results obtained after 22 days of treatment with various surfactants and a spray solution prepared by diluting a concentrate containing glyphosate completely derived from isopropylamine salt,

11 shows the results obtained after 22 days of treatment with a spray solution containing C2 as a surfactant using various spray solutions prepared by reducing the proportion of the surfactant.

The present invention relates to glyphosate preparations with improved herbicidal activity.

(Roundup) 제초제와 같이 상업용 제제는 글리포세이트의 제제는 글리포세이트의 수용성염을 함유하고 있다. 글리포세이트의 모노이소프로필 아민염의 제초능에 대한 계면활성제의 효과에 관한 여러가지 연구 결과가 여러 문헌에 기재되어 있는바, 예를들어, Weed Reserch, 1980, Vol20, 139-146기재에서 터어너(Turner)와 로우더(Loader)등은 HLB값(hydrophile-lipop-hile balance)이 17인 지방아민 에톡시-레이트가 Roundup

제초제 용액의 제초능을 증가시키는데 가장 효과적이라고 밝힌바 있으며, 같은 문헌에서 이들은 암모니움 설페이트와 소수성 계면활성제를 가지는 분무용액에 있어서 계면활성제에 따른 제초 효과가 다른 것임을, 예를들어 HLB값이 6인 지방 아민에톡시 레이트는 더욱 큰 효과를 가지는 것으로 언급하고 있다. 1985년 BCPC 모노그램 No.28 심포지움의 "대체형 글리포세이트 제제에 관한 연구"에서 터어너와 태브버쉬(Tabbush)는 잎에 분무하는 용액으로서 제조한 글리포세이트 산으로 행한 실험의 결과를 설명하고 있는데, 결과의 요약에서 그들은 글리포세이트산은 계면활성제와/또는 암모니움 설페이트를 첨가하지 않은 것은 상대적으로 낮은 활성을 가지지만 첨가했을때의 약해(phytotoxicity)는 Roundup

, 제초제의 약해와 같았다고 언급한바 있다. 글리포세이트산은 순수한 물에서 보다 아민몰당 5몰의 에틸렌 산화물을 포함하는 우지(tallow:동물성 지방)로부터 얻은 3급아민 용액에서 더욱 많이 용해된다는 것이 밝혀진바 있다.Glyphosate (N-phosphonomethylglycine) is widely known as a herbicide acting on leaves, but because of its low water solubility in the free acid form, glyphosate is present as a monoisopropyl amine salt.

Commercial preparations, such as herbicides, contain glyphosate's water-soluble salts. Various studies on the effect of surfactants on the herbicidal activity of monoisopropyl amine salts of glyphosate have been described in the literature, for example, in Turner (Turner, Weed Reserch, 1980, Vol 20, 139-146). ) And loaders are rounded up by fatty amine ethoxy-rates with an HLB (hydrophile-lipop-hile balance) of 17

In the same literature, they have different herbicidal effects of surfactants in spray solutions containing ammonium sulphate and hydrophobic surfactants. Fatty amineethoxylates are said to have a greater effect. In 1985 "A Study on the Alternative Glyphosate Formulations" of the BCPC Monogram No. 28 Symposium, Turner and Tabbbush described the results of experiments with glyphosate acid prepared as a solution sprayed onto leaves. In summary, they show that glyphosate acid has relatively low activity without the addition of surfactants and / or ammonium sulfate, but the phytotoxicity of the addition is Roundup.

It was mentioned that it was like the weakness of herbicides. It has been found that glyphosate acid is more soluble in tertiary amine solutions obtained from tallow (animal fat) containing 5 moles of ethylene oxide per mole of amine than in pure water.

, 제초제와 같이 글리포세이트보다 훨씬 적은 양의 계면활성제를 함유하는 용액의 사용 및 20ℓ/ha의 비율로 분무하는 것에 대하여 언급한바 있다.Herbicides and the like containing appropriate amounts of thiocyanate mixtures belonging to a particular class comprising isopropyl amine salts of glyphosate and ammonium thiocyanate are described in US Pat. No. 4,612,034. In the experiments described in 1985 BCPC Monogram No. 28 concerning the preparation of glyphosate salts or the solubility of glyphosate acid with ethoxylated fatty acid amines, the amount of ethoxylated fatty acid amine surfactant was at least 5 parts by weight In one experiment described in Weed Reserch, 1980, Vol 20, 139-146, a roundup containing a sufficient amount of surfactant in itself was used.

, The use of solutions containing much less surfactants than glyphosate, such as herbicides, and spraying at a rate of 20 l / ha.

However, experiments when sprayed in a typical manner at typical usage rates of about 200 L / ha indicated that the solution used about twice the surfactant of glyphosate.

