CN1033298C

CN1033298C - Improved glyphosate formulations

Info

Publication number: CN1033298C
Application number: CN88104879A
Authority: CN
Inventors: 詹姆斯·卡内基·福布斯; 米迈尔·莫里斯·昂里埃特; 塞缪尔·休伊特; 罗伯特·威廉·米切尔
Original assignee: Monsanto Europe NV SA
Current assignee: Bayer Agriculture BVBA
Priority date: 1987-09-04
Filing date: 1988-08-06
Publication date: 1996-11-20
Anticipated expiration: 2003-08-06
Also published as: GB8720819D0; KR920003974B1; CN1031789A; KR890004611A; HUT49272A; HU205823B

Abstract

Concentrates containing glyphosate herbicide which on dilution give spray solutions having higher herbicidal unit activity than prior art solutions comprise: (a) solubilised glyphosate equivalent to at least 40 grams per litre of glyphosate acid; and (b) a surfactant which is (i) an amine, (ii) a mixture of such amines having different groups R, or (iii) a mixture of such amines having different values of n and n', wherein, R, A, n, or n' are defined in the description; and wherein the weight ratio of (a) (expressed as glyphosate acid equivalent) to (b) is from about 1:1.75 to about 6:1.

Description

Improved glyphosate formulation

The present invention relates to improved glyphosate formulation.

Glyphosate (N-(phosphonomethyl) glycine) is the blade face effect weed killer herbicide of knowing.The glyphosate of free acid form solvability in water is low, therefore, contains the water soluble salt of glyphosate in the commodity preparation.For example, at Roundup ^In the weed killer herbicide, glyphosate exists with its single isopropyl amine salt form.

Reported several the achievements in research of surfactant in the document to the influence of the activity of weeding of glyphosate list isopropyl amine salt.For example, Turner and Loader be at Weed Resear-ch, and 1980,20 volumes were reported in the 139-146 page or leaf, and the HLB value is that 17 ethoxylated fatty amine generally can increase Roundup most effectively ^The activity of weeding of herbicide solution.In same publication, the author points out, uses the spray solution of sulfur acid ammonium, is different to the response of surfactant, uses lipophilic surfactant, and for example the HLB value is the fatty amine of 6 ethoxylation, has more obvious effect usually.

In BCPC Monogram No.28 Symposiumon Aplication and Biology in 1985, Tumer and Tabbush have narrated the result who makes several tests that the foliar spray agent done with glyphosate in " Studies With Alternative Glyphosate FormuLations ".In the summary of result of the test, they point out that if do not add surfactant and/or ammonium sulfate, the specific activity of glyphosate is less, and still, if added above-claimed cpd, then the phytotoxicity of glyphosate just is equivalent to Roundup ^The phytotoxicity of weed killer herbicide.Have a kind of suggestion to think, glyphosate solvability in a kind of tertiary amine that is made by animal fat solution of (every mole of amine contains 15 moles of ethylene oxide relatively) than in pure water is much bigger.

US-A-4612034 has narrated a kind of weed killer herbicide, wherein contains the mixture of a class rhodanate (comprising ammonium thiocyanate) of the appointment of glyphosate isopropyl amine salt and synergy amount.

That narrates in 1985 BCPC Monogram NO.28 makes in the test of glyphosate solubilising about the preparation glyphosate salt or with the fatty acid amine of ethoxylation, the glyphosate of every part relatively (weight), employed ethoxylated fatty acid amine surfactant surpass 5 parts (weight) at least.And at Weed Research, 1980,20 volumes, in the test solutions employed of narrating in the 139-146 page or leaf, contained surfactant is less than glyphosate (as Roundup ^Weed killer herbicide, itself just contain quite a large amount of surfactants), it is used by 20 liters/hectare by control dropping liquid technology.But for some test, solution wherein is with common technology, sprays by about 200 liters/hectare common farmland medication ratio, contains the surfactant that approximately doubles the glyphosate amount in this solution.

In causing research of the present invention, we adopt common spray pesticide ratio, and compare with disclosed surfactant/glyphosate ratio in the prior art of the solution that uses above-mentioned dispenser ratio spraying, surfactant/glyphosate ratio is lower in the solution that we use.We have found that, in our solution, use the ethoxylated fatty amine of oleophylic, still be considered to best, more hydrophilic ethoxylated fatty amine so far, in most of the cases can both obtain better result than using.No matter whether also contain ammonium sulfate in the solution, situation is not always the case.From the viewpoint of prior art, these results are wonderful, and prior art thinks, unless there is ammonium sulfate to exist, otherwise should not select lipophilic surfactant for use.

The invention provides a kind of glyphosate composition that commercial appeal is arranged, it is particularly suitable for going up acceptable inorganic ammonium salt with agricultural such as ammonium sulfate is used in combination, and sprays by common volume ratio.A feature of the present invention is, with respect to the glyphosate total amount, the amount of oxyalkylated amine surfactant can reduce to and be starkly lower than the corresponding ratio in the disclosed common spray solution in the prior art, and the activity of weeding of per unit glyphosate remains unchanged simultaneously.In other words, when the ratio of surfactant/glyphosate is similar to the corresponding ratio in the prior art, can strengthen units activity.

