DD296404A5 - DECAYER FOR LIQUID NETWORKS AND FOAM ARMS FLUID PLANT PROTECTION AGENTS - Google Patents

Abstract

The invention relates to defoamed aqueous surfactant solutions and low-foam concentrated liquid pesticide preparations which contain surfactants containing sulfates or sulfonate groups as wetting agents and surfactants from the group of * and / or alkylphosphonic acids and / or their salts as defoamer.

Description

Defoamer for liquid wetting agents and low-foaming liquid pesticides

The invention relates to the use of certain perfluoroalkylphosphinic acids and -phosphonic acids as defoamers for wetting agents which can be used in spray mixtures and concentrated preparations of plant protection products.

In particular, the invention relates to defoamers for liquid herbicidal preparations having high contents of wetting agents containing sulfate and sulfonate groups.

It is known that the effect of crop protection agents, in particular of leaf herbicides, can be increased if surfactants, in particular wetting agents, are added to the aqueous sprays of the plant protection products before they are used.

Wetting agents lower the surface tension of the spray mixture. As a result, a uniform wetting of the leaf surface and associated often improved drug absorption is guaranteed.

Because of this property, a large number of products have been established on the market for crop protection agents, which are offered as additives to the spray mixture, and which held predominantly the nonionic alkylaryl polyglycol ethers as wetting agents

(eg "Citowett," Triton X45, "Ortho X-47," Agral 90, ®Dash).

It has also been known or proposed to enhance the action of herbicides by adding anionic sulfate and sulfonate surfactants; see. DE-A 3035554, JP-A 86/289004 and German Patent Application P 3809159.3. As a result, the application of the herbicides can be carried out in a particularly economical manner.

However, spray liquors and liquid preparations which according to DE-A 3035554, JP-A 86/289004 and P 3809159.3 contain very large proportions of activity-enhancing anionic surfactants (wetting agents) often still have technical deficiencies.

If, for example, these wetting agents in the form of their aqueous solutions are added to the aqueous sprays of pesticides, then these spray liquors usually foam so much that the irregular spray coatings on the plants and residues of pesticides are the result.

Corresponding disadvantages Effects can occur when using the concentrated pesticide preparations. Because the wetting agent-containing concentrated formulations are usually not used directly as such, but depending on the active ingredient and wetting agent concentrations in the preparations in amounts of 2-10 and more liters per hectare for better dosage and distribution only after dilution and stirring in 50-1000 liters Water / ha applied. The spray liquors contained after dilution usually foaming so strong that they foam from the spray tank and irregularities in the dosage during spraying result in the result not only losses to the active ingredient, but above all a constant good effect can no longer be guaranteed can.

The use of an anti-foaming agent as an additive, which is added separately to the spray liquors, can often remedy the situation.

However, the use of a separately added additive requires, in addition to the crop protection agent and the wetting agent, the use of another agent and is not readily applied in practice because of the required additional dosage and separate storage.

It is therefore an object to find antifoams for the anionic sulfate and sulfonate containing wetting agents, which are well tolerated by the wetting agents, d. H. are also stable on storage, and allow a problem-free application of wetting agents in aqueous systems, especially in spray mixtures of pesticides.

It is a further object to find defoamers which are clearly soluble in concentrated liquid preparations of plant protection products. Defoamers resulting in solid heels, oily deposits or marked turbidity must be excluded, as they give the impression that the preparation has already undergone decomposition. The defoamer to be found must also remain stable during storage of the preparations for 2-4 years and remain effective. The defoamer should additionally be effective in that amounts of up to 5% by weight, preferably 0.1-1% by weight, are sufficient in the formulation. Larger amounts of defoamer can often be incorporated only in solid formulations. In water and surfactant-containing liquid preparations, phase separations often result in surfactant-poor, active substance-rich and surfactant-rich, low-active-substance layers.

There is a variety of defoamers known about the z. From H.-F. Fink and G. Körner in "Ullmann's Encyclopedia of Industrial Chemistry", 4th newly edited and expanded edition, Verlag Chemie, Weinheim, Volume 20, page 411-414 and of

W. Schonfeldt in "Grenzflächenaktive Alkylenoxidaddukte", Scientific Publishing Company MBM, Stuttgart, 1973, pages 805-853 reported in. The review of these substances has been found that a few aqueous preparations of crop protection products containing high levels of sulfate and sulfonate surfactants than Defoamers are effective, but only if they are added separately to the already foaming dilute aqueous spray mixtures from the outset dissolved in the formulations or from the outset with the sulfate or sulfonate groups wetting agents combined as a concentrated aqueous surfactant solution which is added to a spray mixture remain However, the addition of defoamers to the spray mixture independently of the addition of the wetting agent or to the wettable spray mixture has disadvantages and does not satisfy in any way For example, requires shipping and handling an additional pack.

