DD202229A5 - WAITER PESTICIDE CONCENTRATES - Google Patents

Abstract

1. An aqueous solution concentrate comprising alph) a liquid or solid pesticide that is stable in water and less than 1 % soluble in water and has a water number greater than 10, and beta) a salt of an aromatic sulphonic acid having the formula see diagramm : EP0074329,P8,F1 wherein R1 , R2 and R3 have the same or different meanings and each is hydrogen or straight-chain or branched C1 -C6 -alkyl, Z is a direct bond or a straight-chain or branched C1 -C6 -alkylene bridge and R4 is an alkali metal, an ammonium group, a primary, secondary or tertiary amine group, a hydroxyalkylamine group or a morpholine group, in an amount sufficient to form an aqueous solution.

Description

-1 - 23 9 8 0 2 0 Berlin, 1.10.1982

AP A Ol N / 239 802/0 60 853/11

Aqueous pesticide concentrates Field of application of the invention

The present invention relates to aqueous pesticidal concentrates of liquid and / or solid, water-sufficiently stable, water-insoluble active ingredients which can be diluted by consumers for spraying and a process for the preparation of such formulations,

Characteristic of the known technical solutions

From the viewpoint of the formulation chemist, many pesticidal actives may be considered water-insoluble. Their water solubility is usually less than 1.0% wt / volume. However, this value does not limit the invention in any way. The dissolution of these compounds in aqueous medium to an aqueous concentrate has been difficult and impossible in many cases. Where dissolution was possible, the final product had too low a concentration, poor shelf life, poor stability to temperature, and was generally unsuitable for sale, and therefore, traditional anhydrous formulation techniques are commonly used for these actives aqueous suspensions prepared, provided that the active substance has a melting point of at least 70 ⁰ C.

The type of formulation chosen depends on the physicochemical properties of the active substances used. Three categories can be distinguished.

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1. Emulsifiable concentrates (EC) - for oil-soluble active substances,

In this type of processing, an emulsifier or surfactant is necessary to ensure

that the product gives a homogeneous emulsion when it

diluted with water for consumption »The main advantage of this formulation is ea that

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the product is a liquid isc. Disadvantages of this type of formulation are: 1. large quantities of potentially hazardous and acidic solvents are used; and 2. for safety reasons, these formulations are often packaged in expensive aluminum or white-tan containers.

2.> wettable or dispersible powders (WP) - in Ölunlö'sliehen active ingredients.

In this type of formulation, surfactants are needed to ensure complete dispersion of the product when it is diluted with water by the end user. The main drawbacks of this type of forbitalization are: 1. that it is a powder and thus contains a potential risk of dust, and 2. that the powder must be weighed by the user in the field and can not be volumetrically dosed like a liquid.

3. The aqueous suspension concentrates (SC) -at oil - and water-insoluble active substances having a melting point above 70 ⁰ C.

In this type of formulation, the active ingredient is finely ground and suspended in water with the aid of surfactants. The main advantage of this type of fortification is the presence as a liquid. The disadvantages are the tendency to form non-resuspendable dregs and that this type of formulation is not applicable to liquid and low melting agents, even if they are to be used only as a mixing partner.

Consequently, an active substance can be reornulated as a liquid emulsifiable concentrate if it is soluble in oils. On the other hand, if it is not soluble in oils, it is usually formulated as a wettable powder or, if the melting point is sufficiently high, as a suspension concentrate. All three Fonnulierungstypen have significant disadvantages, with the wettable powders are larger than the other two.

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We have now found that many of the disadvantages associated with formulating the active ingredients mentioned in this application can be overcome by the new inventive technique of forgery.

Object of the invention

The object of the invention is to provide aqueous pesticidal solution concentrates of pesticidal active substances which are stable in water and insoluble in water, which are storable and dilutable with water, forming relatively stable emulsions or dispersions.

Explanation of the essence of the invention

It is an object of the present invention to provide a novel formulation method which makes it possible to combine a pesticidal active substance of the type mentioned with a water-insoluble solid active substance which itself can not be formulated by the process according to the invention.

According to the invention, pesticides are combined with aromatic sulfonic acids and their salt derivatives. This group of compounds serves as a hydrotrope.