On the one hand, composition of the present invention is the concentration matter that comprises a kind of aqueous solution, contains

(a) lysed glyphosate is equivalent to whenever rise to few 40 gram glyphosates; With

(b) a kind of surfactant, it is the amine that (I) has following formula,

Wherein R represents to have the straight or branched alkyl or the alkenyl of 8～22 carbon atoms, A represents alkylidene, for example 1,2-ethylidene or 1, the 2-propylidene, n and n ' are integers, the value of n+n ' is about 1～12, (II) have the mixture of the above-mentioned amine of different radicals R, the average carbon atom number in the radicals R is about 8～22, or (III) has the mixture of the above-mentioned amine of different n and n ' value, n and n ' are integers, n+n ' can be about 0～15 in each amine, but in mixture n+n's ' and mean value be about 1～12, R be monodrome or as in the mixture (II), have mean value; And (a) (being expressed as the glyphosate equivalent) and weight ratio (b) are about 1: 1.75 to about 6: 1 in this concentration matter.

Another aspect of the present invention is a kind of spray liquid that is used for by common volume ratio spraying, the surfactant that it contains the glyphosate of dissolving and as above stipulates, glyphosate (being expressed as the glyphosate equivalent) is about 1: 1.75 to about 6: 1 with the weight ratio of surfactant.Herbicidal methods comprise with above-mentioned spray solution by 100～400 liters/hectare to weeds sprays medicine, should to make the rate of application of glyphosate equivalent be 0.125～1.5 kg/ha to the concentration of (a) in the spray solution.

In composition of the present invention, exist one or more agriculturals to go up acceptable cation in the solution, glyphosate can be dissolved.These cations comprise the ammonium cation of cationic form, alkali metal cation (as sodium and potassium) and the ammonium and the replacement of alkoxylated amines surfactant.The latter comprises by primary amine or secondary amine (as isopropylamine or dimethylamine) and the cation that obtained by diamines (as ethylenediamine).Other example of acceptable glyphosate salt has aminoguanidinium salts and triakylsulfonium salts on the agricultural, trimethyl sulfonium salt for example, and these salt are disclosed in respectively among patent EP-A-O088180 and the US-A-4405531.

Contain (a) and preparation (b) can make the method for glyphosate solubilising by independent use surfactant by low-molecular-weight surfactant according to low side (1: the 1.75) ratio of above-mentioned scope.But in most of embodiment, need be in solution except that containing the surfactant cation to the upper limit of dosage of surfactant, also to contain acceptable cation on other the agricultural.In these embodiments, solubilising the source of glyphosate be the use by oneself glyphosate of surface active agent solubilization and the salt that part is become with another kind of agriculture acceptable cation from glyphosate of (I) part, perhaps (II) is all from acceptable another kind of cation became on glyphosate and this agricultural salt.

As discussed later, except that compound (a) with (b), concentration matter of the present invention also can contain acceptable inorganic ammonium salt on a considerable amount of agriculturals.The concentration matter that does not contain a large amount of this salt, different water-soluble according to glyphosate salt can contain 450 grams per liters (as 150～450 grams per liters) or even more glyphosate equivalents at the most under the room temperature.For example, when glyphosate salt was single isopropyl amine salt, the solution that contains 250～400 grams per liter glyphosate equivalents was preparation easily.The glyphosate mono-ammonium demonstrates similar solubility characteristics, but some alkali metal salt, sylvite for example, and solvability is just poor slightly.In this case, the Cmax with glyphosate equivalent glyphosate that represent, getable dissolving approximately is the 250-300 grams per liter.

Say generally, consider that contain the concentration matter of the present invention of minimum water gaging, it is reasonable promptly being in saturated solution basically from economic aspect.According to the weather conditions that solution may will bear in during this period of time before making the back and using, the solution of preparation should be for example-5 ℃, 0 ℃ or+be the solution of saturation state under 10 ℃.Usually should leave sufficient leeway, though so that solution expects can not stand for example temperature environment below 10 ℃, but still can for example keep stable (not being settled out solid) 5 ℃ the time.In addition, concentration matter of the present invention can contain common freezing point depressant, for example ethylene glycol, polyethylene glycol or glycerine.

In composition of the present invention, glyphosate total amount (being expressed as the glyphosate equivalent) is about 1: 1.75 to about 6: 1 to the weight ratio of surfactant.The maximum level of surfactant is mainly determined by the consideration of economic aspect.The higher surface activity agent content can increase the unit weeding ratio of glyphosate, but surpasses certain level, has just no longer saved cost.When concentration matter being considered as also contain agricultural and going up the predecessor of spray solution of acceptable inorganic ammonium salt, used surfactant does not have any benefit during more than the glyphosate equivalent of 1.5 parts/part (weight).At the other end of this scope, glyphosate preferably: surfactant maximum weight ratio is 4: 1.Better ratio range is 1: 1 to 3: 1, and for example 1.5: 1 to 2.5: 1, certainly, according to used concrete surfactant, this restriction can change.