Furthermore, it is necessary to measure the respectively suitable amounts of antifoaming agent during the production of the spray mixture, if at a certain time one wishes to use only a part of the pack of the liquid herbicidal formulation. Another disadvantage is that the antifoam must be thoroughly mixed with the sprayable formulation. The mentioned technical disadvantages are avoided with the invention.

The invention relates to aqueous preparations which contain an anionic wetting agent selected from the group consisting of sulphate- or sulphonate-containing surfactants (wetting agents) in combination with a surfactant (defoamer) from the group of perfluoro (C ₆ -C ₁₈ ) -alkylphosphinic acids and / or perfluorocarboxylic acids. iCg-CKiJ-alkylphosphonsäuren and / or their salts.

The wetting agent / antifoam combination according to the invention can be present as a concentrated aqueous solution which is suitable as an additive for spray liquors of crop protection agents, or can be present in an aqueous concentrated formulation of crop protection agents. The weight ratio of wetting agent to defoamer is preferably from 1: 1 to 500: 1, especially 10: 1 to 200: 1, in particular 20: 1 to 120.Ί.

Of particular interest are aqueous solutions of wetting agent and defoamer, which are essentially 2 to 90% by weight, preferably 20 to 60% by weight, anionic sulphate or sulphonate group-containing surfactants (wetting agent) and 0.05 to 5% by weight, preferably 0.1 alkylphosphinic or alkylphosphonic wt .-% to 1, in particular 0.2 to 0.5 wt .-% of salts of perfluoro (C6-C ₁₈₎ and contain water.

The latter aqueous solutions are suitable as a wetting / defoaming additive to spray liquors of crop protection agents and cause an increase in the effect of pesticides in trouble-free handling of the spray liquors.

Suitable plant protection agents are, for example, herbicides, insecticides and fungicides, preferably herbicides.

Herbicides whose spray mixture can be treated with the wetting / defoaming combination according to the invention are, for. Glufosinates, bialaphos, glyphosates, carbamate-derived herbicides, thiocarbamates, haloacetanilides, imidazolinones, substituted phenoxy, naphthoxy, phenoxyphenoxy, benzyloxyphenoxy and heteroaryloxyphenoxycarboxylic acid derivatives and cyclohexanedione derivatives, sulfonylurea herbicides; Heteroaryloxy-phenoxycarboxylic acid derivatives are e.g. For example, quinolyoxy, quinoxyloxy, pyridyloxy, Benzoxazolyloxy-, Benzthiazolyloxy-phenoxy-carboxylic acid ester. Preference is given to phenoxyphenoxy- and heteroaryloxyphenoxycarboxylic acid esters. Suitable esters are, in particular, lower alkyl, alkenyl and alkinyl esters.

However, the wetting agent / defoamer combination according to the invention can also be present in aqueous liquid formulations of the abovementioned herbicides.

The invention therefore also liquid herbicidal preparations containing at least

a) a herbicidal active substance, preferably from the group, containing glufosinates, bialaphos, glyphosate, fenoxaprop-ethyl, fenoxaprop-P-ethyl, diclofop-methyl, isoproturon MCPA, imazapyr, imazaquin, imazethapyr, in particular glufosinate, or one of its salts,

b) an anionic surfactant from the group of surfactants containing sulphate or sulphonate groups,

c) a surfactant from the group of perfluoro (C6-C alkylphosphinic or -alkylphosphonic ₁₈₎ or one of its salts, preferably from the group of its alkali metal salts, ammonium salts, salts with Ci-Cie-alkyl amines, C-18 Alkylaminoxethylaten or ethylenediamine ethoxylates or mixtures of the surfactants and

d) contain water.

Of particular interest are concentrated preparations according to the invention which are at least

a) 1 to 45% by weight, preferably 5 to 30% by weight herbicidal active ingredient,

b) from 1 to 50, preferably from 5 to 35,% by weight of sulphate- or sulphonate-containing surfactant,

c) from 0.05 to 5% by weight, preferably from 0.05 to 1% by weight, in particular from 0.2 to 0.5% by weight, of a perfluoro (C ₆ -C ₁₈ ) -alkylphosphine or -alkylphosphonic acid or their salt or mixtures thereof and

d) contain water.

The herbicidally active compounds are preferably used in the form of their already mentioned salts from the group of the alkali metal, ammonium, lower or long-chain alkylammonium and alkanolammonium salts and the salts with fatty amine ethoxylates. Particularly preferred are the sodium, ammonium and isopropylammonium salts.