In the study of the present invention the inventors used a conventional spraying rate and used a solution at a ratio lower than the ratio of surfactant to glyphosate in the solution sprayed at the usual rate in the conventional method. The inventors have obtained better results under most conditions than experiments with hydrophilic fatty amine ethoxylates, if the experiments with the solution of the invention containing hydrophobic fatty amine ethoxylates are considered to be the most useful to date. The result was the same whether or not the solution contained ammonium sulfate.

This result is surprising in view of the prior art, which claims that hydrophobic surfactants should not be used as surfactants except in the presence of ammonium sulfate.

It is an object of the present invention to provide a commercially useful glyphosate composition for use with inorganic ammonium salts that can be used in agriculture, such as ammonium sulfate, for spraying at conventional rates of use.

A feature of the present invention is to reduce the amount of alkoxylated amine surfactant to the total glyphosate contained in the conventional spray solution while maintaining the herbicidal per unit of glyphosate below the ratio of the prior art. The unit activity can be increased even when the ratio of the surfactant to glyphosate is similar to that of the present invention. In one aspect, another feature of the present invention provides a composition comprising a concentrate comprising (a) glyphosate in which glyphosate is dissolved at least equivalent to 40 g per liter and (b) an aqueous solution containing a surfactant. will be.

The surfactant here is (i) an amine having the structure

Wherein R is a straight or branched chain alkyl or alkenic group having from about 8 to about 22 carbon atoms, A is an alkylene group such as ethylene or propylene group, n and n 'are from 1 to about 12 Numerical value), (ii) a mixture of amines having other R groups with an average of about 8 to about 22 carbon atoms in the R group, or (iii) n and n 'in each amine are n + n' Is an integer having a number from 0 to about 15, a mixture of amines with n and n 'of different values, but the mean of the sum of n + n' in the mixture is from 1 to about 12 and R is one value in the mixture (ii) I have an average. The weight ratio of (a) (expressed in the amount corresponding to glyphosate acid) to (b) is about 1: 1.75 to about 6: 1.

Another feature of the present invention is a spray containing a dissolved glyphosate and a surfactant and sprayed at a normal rate of use, as defined by the weight ratio of glyphosate (expressed in glyphosate acid equivalents) to the weight ratio of the surfactant. To provide a solution. The weeding method includes spraying weeds with 100-400 liters per hectare of the above-mentioned spray solution in an amount of 0.125 to 1.5 Kg per hectare in an amount corresponding to glyphosate acid in the spray solution.

In the compositions of the present invention, glyphosate is added to and dissolved in a solution of cations available for one or more agriculture. Such cations include alkoxylated amine surfactants in cationic form, alkali metal cations such as sodium and potassium, ammonium and substituted ammonium cations. The latter includes cations derived from primary or secondary amines such as isopropyl amine or dimethylamine and cations derived from diamines such as ethylenediamine. Other salts of glyphosate that can be used in agriculture include trialkylsulfonium salts, such as aminoguanidine salts and trimethylsulfonium salts, such as those described in EP 0088180 and US Pat.

Formulations containing (a) and (b) in a small (1: 1.75) ratio of the above-mentioned range can be prepared from a low molecular weight surfactant by dissolving only glyphosate acid and a surfactant.

In most cases, however, the upper limit of the amount of surfactant is determined by a solution containing not only the surfactant cation but also a cation usable for agriculture. In specific cases the dissolved glyphosate is (i) partly derived from the dissolution of glyphosate by the surfactant and partly derived from glyphosate salts with cations available for other agriculture, or (ii) All can be derived from salts of glyphosate with other cations available for agriculture.

As will be described later, the concentrate of the present invention may contain not only the components (a) and (b) but also inorganic ammonium salts which can be used for appropriate amounts of agriculture. Concentrates containing such salts depend on the degree of water solubility of the glyphosate salt, but may include up to 450 g / l in amounts corresponding to glyphosate acid at room temperature. For example, when the glyphosate salt is a monoisopropyl amine salt, a solution containing 250-400 g / l in an amount corresponding to glyphosate acid is readily prepared. The monoammonium glyphosate, with the exception of some alkali metal salts, exhibits similar dissolution properties as the potassium salts are somewhat less soluble. In general, from the economic point of view, concentrates of the invention containing a minimum amount of water, ie sufficiently saturated solutions, are preferred. To make the solution easy and easy to use depends on climatic conditions, so the solution can be prepared at -5 ° C, 0 ° C or 10 ° C to saturate the solution.

For example, a solution that is stable at temperatures below 10 ° C. is also stable, for example at 5 ° C. (eg, no solids precipitate), thereby producing a normally stable solution. The concentrate of the present invention may also contain conventional antifreeze agents such as ethylene glycol, polyethylene glycol or glycerol.