The amine surfactant of the commodity shown in the following formula often is mixture rather than individualized compound.The alkoxy derivative that comprises " cocoa amine " (" Cocoamine ") in the middle of them, wherein the R group is equivalent to from myristic acid, lauric acid, palmitic acid and stearic alkyl.Average carbon atom number among the R of cocoa amine is 12～14.Other example is the alkoxy derivative of " oleyl amine " (" Oleylamine "), stearylamine (18 carbon atoms) and " tallow amine " (" tallow amine "), the main carbochain of R is equivalent to oleic acid carbochain (18 carbon atoms) in " oleyl amine ", also has a spot of short or long carbochain.In tallow amine, R mainly is the mixture of cetyl and octadecyl.Commercial surfactant also is the mixture of the molecule that has nothing in common with each other of n+n ' value usually, and the surfactant that the mean value of n+n ' is lower may contain the amine of some non-alkoxylate or monoalkoxyization.Alkoxy derivative is an ethoxylated derivative preferably.

In general, the surfactant of lower molecular weight is better than the surfactant of higher molecular weight, and this is because when they be equal in weight, the surfactant that molecular weight is lower has higher molecular concentration.Best surfactant is that wherein A represents 1,2-ethylidene person and wherein carbon number or the carbon atom mean in the R group in the R group be about 10～20.As for value or the mean value of n+n ', the scope of this value is about 1.5～12 in surfactant preferably, more specifically says so about 2～10.The instantiation of surfactant is the ethoxylated derivative of cocoa amine, tallow amine and oleyl amine preferably, and the mean value of n+n ' is about 2, about 5 or about 8 in above-mentioned various situations.

In order to prepare concentration matter of the present invention (wherein the cationic form of surfactant has determined the solvability of glyphosate at least in part), under many circumstances, can room temperature or a little more than under the room temperature in aqueous medium, glyphosate and oxyalkylated amine surfactant are mixed simply, promptly make the solution of the glyphosate of solubilising.Can obtain limpid solution within a few minutes.Make normally about 1: 1 molar equivalent of amount of the needed surfactant of glyphosate solubilising.But more less slightly, 90% molar equivalent for example in some cases may be just enough, and in other cases, may preferably will make surfactant more excessive, and for example molar excess nearly 30%.The various considerations of the maximum consumption of decision table surface-active agent have been discussed above.When part glyphosate in the concentration matter that needs provide when to be glyphosate with another kind of agricultural go up the form of the salt that acceptable cation become, can be with solubilising the solution of glyphosate mix with the solution of glyphosate salt again, the ratio that adopts during mixing should be able to guarantee each required in final concentration matter components contents.If the quantity that exists itself in concentration matter of the present invention just is enough to make the cation of glyphosate dissolving, rather than cationic surface active agent, when then preparing this concentration matter, only need at room temperature mix each component simply.Surfactant is stickum normally, slowly dissolves when the aqueous solution with glyphosate salt stirs.In addition, if desired, can mix acceptable ammonium salt on a kind of agricultural in this operational phase.In general, in the whole process solutions employed be denseer or or even saturated substantially so that make the water yield in the concentration matter reduce to minimum.But if desired, after mixing, also can or add entry, water content is carried out some adjustment by evaporation.

Knownly can increase the herbicidal effect that the water-soluble or water of glyphosate or other adds the dissolubility weed killer herbicide effectively, and the example of acceptable inorganic ammonium salt comprises ammonium sulfate, ammonium nitrate, ammonium phosphate, Amcide Ammate and ammonium thiocyanate on agricultural.Wherein ammonium sulfate generally is preferably.

In containing the concentration matter of ammonium salt, its content depends on when having other component to exist its solvability.But, reach given content in order to make ammonium salt, can adjust other components contents.In general, the component of every part relatively (weight) (a), the weight of ammonium salt are at least 0.5 part, for example are 1～10 part.These concentration matters generally contain the component (a) of at least 70 grams per liters (for example 80～150 grams per liters) and the ammonium salt of 100～500 grams per liters, and component (a) (being expressed as the glyphosate equivalent) was generally about 1: 1 to 1: 1.75 with the weight ratio of component (b).

A kind of example of concrete composition is as follows:

Glyphosate 74 grams per liters

Glyphosate list isopropyl amine salt

(being expressed as acid equivalent) 49 grams per liters,

C2 ^*Surfactant 120 grams per liters

Ammonium sulfate 280 grams per liters

^*The ethoxylated derivative that on average contains the cocoa amine of 2 ethyoxyls of having an appointment.

Better the concentration matter of the ammonium salt-containing of type is such composition: wherein contain the component (a) of 80～130 grams per liters, exist with the form of glyphosate and single isopropylamine institute salify; Component (b) with 100～180 grams per liters; And the ammonium sulfate of 260～320 grams per liters, component (b) is that n+n ' mean value is about 2 ethoxylation cocoa amine derivative.

The present invention includes a kind of weeding spray solution, wherein contain by common volume ratio spraying usefulness:

(a) solubilising the glyphosate component, the existence form of this glyphosate is that (I) part is glyphosate, make its solubilising by the surfactant that limits above, part goes up the salt that acceptable cation is become for glyphosate with another kind of agricultural, (II) all be glyphosate, make its solubilising by above-mentioned surfactant, or (III) all be the salt that become with acceptable cation (rather than cationic form of surfactant) on a kind of agricultural of glyphosate and

(b) surfactant as limiting above (a) (is expressed as the glyphosate equivalent) and weight ratio (b) is about 1: 1.75 to about 6: 1.