The sulfonate or sulfate surfactants are generally used in an amount of 0.5 to 8, preferably 0.5 to 5 parts by weight per part by weight of herbicidal active ingredients and are used primarily to improve the effectiveness of the herbicides. Examples of these anionic wetting agents are described in DE-A 3035554, JP-86/289004 and P 3809159.3. Suitable anionic wetting agents (b) are, for example, (C ₁₀ -C ₁₈ ) fatty alcohol polyglycol ether sulfates, (C ₁₀ -C ₁₈ ) fatty alkyl sulfates, (C ₈ -C ₂₂ ) -α-olefinsulfonates, (C ₄ -C ₁₆ -) Alkyl) -diphenyl ether sulfonates, (C ₁₀ -C ₁₈ ) fatty alkyl sulfonates, (C ₁ -C ₁₅ -fatty-alkyl-arylsulfonates, (C ₁₀ -C ₁₈ ) -fatty alcohol sulfosuccinic acid half-esters, (C 1 -C 8) -fatty alcohol-polyglycol ether-sulfosuccinic acid esters and their derivatives Salts, such as alkali metal, ammonium, alkaline earth metal, alkylammonium or alkanolammonium salts, and mixtures of the wetting agents mentioned are particularly suitable (Ciz-Ciel fatty alcohol polyglycol ether sulfates, especially as alkali metal or ammonium salts.) In the wetting agents with polyglycol ether chains preferred are those which are clearly water-soluble and have a degree of ethoxylation of from 1 to 200, in particular from 4 to 15. The anionic surfactants are commercially available or can be prepared by known methods.

Perfluoroalkyl-containing surfactants (component c) are in particular perfluoro-FCg-C ^ l-alkylphosphinic acids and -phosphonsäuren and their sodium, potassium, ammonium, C _l0 -C ₁₈ -Alkylammoniumsalze and salts with Cm-C ₁₈ -Alkylaminethoxylaten and Ethylenediamine ethoxylates such as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and Ν, Ν, Ν', Ν'-tetrakis (2-hydroxyethyl) ethylenediamine. The perfluoroalkyl-containing surfactants are commercially available, for. B. ®Fluowet PP (mixture of Cg-C ^ -Perfluoralkylphosphin- and -alkylphosphonsäuren, Hoechst) or can also be prepared by known methods. The perfluoroalkylated phosphinic and phosphonic acids are prepared according to DE-A 2111767 by oxidative hydrolysis of perfluoroalkyldiiodide and bis (perfluoroalkyl) iodophosphone; the salts are prepared by neutralization of the acids thus obtained by the corresponding hydroxides or substituted amines in water or polar organic solvents such. As alcohols, DMF, NMP, the salts are then preferably used in dissolved form.

In addition to sulfate and sulfonate containing surfactants and the found effective perfluoroalkyl defoamers, the aqueous solutions can be added to the spray liquors or the preparations containing pesticides contain other conventional formulatory agents, such as. B. nonionic surfactants of the alkylpolyglycol ether series, e.g. Isotridekanolpolyglykolether, nonyl or Octylphenolpolyglykolether or Fettaminethoxylate, further antifreeze as

Ethylene or propylene glycol, propylene glycol monomethyl ether, glycerol, isopropanol and urea and other dispersants and emulsifiers, such as those listed in McCutchenon, organic solvents and fillers such as water-soluble substances, such as ammonium sulfate, urea, sodium sulfate, sodium sulfite and sodium bisulfite. Concentrated formulations preferably comprise one of the herbicides glufosinate (I), bialaphos (II), glyphosate (III), fenoxaprop-ethyl (IV), fenoxyprop-P-ethyl (D-form of (IV)), diclofop-methyl (V) , Isoproturon (VI), MCPA (VII), imazapyr (VIII), imazaquin (IX), imazethapyr (X) or mixtures of two or more of said active substances. The compounds (I) and (III) to (X) are described in the "Pesticide Manual", 8th edition (1987), edited by the British Crop Protection Council The compound (II) (Bialaphos) is described in US-A 4,309,208 The active compounds (I) to (III) and (VII) to (X) are generally used in the form of their sodium, ammonium and monoisopropylammonium salts, and in practice they can also be used in the form of other alkali metal salts or lower alkyl or They can also be used as salts of long-chain C ₈ -C ₈ -alkylamines or fatty amine ethoxylates (cf EP 0290416 and German patent application P 3832147.2) The preparations according to the invention may additionally contain other herbicidal active compounds, eg f 1) other water-soluble herbicidal active ingredients such as those of the phenoxy series such as CMPP, MCPA, 2,4-D or loxynil or Bromoxynil or salts thereof or

f 2) further solid insoluble active substances such as urea-series herbicides such as diuron, linuron, monolinuron, isoproturon, thidiazuron and / or triazine series herbicides such as simazine, atrazine and / or sulphonylureas such as DPX-L-5300, thiameturonmethyl (DPX-L). M-6316) and metsulfuron methyl (DPX-M 6376) and N-alkoxy and

N-alkylsulfonylaminosulfonylureas, as mentioned in EP-A 0131258, in particular in Examples 17, 18, 19, 20 to 124, f3) other liquid or low-melting active substances, such as alachlor, metolachlor, trifluralin, esters of phenoxy herbicides and esters of loxynil and bromoxynil.