In the compositions of the present invention, the weight ratio of total glyphosate (expressed in an amount corresponding to glyphosate acid) to the surfactant is from about 1: 1.75 to about 6: 1. The maximum amount of surfactant should be determined in consideration of economics. Increasing the proportion of surfactant increases the unit herbicidal effect of glyphosate, but at some point the price is not effective. It is advantageous to use more than 1.5 parts of surfactant per part by weight of the corresponding amount of glyphosate acid when the concentrate is also considered a precursor of spray solution containing inorganic ammonium salts for agricultural use. The other end of the range has a maximum preferred glyphosate: surfactant weight ratio of about 4: 1. More preferred ranges of proportions vary from 1: 1 to 3: 1, depending on the particular surfactant used, for example 1.5: 1 to 2.5: 1.

Commercially available amine surfactants in the formulations described above contain more mixtures than single compounds. This includes an alkoxy derivative of "cocoamine" in which the R group corresponding to the alkyl group is derived from myristic acid, lauric acid, palmitic acid, stearic acid. The average number of carbon atoms in R of cocoamine is 12-14. Other examples are alkoxylated derivatives of "oleylamine" wherein the main carbon chain of R is oleic acid (18 carbon atoms), stearylamine (18 carbon atoms) and "tallowamine" main carbon It is equivalent to chain R. Commercially available surfactants are mixtures of molecules in which n + n 'has various values and surfactants in which n + n' have average low values may contain a proportion of non-alkylated or monoalkylated amines. Preferred alkoxylated derivatives are ethoxylated derivatives. In general, the use of low molecular weight surfactants provides higher molecular concentrations than the same weight of high molecular weight surfactants, so low molecular weight surfactants are preferred over high molecular weight surfactants. Most preferred surfactants are those wherein A is an ethylene group and the number or average number of carbon atoms in the functional group or R group is about 10 to about 20. Considering the n + n 'value or average value, preferred surfactants are n + n' value or average value in the range of about 1.5 to about 12, more preferably in the range of about 2 to about 10. Specific examples of preferred surfactants are ethoxy, coco namine with n + n 'having an average value of about 2, resin amine with n + n' having an average value of about 5, and oleylamine with n + n 'having an average value of about 8. Shisa derivatives. In the preparation of the concentrate of the present invention in which the cationic form of the surfactant at least partially determines the solubility of glyphosate, the dissolved glyphosate acid solution is in most cases an acid and alkoxylated amine surfactant at room temperature in an aqueous medium. Many solutions can be prepared in minutes by mixing at or at slightly higher temperatures. The amount of surfactant required to solution glyphosate acid is usually about 1: 1 molar equivalent. However, a slightly smaller amount, eg 90% molar equivalent may be sufficient in some cases, but in some cases a smaller amount, eg 30% molar equivalent, may be desirable. The lighting to consider to determine the maximum amount of surfactant used has already been described above. Where it is necessary to prepare a portion of glyphosate in the form of a glyphosate salt with a cation available for agriculture, mix it with the dissolved glyphosate solution and the glyphosate salt solution, and then Provide each component. Concentrates of the invention in which a sufficient amount of cations other than surfactants in cationic form to dissolve glyphosate are present can be prepared by simply mixing the components at room temperature. Surfactants are usually viscous materials that dissolve at low speeds when stirring an aqueous solution of glyphosate salts. Also, if necessary, a solution of ammonium salt which can be used for agriculture can be mixed in this step.

Generally used solutions can be concentrated or nearly completely saturated to minimize the amount of water in the concentrate. However, if necessary, some adjustments may be made to this effect after mixing, e.g. evaporation or water addition. Examples of inorganic ammonium salts that can be used in agriculture that have been shown to be effective in improving the herbicidal effects of glyphosate and other water-soluble and water-soluble herbicides are ammonium sulfate, ammonium nitrate, ammonium phosphate, and ammonium sulfamate. Ammonium thiocyanate is included, of which double ammonium sulfate is preferred.

The amount of ammonium salt that may be included in the concentrate containing the ammonium salt depends on their solubility in the presence of other factors.

However, the amounts of other components can be adjusted to achieve the desired concentration of ammonium salts.

Generally the amount contained is at least 0.5 parts, for example 1 to 10 parts by weight of the ammonium salt per part by weight of component (a). The concentrate of the present invention contains at least 70 g / l, which has from 80 to 150 g / l of component (a) and from 100 to 500 g / l of ammonium salt and in an amount corresponding to component (a) (glyphosate acid). Expressed weight ratio of component (b) is usually from about 1: 1 to about 1:75. An example of a composition is as follows.

Glyphosate acid 74g / ℓ

Glyphosate Monoisopropylamine Salt 49g / l

(Expressed in the amount corresponding to the mountain)

C2 ^* Surfactant 120g / ℓ

Ammonium Sulfate 280g / ℓ

* An ethoxylated derivative of cocoamine having an average of about 2 ethoxy groups.

A preferred class of concentrates containing ammonium salts is an ethoxylated cocoamine derivative having 80 to 130 g per liter of component (a) present as a salt of glyphosate with monoisopropylamine, with an average of about 2 n + n '. A composition containing 100 to 180 g of phosphorus (b) component and 260 to 320 g of ammonium sulfate per liter.