The concentration of glyphosate is generally in spray solution: when spraying by 100～400 liters of/hectare consumptions, the rate of application of glyphosate equivalent is 0.125～15 kg/ha.

Preferably also contain acceptable inorganic ammonium salt on a kind of water miscible, agricultural in this spray solution.According to weeds situation to be processed, the spraying apparatus that will use, weather conditions etc., can change the consumption of inorganic ammonium salt.But in general, the sprinkling amount of solution is 100～600 liters/hectare, for example 100～400 liters/hectare, and also dosage is at least 0.125 kg/ha glyphosate equivalent, so the weight concentration of the ammonium salt that contains in the solution equals the glyphosate equivalent at least.For example, the weight ratio scope of glyphosate/ammonium salt can be 1: 1 to 1: 10 in the solution.At the low side of above-mentioned scope, along with the increase of this ratio, the usefulness that ammonium salt improves the Gyphosate herbicice activity increases sharply, but surpasses after the mid point, and this increase is slack-off.When using ammonium sulfate, best ratio usually is about 1: 2 to about 1: 7.In weight range, the solution of use contains 5～100 grams per liters, the especially inorganic ammonium salt of 5～30 grams per liters to dispenser dosage at 0.25～1.5 kg/ha glyphosate, and this is effectively.

The better method for preparing above-mentioned weeding spray solution be with concentration matter of the present invention and water and preferably and ammonium salt be mixed together, but if desired, can in the spray liquid bucket, will join each component that solution uses and mix with volume required water.

Concentration matter of the present invention and solution also can contain annexing ingredient arbitrarily.Point out that as top these components comprise antifreezing agent.Other example has dyestuff, thickener, defoamer, and for example siloxanes is the defoamer of matrix, and second kind of surfactant, and non-ionic surface active agent for example is as APEO or ester.Concentration matter of the present invention and solution also can mix with other water soluble herbicide, for example (but being not limited to these), 2, the salt of 4-dichlorphenoxyacetic acid or the salt of methoxone, perhaps mix with water soluble herbicide in small, broken bits, for example (but being not limited to these), the ureas of triazines or replacement.

The present invention is illustrated with following example.

Table 1～3 show solution more of the present invention, and wherein the solubilising of glyphosate depends on the existence of cationic surface active agent at least in part.The preparation method of these solution is, earlier in room temperature or be not higher than under 60 ℃ the temperature, Yu Shuizhong stirs glyphosate (crystal that contains the water of 9% (weight)) and ethoxylated amine surfactant (relative every mole of glyphosate, this dosage of surfactant is about 1.05 molar equivalents), make the glyphosate solubilising.When needing, again gained solution is mixed with single salt (ammonium salt, isopropyl amine salt or sylvite) of glyphosate, if desired, also can add water and mix the solution that obtains having the concentration shown in the following table and glyphosate/surfactant ratio.

In showing the table of each weight percentages of components, surfactant indicates with the first female and ethyoxyl mean of the title of amine.So C2 shows by cocoa amine surfactant that obtain and that on average contain 2 ethyoxyls; O5 shows by oleyl amine surfactant that obtain and that on average contain 5 ethyoxyls; S8 shows by stearylamine surfactant that obtain and that on average contain 8 ethyoxyls; T10 shows the surfactant that also on average contains 10 ethyoxyls that is obtained by tallow amine, or the like.Glyphosate salt is marked with AM (ammonium salt), IP (isopropyl ammonium salt) or K (sylvite).

Solution in the table 1 contains the surfactant of about 300 grams per liter glyphosate equivalents and 150 grams per liters.The latter is equivalent to contain in the solution surfactant of 13.64% (weight).Glyphosate salt is single isopropyl amine salt.

Table 1 solution number 91% glyphosate surfactant glyphosate salt

(％) (％)1 8.92 C2 41.692 6.09 C5 47.303 4.62 C8 50.204 7.22 O2 45.065 5.25 O5 48.976 4.12 O8 51.207 4.15 S8 51.148 5.30 T5 48.869 4.15 T8 51.1410 3.63 T10 52.1711 2.76 T15 53.90

Table 2 has provided the percentage by weight of component in a series of solution of single isopropyl amine salt of containing glyphosate, glyphosate and a kind of ethoxylated surfactant, and solution wherein has the weight ratio of different glyphosate equivalent (a.e.)/surfactants.

Table 2

Grass sweet solution number _91%Glyphosate phosphonium salt surfactant glyphosate glyphosate

(%) (%) (%) code equivalent/table equivalent

2: 1 30,018 4.39 62.55 8.18 T2 of 1: 1 15,117 7.32 44.86 13.64 T2 of 4: 1 38,316 7.67 15.91 14.29 T2 of 1: 1 15,415 2.77 65.75 8.18 C8 of 4: 1 36,014 4.85 21.51 14.29 C8 of 1: 1 14,513 5.10 57.74 7.80 C2 of surface-active agent grams per liter 12 8.92 12.02 13.64 C2 4: 1 379

Table 3 has provided the percentage by weight of each component in the solution (wherein glyphosate salt is ammonium salt (AM) or sylvite (K)).The weight ratio of glyphosate equivalent/surfactant is 2: 1 in all solution.