In this case, the active ingredients of class f 1) can be formulated as aqueous solution concentrates, of class f 2) in the form of suspension concentrates, the concentrates containing water-soluble active substances such as e.g. Active ingredients (I) to (III) in the aqueous carrier phase and the insoluble active ingredients as a solid phase in the finest distribution. The active substances of class f 3) are z. B. formulated as suspoemulsions, the water-soluble active ingredients in the aqueous phase z. B. (I) to (III) and in the oily phase, the liquid or low melting active compounds as such or dissolved in conventional solvents, eg. B. from the group of aromatic, optionally halogenated hydrocarbons or aliphatic esters or ketones. Compounds of class f 2) can sometimes be beneficially processed into water-dispersible granules with water-soluble herbicides (e.g., herbicides (I) to (IM)) and the sulfate and sulfonate surfactants. Again, the perfluoroalkylated compounds used in the invention act as defoamers.

The active substances mentioned under f 1), f 2) and f 3) are known in large part from the already mentioned "Pesticide Manual" (by the Britishl Crop Protection Council) The sulfonylureas DPX-L-5300, DPX-M-6316 and DPX-M-6376 are described in "Farm Chemicals Handbook 89 (Meister Publishing Company, Willoughby, OHIO, 1989).

The defoamers (c) are also effective when they are in the aqueous active ingredient solution or dispersion in amounts of preferably 0.05 to 5Gew .-%, especially 0.05-1 wt .-%, in particular 0.2 to 0, 5Gew .-% dissolved are included and this drug solution or dispersion in water is used, the then dilute solution prior to application sulfate and sulfonate surfactants (c) and, if necessary. Other aids (e), such as Alkylpolyglykolether or Fettaminethoxylate be added separately.

The defoamers are also effective when contained in the surfactants in amounts of preferably 0.05-5 wt .-%, in particular 0.05-0.5 wt .-%, and to contain such a surfactant mixture the spray liquors of liquid formulations the herbicidal active ingredients added.

The invention therefore also relates to the dilute preparations (spray liquors) which contain the constituents of the abovementioned concentrated preparations in approximately 5 to 500 times diluted form. The invention also provides the process for the preparation of the preparations according to the invention, characterized in that the perfluorinated surfactants (c), optionally dissolved in water and optionally together with the anionic wetting agents (b), with the aqueous solution or dispersion of the active ingredients (a ), which may already contain anionic wetting agents (b) and / or other active ingredients (f) and / or conventional adjuvant (s) before or after dilution with water or without dilution with water and, if necessary, still anionic wetting agents (b) or residual Add ingredients.

The perfluoroalkyl-containing surfactants (c) used according to the invention make it possible to comprise the herbicidally highly active preparations, in particular the aqueous liquid preparations of the water-soluble active compounds (I), (II) and (III), which contain effective amounts of anionic surfactants containing sulfate or sulfonate groups, to be provided with effective defoamers. The same applies to the dilute aqueous spray mixtures. The herbicidal compositions can thus be marketed for practical use

 In the following examples, percentages are by weight unless otherwise specified.

Examples

1. To a solution of

18.00g glufosinate-ammoniumin

41.75g of water

30.00 g (Cu-CieJAIkohol polyglycol ether sulfate Na (70% in water) and

Added 10.00 g of propylene glycol monomethyl ether.

It is stirred at 40 ° C until a clear solution is formed. Then 0.25 g of Fluowet PP (80% in water) are added and it is briefly stirred.

2. To a mixture of 17.0 g of water,

10.0 g of propylene glycol monomethyl ether and

0.5g Fluowet PP (80% in water)

13.5g glufosinate-ammonium and

59.0 g (C ₁₂ -C, ₆ ) Alkoho! Polyglycol ether sulfate Na (70% in water). It is stirred at 40 ° C until, until

a solution has emerged.

3. To a solution of

17.00 g of L-2-amino-4- (hydroxy) (methyl) phosphinoyl butyryl-alanyl-L-alanine Na salt in

52.75 g of water

20.00 g (C, 2-C, ₆ ) alcohol polyglycol ether sulfate Na (70% in water),

0.25g of Fluowet PP (80% in water) and

Add 10.00 g of methyl glycol.

It is stirred at 4O ⁰ C until a solution has formed.

4. To a mixture of 35.50 g of water,

5.00 g of propylene glycol methyl ether and

0.50g Fluowet PP (80% in water)

29.00g glyphosate isopropylammonium salt (62% in water)

30,00g _(C12-ie) alcohol polyglykolethersulfat-Na (70% strength in water)

added and stirred at 25 ° C until a solution has formed.