The present invention includes a herbicidal spray solution for spraying at conventional usage, wherein the spray solution comprises (a) glyphosate, (i) some of which are glyphosate dissolved by the aforementioned surfactants, and some of which Glyphosate salts with cations available for use, or (ii) all of them are glyphosate acids dissolved by the above-mentioned surfactants, or (iii) all have cationic forms of surfactants and other cations available for agriculture. A dissolved glyphosate component, which is a salt of glyphosate, (b) containing the above-mentioned surfactant, wherein the weight ratio of component (a) (expressed in the corresponding amount of glyphosate acid) to component (b) is about 1: 1.75 To about 6: 1 solution.

The concentration of glyphosate in the spray solution is usually that when spraying the spray solution with 100-400 liters per hectare, the use rate of the corresponding glyphosate acid is 0.125 to 1.5 Kg per hectare.

In addition, it is preferable that such a spray solution contains an inorganic ammonium salt which is water-soluble and can be used for agriculture. The amount of inorganic ammonium salt used may vary depending on the type of weed to be treated, the spraying apparatus to be used, the climatic conditions, and the like. Typically, however, the solution will be sprayed at 100-600 L / ha, for example 100-400 L / ha, where the amount corresponding to glyphosate will be at least 0.125 Kg / ha and the solution should be at least It will include ammonia salt in a weight concentration such as that corresponding to lipoacetic acid. For example, the weight ratio of glyphosate acid to ammonium salt in the solution will range from 1: 1 to 1: 10. The effect of ammonium salts in improving the herbicidal activity of glyphosate is that this ratio range increases rapidly at the lower end of the range but much later in the middle and above. Optimal use ratio with ammonium sulfate is about 1: 2 to about 1: 7. It is very effective to use a solution containing 5-100 g / l, preferably 5-30 g / l, of inorganic ammonium salts when the amount corresponding to glyphosate acid is in the range of 0.25-1.5 Kg / ha.

A preferred method for preparing the herbicidal spray solution as described above is to mix the concentrate of the invention with water, preferably with the ammonium salt, but if desired each component of the solution is mixed with the required amount of water in the spray tank. You can.

The concentrates and spray solutions of the present invention may optionally contain additional components, as described above, which include antifreeze agents and include antifoams such as dyes, thickeners, silicone-based antifoams and nonionic surfactants such as polyethyleneethers or esters. Secondary surfactants. In addition, the concentrate and spray solution of the present invention are mixed with other water-soluble herbicides, such as 2,4-dichlorophenoxy acetic acid or 4-chloro-2-methyl phenoxyacetic acid salts, and finely divided water-soluble herbicides, ie triazines or substituted ureas. It may, but is not limited to.

The invention is explained in more detail by the following examples.

Tables 1-3 show solutions of the invention wherein the dissolution of glyphosate acid is at least partially affected by the presence of surfactants in cationic form. This solution first dissolves the cliphosate acid (crystal corresponding to 9% of the water weight) by stirring the water at room temperature or at a temperature not exceeding 60 ° C. and about 1.05 moles of ethoxylated amine surfactant per mole of glyphosate acid. It is prepared by dissolving an equivalent. When necessary, the monophosphate (ammonium, isopropylamine, or potassium) solution of glyphosate is mixed with water, if necessary, with water, and the amount corresponding to glyphosate acid shown in the following table: A solution representing the concentration was prepared.

In the table, various components are expressed in weight percent, and the surfactant is described as the first letter of the amine and the average number of ethoxy groups.

That is, C2 represents a surfactant derived from cocoamine having two ethoxy groups, O5 is an average of 5 ethoxy groups and is derived from oleylamine, and S8 is an average of 8 ethoxy groups and is derived from stearylamine. T10 represents a surfactant derived from teloamine with an average of 10 ethoxy groups. Glyphosate salts were described as AM (ammonium), IP (isopropylammonium) or K (potassium).

The solution in Table 1 contains approximately 300 g / l of glyphosate acid and 150 g / l of surfactant. The surfactant corresponds to 13.64 wt% of the surfactant in solution and the glyphosate salt is a monoisopropylamine salt.

TABLE 1

Table 2 shows the weight percentages for each component in various solutions containing glyphosate, monoisopropyl amine salt of glyphosate, and an ethoxylated surfactant, corresponding to glyphosate in each solution. The weight ratio of the amount to the amount of surfactant is different.

TABLE 2

Table 3 shows the weight percentages of the components in the solution wherein the glyphosate salt is an ammonium (AM) or potassium (K) salt. The weight ratio of acid and surfactant corresponding to glyphosate acid in the solution is 2: 1.

TABLE 3

Solutions 21 and 25 contain 280 g / l and 140 g / l of surfactant in amounts corresponding to glyphosate acid, while other solutions contain 300 g / l of the former and 150 g / l of the latter.