Table 3 solution number _91%Glyphosate glyphosate salt surfactant

(%) (%) code (%) code 19 8.92 67.04 K 13.64 C220 8.92 60.23 AM 13.64 C221 3.73 77.25 K 12.73 C1022 3.98 74.36 AM 13.64 C1023 7.32 72.13 K 13.64 T224 7.32 64.81 AM 13.64 T225 3.39 78.30 K 12.73 T1026 3.63 75.37 AM 13.64 T10

Solution 21 and 25 contains the glyphosate equivalent of about 280 grams per liters and the surfactant of about 140 grams per liters respectively.In other solution, corresponding digital is 300 grams per liters and 150 grams per liters.

Table 4 is expressed some compositions of the present invention, and its preparation method is, at room temperature the aqueous solution of the glyphosate list isopropyl amine salt of 62% (weight) surfactant with aequum is stirred, and then, if desired, stirs with the ammonium sulfate saturated solution.

(acid is when the ammonium sulfate weight ratio for table 4 solution surfactant glyphosate

Code-grams per liter amount) the glyphosate equivalent/

Grams per liter grams per liter surfactant 27 C2-180 360-2: 128 C2-200 400-2: 129 C2-120,120 280 1: 130 C2-140,90 300 1: 1.5631 C5-202 404-2: 132 C10-204 407-2: 133 O8-203 405-2: 134 S10-203 406-2: 135 T5-201 402-2: 136 C2-220 120-1: 1.7537 C2-150 150-1: 138 C2-100 399-4: 139 C2-59 356-6: 140 C2-100,100 320 1: 141 C2-120,100 300 1: 1.242 C2-180,110 260 1: 1.6443 C2-120,120 260 1: 144 C2-100 130 260 1.3: 1

In the accompanying drawings, Fig. 1 shows the result who in the greenhouse wheat is tested, Fig. 2,3,4,10 and 11 shows the result who in the greenhouse common rush (Alopecurus myosur-oides) is tested, and Fig. 5 and 6 shows the result who the wheat stubble is tested in the field.As spontaneous wheat, itself be exactly a kind of evil grass.And it is general also within the reaction range of injurious weed to the reaction of glyphosate.Fig. 7 and 8 is illustrated in the result who carries out the field experiment gained in the herbage of the sowing that contains English ryegrass (Lolium perenne) and butch clover (Trifoliumrepens), and Fig. 9 represents the perennial weed lalang grass rhizome in the paddy stubble (Elymus repens) the resulting result that does experiment.

With the herbicidal effect of following method evaluation in little greenhouse.With the plant seed kind in 13 centimetres the basin that contains natural sandy loam.Realize irrigating by the below self water feeding, as requested inorganic nutrient substance is added in the irrigation water.Basin is placed in the little greenhouse of Conviron, and illumination period is 14 hours, and illumination is 600 little Einstein/rice ²Second, temperature range is 15 ℃ (daytimes), 9 ℃ (night).About two weeks (2～4 weeks after planting) before the spray medicine, plant is carried out manual thinning, plant is evenly distributed.

At the latest when handling the last week, plant is moved on in the relative moisture and temperature controlled big greenhouse with precision; The relative moisture that is adopted is 50% (daytime) and 65% or 75% (night).In the experimental stage afterwards, plant is placed in this greenhouse always.Before the spray medicine, select those consistent each other basins as far as possible, the person of not being true to type gives it up.With the laboratory of Mardrive precision atomizers spray soup, be calibrated to that being equivalent to once sprays reaches 200 liters of/hectare soups.All each basins (every kind each handle 3-5 basin) that are used for replica test all by sprayer once by spraying.

After the processing, undressed contrast basin is placed between the treated basin randomly.By comparing with untreated contrast basin, estimate " % phytotoxicity " with optional scale 0～100%, wherein 0 expression does not observe effect, and 100% expression is all die.Once estimate for any, all basins are all by same personal assessment and provide assessment result, and are to carry out " blindly formula " assessment under the situation of not knowing processing mode in advance.Pane among Fig. 2,3,4,10 and 11 is represented the mean value to the observed result of 3-5 repeated test.

The test that obtains result shown in Fig. 5 and 6 is to carry out in the big field of wheat stubble that is covered 75% by weeds.About 35% weeds are spontaneous wheats, and remaining is annual broad leaved plant mixture, 35% chickweed (Stellaria media), 10% big field viola (Viola arvensis) and 10% colored glaze chickweed (Anagallisarvensis).Air themperature is 23 ℃, and soil temperature is 15 ℃, relative moisture 48%, and wind speed is zero.Pilot region is the complete square of appointment at random, gets four and does repeated test, and the monolithic size is 18 meters ²The observed result of record is the dead leaf percentage in 3 whens week after processing.