5. To a solution

18.6 g glufosinate-ammoniumin

61.5 g of water

20.0 g of isodecyl-sulfosuccinic half-ester dinatrium salt. It is stirred until a solution

originated. Then 0.5 g of Fluowet PP (80% in water) is added and it is stirred briefly.

6. To a solution of

17.6 g glufosinate-ammoniumin

43.2 g of water

24.0 g lsodecyl-sulfosuccinic acid half-ester disodium salt (50% in water) and

14.7 g (C, 2-C _ie ) alcohol polyglycol ether sulfate Na (70% in water) and

Add 0.5g of Fluowet PP (80% in water). It is stirred at 4O ⁰ C until a solution has formed.

Suspensions in formulations 1 to 6, which cause a slight haze, can be removed by filtration.

froth

A 250 ml graduated cylinder which can be closed with glass stopper is filled with 190 ml standard water D (342 ppm hardness according to CIPAC Handbook I, p878) and admixed with 10 ml of the formulation to be tested.

The sealed cylinder is rotated by 10 degrees by 180 degrees and back. Immediately thereafter, a stopwatch is turned on to measure the time to collapse of the foam.

Result

When using formulations containing the defoamers according to the invention, 90% of the foam disappear within 1 min, often even the entire foam collapses within 30 s. When using formulations that do not contain a defoamer, the foam often remains stable for 1 hour. Analogously to Examples 1 to 6, it is also possible to use those salts of this acid which have good solubility in water and / or organic solvents instead of perfluoroalkylphosphinic acidZ-phosphonic acid (Fluowet PP). The salts are advantageously used in dissolved form with 0.05 to 1.0 wt% acid equivalent, preferably 0.2 to 0.5 wt% acid equivalent. However, they can also be formed in the course of the formulation process by neutralization with the corresponding bases. With the salts of ®Fluowet PP prepared in Examples 7 to 9, formulations are prepared analogously to Examples 1 to 6 and correspondingly good defoamer action is determined.

7. Salt of Fluowet PP with coconut fatty amine + 2 EO. To a solution of

29.50g coconut fatty amine + 2EO (EO = ethyleneoxy moiety

29.50 g of propylene glycol monomethyl ether are allowed to stir slowly with a solution of

51,90g Fluowet PP (80% in water) in

Run 31.14 g of propylene glycol monomethyl ether. This gives a solution with 50Gew .-% of the Fluowet PP salt, the

has a pH of 6.9.

8. Salt of Fluowet PP with triethanolamine. To a solution of

51,90g Fluowet PP (80% in water) in

31.14g of water are allowed while stirring slowly a solution of

14.92g triethynolamine

14.92g watercourse

This gives a solution with 50 wt .-% of the Fluowet PP salt, which has a pH of 6.8.

9. Salt of Fluowet PP with N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine * To a solution of

51.90 g Fluowet PP (80% in water)

31.14g of propylene glycol monomethyl ether is allowed to slowly dissolve a solution while stirring

21.90g HOES3528in

Run 21.90 g of propylene glycol monomethyl ether.

This gives a solution with 50 wt .-% of the Fluowet PP salt and a pH of 6.4. * HOE S-3528 (Hoechst) or®Quadrol L (BASF)

10. Salt of Fluowet PP with ®Genamin T150 To a solution of

50.79 g of propylene glycol monomethyl ether,

7.57 g of polyethylene glycol 600 and

26.57 g tallow fatty amine ethoxylate (Genamin T150) is allowed to stir slowly with stirring

Run 15.07 g of Fluowet PP (80% in water). The result is a slightly turbid solution with a pH of 6.8. The

Turbidity largely dissipates after standing for 24 hours. Before use to aqueous surfactant solutions is briefly stirred again.

11. Example for the defoaming of surfactant solutions when used in aqueous spray mixtures

To 98.72 g of C ₁₂ -C ₁₄ alkyl diglycol ether sulfate Na (28% in water.RTM.Genapol LRO flüssig, Hoechst) are added 1.28 g of N, N, N ', N'-tetrakis-2- (hydroxypropyl) -ethylenediamine salt of Fluowet PP, 50% in

Propylene glycol monomethyl ether from Example 9 and stirred briefly. This results in a clear solution. If 10 g of this solution are diluted with 238 g of water in a 250 ml standard cylinder and then 2 g of glufosinate-ammonium (50% in water) are added, the foam which has been rotated 10 times by 180 ° and the foam formed is broken within 1 minute together.

12. Further examples of the defoaming of surfactant solutions when used in aqueous spray mixtures of surfactant solution A:

To 98.6 g of C ₁₂ -C ₁₄ alkyl diglycol ether sulfate Na (28% in water, ®Genapol LRO liquid, Hoechst) was added 1.4 g of the Fluowet PP / Genamin T 150 salt of Example 10. After a short stirring results in a clear, application-free solution.