Table 4 shows the composition of the present invention prepared by stirring 62 wt% of an aqueous solution of monoisopropyl amine salt of glyphosate and the required amount of surfactant at room temperature and then mixing a saturated solution of ammonium sulfate if necessary. .

TABLE 4

In the figure, FIG. 1 shows the results obtained from greenhouse experiments on the growth of wheat, and FIGS. 2, 3, 4, 10 and 11 show the results obtained from greenhouse experiments on blackgrass (Alopecurus myosuroides), and FIG. Figure 6 and Figure 6 show the results obtained in the field experiments on the stubble of the wheat. Wheat, such as wild wheat, is weed within its own range. In addition, the effect of native wheat on glyphosate is representative of the effect in the range of weeds. Figures 7 and 8 show the results of field experiments in pastures sown with perennial Lolium perenne and Clover (Trifolium repens), and Figure 9 shows perennial wheat weeds in fields with only stumps of grain. Elymus repens) shows the experimental results.

The herbicidal activity in the greenhouse was measured using the following method.

The plants were sown in 13 cm pots containing a natural sandy loam soil. All pots were automatically watered from the bottom and mineral nutrients were added to the water as needed. Pots were grown in a Conviron greenhouse at 14 hours of photoperiod, 600 micro Einstein m ⁻² s ⁻¹ , and 15 ° C. (day) and 9 ° C. (night) temperature. About 2 weeks (2-4 weeks after sowing) before spraying the herbicide solution, the plants are adjusted by hand to produce a uniform form.

At least a week before treatment, plants are transferred to larger greenhouses with sophisticated climate control, as well as fine control of relative humidity to 50% during the day and 65% or 75% at night. Do not transfer the plant to be used as a control for the experiment. Before spraying, the pot should be as uniform as possible and discard any irregularities. The spray solution was sprayed using a Mardrive precision laboratory sprayer, which was intended to spray the spray solution at 200 L / ha in one use. All uniform pots (3-5 per species per treatment) were sprayed through a nebulizer once.

After treatment, untreated control pots were randomly placed between treated pots. The measurement of "% weak" was made in comparison to the untreated control on a suitable scale from 0 to 100%, where 0% means no effect and 100% means complete death. In any one measurement, all pots were measured in comparison to the same population and the unknown results were "blind". The blocks in 2nd, 3rd, 4th, 10th and 11th represent the average value of the experimental results performed with 3-5 uniform pots used.

Experiments with the results shown in FIGS. 5 and 6 were conducted in wheat stubble fields covered with 75% of weeds. About 35% of the weeds are wild wheat, and the rest are annual broad-leaved tobacco, 35% are Stellaria media, 10% are Viola arvensis, and 10% are crimson Anagallis arvensis. to be. Air temperature was 23 ℃, soil temperature 15 ℃, relative humidity 48%, and wind speed was 0. In the experimental method, four randomly selected blocks with uniform weeds having a unit area of 18 m ² were sprayed with a solution.

The experimental results described are expressed in% of leaves dead 3 weeks after treatment.

The experiments in which the results shown in Figures 7 and 8 were obtained were carried out on pastures with one part perennial grass and the other part mixed grasses and clover. Experimental results showed only poisonous grasses and clover.

The air temperature during the spraying was 18 ° C with a slight wind and no rainfall for 2 days after spraying. The experimental method randomly selected three uniform pots for each treatment and the uneven plots selected 12 uniform pots. The area of perennial poisonous grassland was 16m ² and the area of the mixture of weeds and clover was 16m ² . The experimental results recorded are expressed in% of leaf death at 47 days after treatment.

The experiments with the results shown in FIG. 9 were carried out in a field of grain stubble where the wheat, which is almost uniformly distributed in the area under test, caused some interference. The temperature of the air at the time of spraying was 15 ° C., there was a slight wind, and there was no rainfall for 5 days after spraying. In the experimental method, three uniform pots having a pot area of 30 m ² were randomly selected and treated with a spray solution. Recorded results are reported as% of leaf death 25 days after treatment.

The concentrations listed on the table in the preparation of the spray solution were diluted with water to a spray amount of 200 L / ha and the use rates as the amounts corresponding to glyphosate acid per hectare are described in FIGS.

The spray solution containing the ammonium sulfate used in the experiment of FIG. 1 contains 6 parts by weight of ammonium sulfate per part by weight of the amount corresponding to glyphosate acid. The spray solution containing ammonium sulfate used in the experiments of FIGS. 2, 3 and 4 and the field experiments of FIGS. 5 and 6 contains 10 g / L of ammonium sulfate.

The spray solution containing ammonium sulfate used in the field experiments of FIGS. 7, 8 and 9 contains 3.6 parts by weight of ammonium sulfate per part by weight of the corresponding amount of glyphosate acid.