The test that obtains result shown in Fig. 7 and 8 is to contain simple English ryegrass thick grass and another part contains in the sowing herbage of various grass and butch clover mixture and carries out in a part.Only will list the result of the test of English ryegrass and butch clover.Air themperature is 18 ℃ in the spray process, and the light moderate wind that arrives is arranged, and no rain on the two behind the spray medicine: pilot region is the complete square of appointment at random, and every kind of processing mode is done repeated test with three, and untreated fritter selects 12 places to do repeated test, and the fritter area is 16 meters ²The English ryegrass turf adds 16 meters ²Mix grass and butch clover turf.The observed result of record is the dead leaf percentage when handling back 47 days.

The test that obtains result of the test shown in Figure 9 is to carry out in the big field of paddy stubble that the lalang grass rhizome moderate that quite is evenly distributed in the whole test zone spreads.Air themperature is 15 ℃ during the spray medicine, and light to moderate wind is arranged.No rain on the 5th behind the spray medicine.Pilot region is the complete square of appointment at random, does a kind of repeated test for per 3, and the fritter area is 30 meters ²The observed result that is write down is at the dead leaf percentage of processing in the time of back 25 days.

During spray solution,, make the hydrojet volume be equivalent to 200 liters/hectare in preparation with concentration matter dilute with water described in the above-mentioned table, and the dispenser rate with its numerical value of a kilogram glyphosate equivalent/when hectare is represented shown in Fig. 1～11.

In test shown in Figure 1 in the spray solution of sulfur acid ammonium, the glyphosate equivalent of every part relatively (weight) contains the ammonium sulfate of 6 parts (weight).Shown in Fig. 2,3 and 4 in the test and contain the ammonium sulfate of 10 grams per liters in the field experiment shown in Fig. 5 and 6 in the spray solution of used sulfur acid ammonium.Shown in Fig. 7,8 and 9 in the field experiment in the spray solution of used sulfur acid ammonium, the glyphosate equivalent of every part relatively (weight) contains the ammonium sulfate of 3.6 parts (weight).

Contain glyphosate (all being single isopropyl amine salt) and on average contain the tallow amine based surfactants of the ethoxylation of 15 ethoxy units in the spray solution of contrast usefulness.In check experiment 1, surfactant is 2.94: 1 to the weight ratio of glyphosate equivalent; In check experiment 2, aforementioned proportion is 2: 1, and in check experiment 3, aforementioned proportion is 1: 2.This class ratio in these ratios and the existing glyphosate commercial formulation is close.

In these figure, spray solution is called " preparation ", and according to the used number of concentration matter in above-mentioned table of these preparations of preparation said preparation is numbered.

Fig. 1 shows, although in check experiment, relative per unit glyphosate equivalent, the surfactant that exists is almost 6 times of surface-active contents in the preparation of the present invention, but the test of the various dispenser rates that wheat is carried out all proves, glyphosate equivalent/surfactant weight ratio is 2: 1 and contains the activity of weeding of No. 1 preparation of the present invention of ammonium sulfate the activity with the preparation of contrast 1 is the same high at least.When with contrast 3 (it contains the glyphosate/surfactant of same ratio with No. 1 preparation of the present invention) when comparing, (preparation that is respectively the contrast 3 that 0.36,0.72 and 1.44 kilogram of acid equivalent/hectare dosage is used does not have equal activity with the dosage of 0.18,0.36 and 0.72 kilogram of acid equivalent/hectare the time and by being twice in above-mentioned dosage for the sulfur acid ammonium No. 1 preparation.When in No. 1 preparation, adding ammonium sulfate, if use by 0.09,0.18 and 0.36 kilogram of acid equivalent/hectare dosage, said preparation and almost have same isoreactivity then by the preparation that is four times in the contrast 3 that above-mentioned corresponding dosage uses.

Fig. 2 shows the result who obtains when as the spray solution of surfactant common rush being handled back 14 days with C2.Activity reduces along with the minimizing of surface-active contents, but concerning the solution of sulfur acid ammonium, the speed of reduction is obviously lower.The preparation 1 of sulfur acid ammonium (the glyphosate equivalent: the ratio of surfactant is 2: 1), although its surface-active contents is low, but when low dosage uses, still have activity preferably, and when maximum dose level uses, have same isoreactivity with the preparation that contrasts 2 basically.When the preparation 12 of sulfur acid ammonium (the glyphosate equivalent: the ratio of surfactant is 1: 1) used at various dosage levels, its activity all was better than contrasting 2 preparation.When the dosage by 0.5 kilogram of glyphosate equivalent/hectare uses the preparation 13 of sulfur acid ammonium, although surfactant (with respect to glyphosate) content is very low, but in fact preparation 13 has equal phytotoxicity with the preparation of contrast 2, and the preparation of comparing according to 3 has stronger phytotoxicity.

Fig. 3 shows the result who obtains when as the spray solution of surfactant common rush being handled back 14 days with C8.Compare with the solution that contains the C2 surfactant, active situation about reducing is more obvious along with the minimizing of surface-active contents ratio for this solution.But contain ammonium sulfate and wherein the ratio of glyphosate equivalent/surfactant be 1: 1 preparation 14, under all using dosages, have essentially identical activity with the preparation of the contrast 2 of the surfactant that contains two times of content.When minimum rate of application, preparation 3 has obviously higher activity than the preparation of the contrast 3 with similar face activating agent/glyphosate ratio.