Surfactant solution B:

To 98.6 g alpha-olefinsulfonate-Na

(40% in water, ®Hostapur OS, Hoechst) add 1.4 g of the Fluowet PP / Genamin T150 salt of Example and stir until a homogeneous solution is obtained which has a slight turbidity.

Surfactant solution C:

To 98.6 g of alkanesulfonate-Na

(30% in water, ®Hostapur SAS, Hoechst) is added 1.4 g of the Fluowet PP / Genamin T150 salt of Example 10 and stirred briefly until a homogeneous solution is obtained, which is slightly cloudy.

Surfactant LösungD:

To 98.6 g Isodecylsulfobernsteinsäurehalbester-disodium (30% in water, ®Netzer iS, Hoechst) are added 1.4 g of Fluowet PP / Genamin T150 salt of Example 10 and stirred for a short time.

The surfactant solution was mixed with the standard formulations of crop protection products

Glufosinate (®Basta, Hoechst, 200g active ingredient per liter)

Fenoxyprop-P-ethyl (®Puma Super, Hoechst, 75g active ingredient per liter)

Isoproturan (®Arelon liquid, Hoechst, 500g active ingredient per liter)

Diclofopmethyl (®llloxan, Hoechst, 378 g of active ingredient per liter)

tested by mixing in each case 5 ml of the respective crop protection formulation (PSM) with each osmotic surfactant solution in a 250 ml standard cylinder with 185 ml of water (standard water D according to CIPAC Handbook 1970, p. 878) so that the sealed cylinder is rotated 180 times and 180 times back and forth the time elapsed until the foam collapsed was measured. The results are summarized in the following table:

PSM A B Surfactant solution C D Basta Puma Super Arelon liquid llloxan 45 see 30 see 30 see 30sec 2 min 2min 3min 3min 1 min 3 min 2 min 1 min 1 min 30 see 1 min 30 see

From the table it can be seen that the foam collapses within 30 to 3 minutes. If the test is carried out with the surfactant solutions that contain no defoamers, the Ziet is usually up to the collapse of the foam over 10 min

 13. Defoamer Test (with Comparative Examples)

To a clear solution containing 20% by weight of glufosinate ammonium salt and 20% by weight of (C ₁₂ -C ₁₆ ) fatty alcohol ether sulfate Na, commercial defoamers are added compared to ®Fluowet PP. Depending on the effectiveness and solubility, up to 5% by weight defoamer is added, with silicones and fluorinated substances about 0.2 to 0.3% by weight. The defoaming action or the foaming behavior is tested after dilution to give a spray mixture containing 2% by weight of glufosinate-ammonium (see Table 1). As Table 1 shows, the substances which are offered as defoamers in the market, do not work if they are incorporated from the outset in the anionic surfactant-containing active compound preparations. Moreover, the majority of antifoam agents are not clearly soluble. A few that are soluble lose their effectiveness in storage of the herbicidal preparations. Here, known defoamers of chemically different nature are tested. Since the suppliers only provide information about the chemical composition, table 1 shows the trade names of the defoamers, the manufacturers and the affiliation to a chemical group.

It is surprising to note, inter alia, that other perfluoroalkyl-containing surfactants, apart from those according to the invention, show no good defoaming action in the test.

In comparative experiments in which glufosinate-ammonium has been replaced by glyphosate and bialaphos, analogous results are obtained.

Table 1 Defoamer test for aqueous glufosinate formulations with high anionic wetting agent contents