The spray solution (control solution) used for the comparative purposes contains, as glyphosate, a surfactant whose main subject is an ethoxylated tallow amine salt having all monoisopropyl amine salts and having an average of 15 ethoxide units. Control solution 1 had a weight ratio of 2.94 parts of surfactant per 1 part in an amount corresponding to glyphosate acid, control solution 2 was the latter 2 parts with respect to 1 part of the former, and control solution 3 was the latter 1 with 2 parts of the former. It is wealth. This ratio is similar to that of commercial glyphosate formulations.

In the figure, the spray solution is described as "formalation", and the numbers are listed according to the number of the concentrate in the above-mentioned table in which the concentrate is derived.

1 shows that the control solution 1 has a weight ratio of the amount corresponding to the glyphosate acid, although the amount of the surfactant equivalent to the glyphosate acid is almost six times as large as that of the glyphosate acid. Formulation No. 1 of the present invention with 2: 1 and ammonium sulfate exhibits at least ground herbicidal activity against wheat at all usage rates than Control Solution 1.

As in preparation No. 1 of the present invention, the preparation No. 1 of the present invention is 0.18, 0.36 0.72 Kg compared with the control solution 3 having the same glyphosate: surfactant ratio and the preparation No. 1 without the addition of ammonium sulfate. When sprayed at ae / ha, Control 3 showed the same activity as sprayed twice at the same amount, 0.36, 0.72 and 1.44 Kg ae / ha. Compared with the addition of Ammonium sulfate to Formulation No. 1, spraying with 0.09, 0.18 and 0.36 Kg a.e./ha showed the same activity as spraying Control Solution 3 in the same amount four times.

2 shows the results obtained after 14 days of treatment with blackgrass with a spray solution containing C2 as a surfactant. The decrease in activity occurs as the proportion of surfactant decreases but the rate of decrease is much less than in solutions containing ammonium sulfate. Formulation No. 1 with ammonium sulfate (amount equivalent to glyphosate acid: surfactant ratio of 2: 1) showed better activity at low utilization and control solution 2 despite low ratio of surfactant. It showed the same activity as the highest ratio of. Formulation No. 12 with ammonium sulfate (amount corresponding to glyphosate acid: 1: 1 ratio of surfactant) showed better activity in all grades than in Control 2. At the lowest usage rate, Formulation 3 was more active than Control Solution 3, with the same proportion of glyphosate and surfactant.

4 shows the results obtained after 14 days of treatment with a preparation containing monoisopropyl amine glyphosate (1 and 10), ammonium glyphosate (20 and 26) and potassium glyphosate (19 and 25). It represents.

All formulations have a weight ratio of 2: 1 equivalent to glyphosate acid, as in Control 3. It is clear that the herbicidal ability of the formulations of the invention is improved compared to the control solutions and in any case the formulations with ammonium sulphate have at least the same weakness as Control 2, which has a ratio of four times the surfactant.

5 shows that the herbicidal power of Formulation No. 1 shows the same activity as Control Solution 1 by adding ammonium sulfate, although the ratio of the amount of surfactant to glyphosate acid is much lower. The addition of ammonium sulfate at 0.54 Kg a.e./ha has little effect on the herbicidal capacity of Formulation No.1. It has the same activity as the control solution, with or without ammonium sulfate.

6 shows the herbicidal effects of glyphosate preparations on annual broad leaf tobacco. The formulation of the present invention has the same herbicidal capacity as Control Solution 1 at 0.54 Kg a.e./ha despite the low surfactant ratio.

7 and 8 show the herbicidal effects of Formulation No. 1 on perennial green grass and clover. For both species, the formulation of the present invention is equal to or superior to the activity of Control Solution 1, despite the low proportion of surfactant, and is active with Control Solution 3 with the same surfactant ratio, except that it is used twice at the same rate of use. Show equal or superior. The addition of ammonium sulfate slightly increased the activity of Formulation No. 1.

9 shows the herbicidal effect of the formulation of the invention on wheat. Both Formulations No. 1 and No. 13 to which ammonium sulfate was added were more active than Control Solution 1, which had about 6 times the surfactant per unit of the amount corresponding to glyphosate acid of Formulation 1 and nearly 12 times that of Formulation No. 13. There was this. At 0.18 and 0.36 Kg a.e./ha, all of the formulations of the present invention had the same activity as Control 3, which was used four times at this usage rate, namely 0.72 and 1.44 Kg a.e./ha.

FIG. 10 shows the results obtained after 22 days of treatment with a spray solution prepared by diluting a concentrate containing glyphosate derived from both various surfactants and isopropylamine salts. In all solutions glyphosate and surfactant are present in a ratio of 2: 1. At the lowest utilization rate, all solutions of the present invention were more active than the control solution. All solutions except C10 or O8 as surfactant at the amount / ha corresponding to 0.25 Kg glyphosate acid were more active than the control solution. In experiments with a solution containing ammonium sulphate (not shown), all solutions were more active than the control solution at amounts / ha corresponding to 0.125 Kg glyphosate acid, containing C10 as a surfactant. All solutions were more active than the control at amounts / ha corresponding to 0.25 Kg glyphosate acid.