Fig. 4 shows with containing glyphosate list isopropyl amine salt (1 and 10), the result that the preparation of ammonium glyphosate (20 and 26) and glyphosate potassium (19 and 25) obtains when handling back 14 days.The weight ratio of the glyphosate equivalent/surfactant of all preparations is 2: 1, and is identical with contrast 3.Very clear, these preparations are compared generally and are all had higher activity of weeding with contrast 3, and in some cases, and the preparation of sulfur acid ammonium has high phytotoxicity equally with the preparation of the contrast 2 of the surfactant that contains four times of amounts at least.

Fig. 5 shows, when spontaneous wheat being tested by 0.27 kilogram of acid equivalent/hectare rate of application, although surfactant in No. 1 preparation/glyphosate equivalent ratio is much lower, by adding ammonium sulfate therein, it is basic identical just can to make its usefulness be increased to and contrast the usefulness of 1 preparation.When rate of application was 0.54 kilogram of acid equivalent/hectare, adding ammonium sulfate did not in fact have any influence to the usefulness of No. 1 preparation.Whether add ammonium sulfate, its usefulness is all basic identical with control formulation usefulness.

Fig. 6 shows the herbicidal effect of glyphosate formulation to annual broad leaved plant.Although surface-active contents is lower in the preparation of the present invention, when 0.54 kilogram of acid equivalent/hectare rate of application, it still is equivalent to contrast 1 preparation.

Fig. 7 and 8 shows No. 1 preparation activity of weeding to English ryegrass and butch clover.Although the surface-active contents of preparation of the present invention is much lower, but it still is parity with or superiority over the preparation of contrast 1 to the weeding of these two kinds of grass, and its this activity also is parity with or superiority over the activity of contrast 3 preparations (have identical surface-active contents, but use with two times dosage).Adding ammonium sulfate slightly increases the activity of No. 1 preparation again.

Fig. 9 shows the herbicidal effect of preparation of the present invention to lalang grass rhizome.Be almost in the preparation 16 times with respect to the surface-active contents of per unit glyphosate equivalent in contrast 1 the preparation, and several 12 times of being almost in the preparation 13, but be added with and preparation that No. 13 two kinds of preparations are all compared according to 1 has higher activity No. 1 of ammonium sulfate.When these two kinds of preparations of the present invention are used by the dosage of 0.18 and 0.36 kilogram of acid equivalent/hectare, has equal effect with the preparation of the contrast 3 of using to this dosage (promptly being respectively 0.72 and 1.44 kilogram of acid equivalent/hectare) by 4 times.

Figure 10 shows the result who obtains when handling back 22 days with spray solution, and this solution is to contain various surfactants and all be that the concentration matter of the glyphosate of isopropylamine salt form makes by dilution.In all solution, the ratio of glyphosate and surfactant is 2: 1.When minimum rate of application, all solution of the present invention are all compared according to having higher activity with preparation.When rate of application was 0.25 kilogram of glyphosate equivalent/hectare, except that containing C10 or O8 as the surfactant person, all solution were all compared according to having higher activity with preparation.When using the solution of sulfur acid ammonium (unlisted), by 0.125 kilogram of glyphosate equivalent/when hectare is used, all solution are all compared according to having higher activity with preparation, by 0.25 kilogram of glyphosate equivalent/when hectare is used, except that containing C10 as the surfactant person, all solution are all compared according to having higher activity with preparation.

Figure 11 shows the result that a series of spray solutions that reduce gradually as surfactant and surface-active contents with C2 obtain when handling back 22 days.Glyphosate in these solution is all from its single isopropyl amine salt.Activity of weeding reduces and reduces along with surface-active contents, but when minimum rate of application, the activity that contains the solution of the present invention (formulated by No. 38 concentration matters) of glyphosate and surfactant (its ratio is 4: 1) surpasses the twice of contrast with preparation (surfactant that contains qdx) activity.When higher rate of application, its activity is used the active identical of preparation with contrast at least.Observe similar result (unlisted) with the spray solution that contains 1% ammonium sulfite.Under various rate of application situations, the ratio that contains glyphosate and surfactant is that 4: 1 solution all has higher activity than the contrast that contains the qdx surfactant with preparation.

Claims

1. a composition is characterized in that comprising a kind of following (a) and aqueous solution (b) of containing, and wherein (a) (being expressed as the glyphosate equivalent) and weight ratio (b) are 1: 1.75 to 6: 1.

(a) solubilising glyphosate, in an amount equivalent to every liter of 40-450 gram glyphosate,

(b) a kind of surfactant, promptly (I) has the amine of following formula

Wherein R represents to have the straight or branched alkyl or the alkenyl of 8 to 22 carbon atoms, A is 1,2-ethylidene or 1, the 2-propylidene, n and n ' are integer, it is 1 to 12 that n+n ' is worth, (II) has the mixture of the above-mentioned amine of different R groups, the mean value of the carbon number in the R group is 8 to 22, or (III) having the mixture of the above-mentioned amine of different n and n ' value, n and n ' they are integers, and the value of n+n ' is 0 to 15 in each amine, but the mean value of n+n ' sum is 1 to 12 in the mixture, R be monodrome or as in the mixture (II), have mean value.