Ser. trade name supplier chem. solubility perfluoroalkyl clear Defoaming effect 1 month 2 months 3 months No. active substance in Basta Perfluoralkyltri- clear after storage of the formulation at 50 ⁰ C. _ _ _ Forsul methyl ammonium salt immediately 1 EntschäumerTIP Hoechst AG triisobutyl cloudy perfluoroalkylbetaine clear none - _ _ in isobutanol Perfluoralkylpoly- clear 2 Defoamer KH Hoechst AG nonionic clear g Iy ко lather none - - - connection Perfluoralkylpoly- clear 3 Defoamer SF Hoechst AG neutralized mixture clear glycol ether none of phosphinphosphonic _ _ _ acids 4 Anti-m brave Siloxane-based clear Well low o. Wirk. - pulverSP3 5 antifoam brave Siloxane + polyvinyl practically Well Well low o.Wirk. pulverSP8 alcohol + silicic acid insoluble 6 foam stop brave polydimethylsiloxane cloudy Well 7 Hoe S 3181 Hoechst AG mineral oil-free Ent cloudy none o. Wirk. - - frother low o.Wirk. 8th Defoamer STE brave polydimethylsiloxane clear Well - - - 9 Defoamer SRE brave polydimethylsiloxane clear Well 10 Hoe S 2736 Hoechst AG 85% polyglycol + cloudy none Perfluoroethanol + _ - - Isononansäureamid very well very good very good 11 Defoamer KS1 Hoechst AG - clear none 12 FluowetPP Hoechst AG perfluorinated alkyl clear very well phosphine-phosphonic - - - acid 13 NopcoKX2 Diamond Siloxane + aliphatic. clear none - - - Shamrock KW substances 14 Nopco NDW Diamond Siloxane + aliphatic. cloudy none - - _ Shamrock KW substances 15 antifoam brave Siloxane-based cloudy none Well o.Wirk. - medium 5882 16 antifoam brave Siloxane-based cloudy Well low o.Wirk. - medium 5155 17 Anti-foaming agents brave Siloxane-based clear Well low o.Wirk. - S LA 54289 18 Defoamer RD Dow / Siloxane-based almost clear Well - - - Corning 19 RD-emulsion Dow / Siloxane-based clear none Well low o.Wirk. 500CC Corning 20 defoamers Dow / Siloxane-based clear Well Well o.Wirk. - DB31 Corning 21 defoamers Dow / Siloxane-based cloudy Well o. Wirk. - MSA Corning 22 defoamers Dow / Siloxane-based cloudy low - - - DB100 Corning 23 defoamers Dow / Siloxane-based insoluble none - - - Q 2-3 / 68 Corning - - - 24 Surfion S-111 Asaki Chem. Perfluoroalkylcarboxylic acid clear none - - - 25 SurflonS-112 Asaki Chem. none 26 Surfion S-121 Asaki Chem. none - - - - - - 27 Surfion S-131 Asaki Chem. none 28 Surfion S-141 Asaki Chem. none - - - 29 Su rf lon S-145 Asaki Chem. none

Table!, Cont trade name supplier chem solubility Defoaming effect 1 month 2 months 3 months YTD active substance in Basta after storage of the formulation at 50 ° C _ _ _ No Forsul immediately _ _ _ K-Palmital Soap cloudy none _ _ _ 30 Mg stearate Soap cloudy none 31 defoamers SWS Siloxane-based practically none _ _ _ 32 Q75 Silicone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 33 Q 93 Silicone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 34 Q 94 Stlicone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 35 Q101 Silicone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 36 SWS 203 Silicone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 37 SWS211 Sihcone's insoluble defoamers SWS Siloxane-based practically none _ _ _ 38 SWS213 Silicone's insoluble defoamers Dow / Siloxane-based insoluble none not applicable, cloudy 39 Q 2-3241 Corning defoamers Dow / Siloxane-based insoluble Well _ _ _ 40 Q 2-3242 Corning defoamers Dow / Siloxane-based cloudy none _ _ _ 41 DB110A Corning defoamers Dow / Siloxane-based cloudy none _ _ _ 42 1520 Corning Antimoussol Rhone Siloxane-based oligeAb- none _ _ _ 43 454 Poulenc divorce Antimoussol Rhone Siloxane-based oligeAb- none not usable 44 416 Poulenc divorce Antimoussol Rhone Siloxane-based oligeAb- Well _ _ _ 45 426 R Poulenc divorce Antimoussol Rhone modified insoluble none _ _ _ 46 20417 Poulenc silicone oil FoammasterDOI Diamond Silicone emulsion insoluble none _ _ _ 47 Shamrock FoammasterUD8 Diamond Silicone emulsion cloudy none _ _ _ 48 Shamrock Polysekon133 gold Siloxane-based clear none _ 49 schmidt Polysekon720 gold Siloxane-based clear none _ _ _ 50 schmidt _ _ _ Beraloid6420 Erbsloh "Polymer substance clear none _ _ _ 51 Beraloid581 B Erbsloh metal soaps clear none 52 Beraloid5581 Erbsloh no silicone oil, clear none - - - 53 otherwise no information DehyponLT24 handle Fatty alcohol AEO clear none low о effective - 54 Pyoglykol _ _ _ Dehydran handle Siloxane-based clear Well 55 Dehydran 131 handle Mixture ν fat cloudy none 56 acid esters and _ silicone oil Dehydran 240 handle modified clear none - - - 57 Polyathylenglykol - - - Dehydran 242 handle Siloxane-based clear none - - - 58 Dehydran 243 handle Siloxane-based clear none 59 Dehydran 490 handle "hydroxyl clear none 60 containing "

Table 1 (continued)

YTD

 No.

trade name

supplier

former active substance

Solubility Defoaming effect

in Basta after storage of the formulation at 50 ° C

Forsul immediately! Month 2month 3months

61 CetielHE

62 trial product KE 1445

63 defoamer KE1393

64 defoamer KE1102A

65 defoamer BE7249

66 defoamer K 975

67 Antimous sol A6

68 AntimoussolWLN

69 Rheolate

70 Elenor C22R

Henkel unknown no clear

Henkel unknown no clear

Henkel polyglycerol + 22PgO clear no

Henkel unknown no clear

Henkel unknown no clear

Henkel unknown no clear

Sandoz Glycerine dialkyl ether clear no

Sandoz Glycerine dialkyl ether clear no

+ Wetting agent

unknown unknown cloudy none

unknown unknown cloudy none

Claims (13)