FIG. 11 shows the results obtained after 22 days of treating a spray solution containing C2 as a surfactant with various spray solutions prepared with a decrease in the proportion of the surfactant.

All of these glyphosates are derived from monoisopropyl amine salts. The decrease in activity occurs as a result of reducing the proportion of surfactant, but when the solution of the present invention (concentrate No. 38) containing glyphosate and surfactant in a ratio of 4: 1 is used at the lowest utilization rate There was more than twice the activity of the control solution containing twice.

At higher rates of use there was at least the same activity as the control. Similar morphology was observed (not shown) in solutions containing 1% ammonium sulfate. At all rates, the solution containing glyphosate and surfactant in a ratio of 4: 1 was more active than the control solution containing twice the surfactant.

Claims (43)

(a) at least 40 g of dissolved glyphosate per liter of glyphosate acid and (b) a surfactant with (i) an amine having the structure

Wherein R is a straight or branched chain alkyl or alkenyl having about 8 to about 22 carbon atoms, A is an alkylene group, n and n 'are integers with n + n' numbers from 1 to about 12 .) (ii) a mixture of amines having other R groups with an average number of carbon atoms in the R group of about 8 to about 22, or (iii) n and n 'each having a number of n + n's of 0 to 15 N and n 'as in is a mixture of amines where n and n' have different values, but the mean of the sum of n + n 'in the mixture is from 1 to about 12, and R is one value as in mixture (ii) (B) an herbicidal composition characterized in that the weight ratio of (a) (expressed in an amount corresponding to glyphosate acid) to (b) is from about 1: 1.75 to about 6: 1 . The herbicide composition of claim 1 wherein the weight ratio of component (a) to surfactant is from about 1: 1 to about 4: 1. 3. The herbicide composition of claim 2 wherein the weight ratio of component (a) to surfactant is from about 1.5: 1 to about 3: 1. The herbicide composition according to any one of claims 1 to 3, wherein in the structure of the surfactant A represents an ethylene or propylene group and the surfactant is a mixture in which n + n 'has an average value of about 1.5 to about 12. . 5. The herbicide composition according to claim 4, wherein A is an ethylene group. 6. The herbicide composition according to claim 5, wherein the number or average number of carbon atoms in R is about 8 to about 18 and the average value of n + n 'is about 2 to about 10. 7. The herbicidal composition of claim 6, wherein the surfactant is an ethoxylated derivative of cocoamine, teloamine or oleylamine with n + n 'having an average of about 2, about 5 or about 8. 8. The method according to any one of claims 1 to 3 or 5 to 7, wherein the glyphosate is (i) a part of the glyphosate acid dissolved by the surfactant (b) and a part of the surfactant in cation form. A herbicide composition, characterized in that the glyphosate salt with a cation usable for other agriculture, or (ii) the glyphosate acid is dissolved in its entirety by a surfactant. 9. The herbicide composition of claim 8 wherein the amount of surfactant is at least 90% of a 1: 1 molar equivalent of glyphosate acid. 9. The herbicide composition according to claim 8, wherein the salt of glyphosate is isopropylamine salt. 8. The glyphosate of claim 1, wherein all glyphosates are present as glyphosate salts with surfactants in cationic form and other agriculturally available cations. Herbicide composition. The herbicide composition of claim 11 wherein the glyphosate salt is an isopropylamine salt. 12. The surfactant according to claim 11, wherein the glyphosate salt is an ethoxylated cocoamine derivative containing 340-420 g per L of component (a), which is a monoisopropylamine salt and n + n 'has an average value of about 2. A herbicidal composition comprising an aqueous solution containing the solution, wherein the weight ratio of (a) and (b) is about 2: 1. The ethoxylated cocoamine derivative according to claim 11, wherein 100 to 130 g of isopropylamine salt of glyphosate as component (a) and n + n 'is approximately 2 per component as component (b). A herbicide composition characterized in that it contains 100-180 g and 260-320 g of ammonium sulfate per liter. (a) the dissolved glyphosate and (b) the surfactant are (i) an amine having the structure