2. according to the composition of claim 1, it is characterized in that the component (a) and the weight ratio of surfactant are 1: 1 to 4: 1.

3. according to the composition of claim 2, it is characterized in that the component (a) and the weight ratio of surfactant are 1.5: 1 to 3: 1.

4. according to the composition of claim 1, it is characterized in that A represents one 1 in the chemical formula of surfactant, 2-ethylidene or 1, the 2-propylidene, and surfactant is that a kind of its n+n ' mean value is 1.5 to 12 mixture.

5. according to the composition of claim 4, it is characterized in that A represents 1, the 2-ethylidene.

6. according to the composition of claim 5, it is characterized in that among the R that carbon number or its mean are 8 to 18, and the mean value of n+n ' is 2 to 10.

7. according to the composition of claim 6, it is characterized in that surfactant is the ethoxylated derivative of cocoa amine (Cocoamine), tallow amine or oleyl amine, wherein the mean value of n+n ' is about 2, about 5 or about 8.

8. according to composition arbitrary in the claim 1 to 7, the existence form that it is characterized in that glyphosate is that (I) part is the glyphosate of solubilising by adding surfactant (b), part is the salt that acceptable cation generated on glyphosate and this surfactant cation agricultural in addition, and perhaps (II) all is the glyphosate of solubilising by adding surfactant.

9. composition according to Claim 8, the amount that it is characterized in that surfactant for by 1: 1 molar equivalent glyphosate 90% to excessive 30% molar equivalent.

10. according to the composition of claim 9, the salt that it is characterized in that glyphosate is its isopropyl amine salt.

11. according to each composition in the claim 1 to 7, it is characterized in that glyphosate all with its with the cationic form of surfactant beyond agricultural on the form of the salt that acceptable cation was become exist.

12. according to the composition of claim 11, the salt that it is characterized in that glyphosate is its isopropyl amine salt.

13. composition according to claim 11, it is characterized in that forming by the following aqueous solution basically, contain 340 to 420 gram components (a) in every premium on currency solution, and the glyphosate salt (a) is its single isopropyl amine salt, surfactant in the solution is the ethoxylated derivative of cocoa amine, its n+n ' mean value is about 2, and weight ratio (a) and (b) is about 2: 1.

14. according to each composition in the claim 1 to 7, it is characterized in that except that comprise component (a) and (b), also comprise and contain the aqueous solution that agricultural goes up acceptable inorganic ammonium salt.

15., contain 80 to 150 gram components (a) and 100 to 500 in it is characterized in that every liter and restrain ammonium salts according to the composition of claim 14.

16., it is characterized in that described ammonium salt is an ammonium sulfate according to the composition of claim 15.

17. composition according to claim 11, contain 100 to 130 gram components (a) in it is characterized in that every liter, 100 to 180 gram components (b), with 260 the gram to 320 the gram ammonium sulfate, component (a) is the isopropyl amine salt of glyphosate, is about the cocoa amine derivative of 2 ethoxylation and component (b) is n+n ' mean value.

18. a herbicidal methods, it is characterized in that comprising ratio by 100 to 400 liters of solution of per hectare with spray solution to the spraying of evil grass, contain (a) solubilising in the above-mentioned solution glyphosate and

(b) surfactant, i.e. amine shown in (I) following formula

Wherein R represents to have the straight or branched alkyl or the alkenyl of 8 to 22 carbon atoms, and A is 1,2-ethylidene or 1,2-propylidene, n and n ' are integer, and n+n ' to be worth be 1 to 12; (II) has the mixture of the above-mentioned amine of different R groups, carbon atom mean is 8 to 22 in the R group, or (III) has a mixture of the above-mentioned amine of different n and n ' value, n and n ' are integers, and n+n ' can be 0 to 15 in each amine, but the mean value of n+n ' sum is 1 to 12 in mixture, and R has single value or has mean value as in the mixture (II);

(a) (being expressed as the glyphosate equivalent) and weight ratio (b) are 1: 1.75 to 6: 1 in the spray solution, and the concentration of (a) should be able to make that the rate of application of glyphosate equivalent is 0.125 kg/ha to 1.5 kg/ha in the spray solution.

19., it is characterized in that also containing in the spray solution agricultural and go up acceptable inorganic ammonium salt according to the method for claim 18.

20., it is characterized in that the glyphosate in the solution (being expressed as the glyphosate equivalent) and the weight ratio of ammonium salt are 1: 1 to 1: 10 according to the method for claim 19.

21., it is characterized in that above-mentioned ammonium salt is an ammonium sulfate according to each method in claim 19 and 20.

22., it is characterized in that the glyphosate (being expressed as the glyphosate equivalent) and the weight ratio of ammonium sulfate are 1: 2 to 1: 7 according to the method for claim 21.

23., it is characterized in that used spray solution is by mutually mixed with acceptable inorganic ammonium salt on the described composition of claim 13 and water and a kind of agricultural according to the method for claim 18.

24., it is characterized in that used spray solution is by with mixed with water the making of the described composition of claim 17 according to the method for claim 18.