1. An aqueous preparations which alkylphospinsäuren an anionic wetting agent from the group of sulfate or sulfonate surfactants (wetting agents) in combination with a surfactant (defoamer) from the group of perfluoro (Cg-Ci ₈₎ and / or perfluoro- (C6 C ₁₈ ) alkylphosphonic acids and / or salts thereof. 2. Aqueous preparation according to claim 1, characterized in that it contains wetting agent and defoamer in a weight ratio of 1: 1 to 500: 1. 3. Aqueous preparation according to claim 1 or 2, characterized in that it consists essentially of 2 to 90 wt .-% wetting agent, 0.05 to 5Gew .-% defoamer and water. 4. Aqueous preparation according to claim 1 or 2, characterized in that it is a liquid herbicidal preparation containing at least a) a herbicidal active ingredient, b) an anionic surfactant from the group of surfactants containing sulphate or sulphonate groups, c) a surfactant from the group of perfluoro (C ₆ -C ₁₈ ) alkylphosphinic acids or alkylphosphonic acids or one of its salts or mixtures of the surfactants and d) water
contains. 5. Preparation according to claim 4, which is at least a) 1 to 45% by weight, preferably 5 to 30% by weight herbicidal active ingredient, b) from 1 to 50, preferably from 5 to 35,% by weight of sulphate- or sulphonate-containing surfactant and c) from 0.05% to 5% by weight of perfluoro (C 6 -C ₈ ) alkylphosphine or alkylphosphonic acid or its salt or mixtures thereof and d) contains water. 6. Preparations according to one or more of claims 1 to 5, characterized in that it contains as sulfate or sulfonate surfactant (C-iQ-C-isJ-fatty alcohol polyglykolethersulfate, (Cio-C ₁₈ ) -Fettsalkylsulfate, (C8-C ₂ 2) -α-olefinsulfonates, (C ₄ -C ₁₆ -alkyl) -diphenyl ether sulfonates, (C ₁₀ -C ₁₈ ) -fatty alkyl sulfonates, (C ₁ -C ₁₈ -fatty alkyl) -arylsulfonates, (C ₁₀ -C ₁₈ ) - Fatty alcohol sulfosuccinic acid semi-esters, (Ci ₀ -C ₁₈ ) -Falalkoholpolyglykolethersulfobernsteinsäurehalbester or salts thereof or mixtures of the above surfactants. 7. Preparations according to one or more of claims 1 to 6, characterized in that they are perfluoroalkyl-containing surfactants (c) perfluoro (C6-C ₁₂ ) alkylphosphinsäuren or -alkylphosphonsäuren or their alkali metal, ammonium, alkylammonium or salts thereof Alkylaminoxethylaten or Ethylenediaminoxethylaten or mixtures of the above surfactants. 8. Preparations according to one or more of claims 1 to 4, characterized in that they contain in addition to the constituents mentioned further customary formulating agents selected from the group of nonionic surfactants, antifreeze agents, dispersants, emulsifiers, organic solvents and fillers. 9. Preparations according to one or more of claims 4 to 8, characterized in that they additionally f 1) water-soluble herbicidal active compounds, from the phenoxy series, loxynil, bromoxynil or salts thereof or f 2) solid insoluble herbicides from the urea, triazine or sulfonourea series, f 3) liquid or low-melting active substances from the group alachlor, metolachlor, Trifluralin, esters of phenoxy herbicides and esters of loxynil and bromoxynil. 10. A process for preparing aqueous preparations according to one or more of claims and 6 to 8, characterized in that one dissolves the wetting agent and the defoamer in any order or together, optionally with other conventional excipients in water. 11. A process for the preparation of the preparations according to one or more of claims 4 to 6, characterized in that the perfluorinated surfactants (c), optionally dissolved in water and optionally together with the anionic wetting agents (b), with the aqueous solution or dispersion the active substances (a) which may already contain anionic wetting agents (b) and / or other active ingredients (f) and / or conventional adjuvants, before or after dilution with water or without dilution with water and, if necessary, anionic wetting agents ( b) or residual constituents. 12. Use of perfluoro _(C6-C18) alkylphosphinic or-alkyl phosphonic acids or their salts from the group of alkali metal, ammonium, alkyl ammonium salts or salts with Alkylaminoxethylaten or Ethylendiaminoxethylaten or mixtures of the above surfactants as defoamers for sulfate or sulfonate surfactants in aqueous media. 13. Use according to claim 12, characterized in that the aqueous medium is a liquid herbicidal preparation.