Where R is a straight or branched chain alkyl or alkenyl having from about 8 to about 22 carbon atoms, A is an alkylene group, and n and n 'are integers having values of n + n' from 1 to about 12 ), (ii) a mixture of amines having other R groups having an average number of carbon atoms in the R group of about 8 to about 22, or (iii) n and n 'are each amines having a value of n + n' of 0 to 15, and A mixture of amines having different values n and n 'of the same integer but containing an average of 1+ about 12 sums of n + n' in the mixture and having R having one value or average in the mixture (ii), The weight ratio of (a) (expressed in an amount corresponding to glyphosate acid) to (b) is about 1: 1.75 to about 6: 1 and the concentration of (a) in the spray solution corresponds to glyphosate acid A spray solution with a usage rate of 0.125 Kg to 1.5 Kg per hectare at a rate of 100 to 400 L per hectare Spraying the weeds, characterized in that the manufacturing method. 16. The method of claim 15, wherein the spray solution comprises inorganic ammonium salt that can be used for agriculture. 17. The method of claim 16, wherein the weight ratio of glyphosate (expressed in an amount corresponding to glyphosate acid): ammonium salt in the solution is from about 1: 1 to about 1:10. 18. The method of any one of claims 16 and 17, wherein the ammonium salt is ammonium sulfate. 19. The method of claim 18, wherein the weight ratio of glyphosate (expressed in an amount corresponding to glyphosate acid) to ammonium sulfate is about 1: 2 to about 1: 7. The method according to claim 15, wherein the spray solution is a solution prepared by mixing the composition according to claim 13 with water and inorganic ammonium salt which can be used for agriculture. The method of claim 15, wherein the spray solution is a herbicidal method, characterized in that the solution prepared by mixing the composition and water according to claim 14. The glyphosate salt of claim 4, wherein the glyphosate is (i) a glyphosate salt, some of which is dissolved by the surfactant (b) and some of which are cationic forms of the surfactant and other cations available for agriculture. Or (ii) all are glyphosate acids dissolved by a surfactant. 23. The herbicidal composition of claim 22, wherein the amount of surfactant is at least 90% of a 1: 1 molar equivalent of glyphosate acid. 24. The herbicide composition according to any one of claims 22 to 23, wherein the salt of glyphosate is an isopropylamine salt. 5. The herbicidal composition of claim 4, wherein the glyphosate is present in all glyphosate salts with agriculturally available cations that are different from the surfactant in cationic form. 26. The herbicide composition of claim 25, wherein the glyphosate salt is an isopropylamine salt. 5. Herbicide composition according to claim 4, consisting essentially of an aqueous solution of components (a) and (b) and containing from 150 to 450 g per L of component (a). The herbicide composition according to claim 8, which is essentially composed of an aqueous solution of components (a) and (b) and contains from 150 to 450 g per L of component (a). 12. The herbicide composition according to claim 11, consisting essentially of an aqueous solution of components (a) and (b) and containing from 150 to 450 g per L of component (a). 25. The herbicide composition according to claim 24, consisting essentially of an aqueous solution of components (a) and (b) and containing from 150 to 450 g per L of component (a). 26. The surfactant according to claim 25, wherein the glyphosate salt is a monoisopropylamine salt (a) which is an ethoxylated cocoamine derivative containing 340-420 g per L and n + n 'has an average value of about 2. A herbicidal composition comprising an aqueous solution containing the solution, wherein the weight ratio of (a) and (b) is about 2: 1. 5. The herbicide composition according to claim 4, comprising an aqueous solution containing inorganic ammonium salt which can be used for agriculture as well as components (a) and (b). 9. The herbicide composition according to claim 8, which comprises an aqueous solution containing the inorganic ammonium salt which can be used for agriculture as well as the components (a) and (b). The herbicide composition according to claim 11, which comprises an aqueous solution containing the inorganic ammonia salt which can be used for agriculture as well as the components (a) and (b). 25. The herbicide composition according to claim 24, comprising an aqueous solution containing the inorganic ammonia salt which can be used for agriculture as well as the components (a) and (b). 36. The herbicidal composition of any one of claims 32-35, wherein component (a) contains 80-150 g per L and ammonium salt contains 100-500 g per L. 37. The herbicide composition of claim 36, wherein the ammonium salt is ammonium sulfate. 26. The ethoxylated cocoamine derivative according to claim 25, wherein (a) is 100-130 g of isopropylamine salt of glyphosate as component, and (b) n + n 'is an average value of about 2 per component. A herbicide composition characterized in that it contains 100-180 g and ammonium sulfate 260-320 g per liter. The method according to any one of items 1-3, 5-7, 9, 10, 12, 22, 23, 25, and 26, which is essentially composed of an aqueous solution of components (a) and (b) and (a) component per L Herbicide composition characterized in that it contains 150 to 450g. The inorganic ammonium salt according to any one of claims 1-3, 5-7, 9, 10, 12, 22, 23, 25, and 26, as well as the components (a) and (b). Herbicide composition characterized in that it comprises an aqueous solution. 41. The herbicide composition of claim 40 wherein component (a) contains 80-150 g per L and the ammonium salt contains 100-500 g per L. 41. The herbicidal composition of claim 40, wherein the ammonium salt is ammonium sulfate. 43. The herbicide composition of any one of claims 32-35, 41, wherein the ammonium salt is ammonium sulfate.

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