According to the invention, therefore, an aqueous solution concentrate is provided which

CiC) contains a pesticide which is stable in water and substantially insoluble in water, and

ß) an aromatic sulfonic acid or a salt thereof having the formula I.

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2-SO ₃ R ₄

^R i

^R 2

contains, in which R *, R ₂ and R_ may have the same or different meaning and are hydrogen or straight or branched ^C -i- ^c ₆

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Alkyl, Z is a geradkectige or branched C-C, alkylene bridge or a direct bond and R, hydrogen, an alkali metal, an ammonium group, a primary, secondary or carboxy amino group, a hydroxyalkylamino group or a morpholino group. The aqueous solution concentrates according to the invention can be prepared by simply dissolving a compound (α) in an aqueous solution of a compound (β).

Preferably, the aqueous solution concentrates according to the invention comprise up to 75% by weight / volume of active ingredient (component α), in particular 5 to 50% by weight / volume, and up to 70% by weight / volume of pure hydrotrope (component β). , in particular 15 to 50% by weight / volume.

Typical examples of compounds of formula I are ammonium cumene sulfonate (commercially available as a 60% aqueous concentrate), potassium xylene sulfonate (commercially available in solid, pure form and as a 40% aqueous solution), sodium cumene sulfonate (commercially available in solid, pure form ), Sodium toluenesulfonate (commercially available in solid, pure form and as a 40% aqueous solution), and xylenesulfonic acid (commercially available as a 90% water-reducible liquid).

The degree of solubility of the pesticide in the hydrotrope is dependent on three properties:

1) the water solubility of the pesticide (or an indirect parameter of its water solubility, such as the "water number," which can be determined by the method of Greenuald, Brown and Finemann, Anal. Chem., 28 , 1693 (1956)),

2) the chemical structure of the hydrotrope and

3) the concentration of the hydrotrope in the formulated product.

In general, liquid pesticides having a "water number" of less than 10 are too lipophilic and are not soluble in an aromatic sulfonic acid (salt) solution to a commercially interesting degree. On the other hand

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For example, pesticides having "water numbers" greater than 10 may be formulated using commercially available water-based products using appropriate aromatic sulfonic acids or salts thereof. Surprisingly, it has been found that the pesticide, once dissolved in this hydrocrop, forms an emulsion or dispersion upon dilution with water. This phenomenon can occur without the use of emulsifiers or surface active agents which are necessary in a conventional emulsifiable concentrate in a hydrocarbon solvent.

Nevertheless, it may be helpful to the aqueous concentrates according to the invention functional aids such as surfactants and additional solvents (for better leaf moistening and drug penetration and to avoid crystallization of solid drugs from dilute aqueous solutions, ie from the spray mixture), adhesion and thickening agents (for better adhesion on the leaves and to adjust the droplet size in use) and antifoaming agents to prevent foaming.

Examples of such functional aids are:

a) surfactants and additional solvents: nonyl

(D phenol ethoxylates, e.g., those from the commercial ethylan N series, alcohol and fatty acid ethoxylates, e.g., those from the commercial Ethylan C series, and hydrocarbon solvents such as vegetable oils, mineral oils, methylphenols, and polyglycol ethers,

b) adhesives and thickeners: polyethylene glycols, polyacrylamide solutions and polyvinylpyrrolidones and

c) antifoam agents: silicone-based compounds and emulsions, fatty acids e.g. Coconut oil and ethylene oxide / propylene oxide block copolymers such as the commercial oils of luronic polyalcohols.

Examples of liquid and solid active ingredients which are particularly suitable for use as components (α) in the novel concentrates are listed in the following tables:

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Table 1:

Liquid agents Wirkstoffklasse usual formulation (500 G AS / 1) New «on } i formulation jasis of water g AS / 1) active substance acetanilide EC (250 (250 g g AS / 1) ECW (300 g AS / 1) Mecolachlor triazole EC WP (500 G AS / 1) ECW (250 g AS / 1) propiconazole diazole EC (750 G AS / 1) ECW (500 g AS / 1) Emazalil morpholine EC (300 G AS / 1) ECW (500 g AS / 1) tridemorph phosphate EC ECW (300 chlorfenvinphos

Table 2:

Solid active ingredients

active substance Wirkstoffklasse Common formulation New formulation based on water Metalaxyl 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-criazol-1-yl) -pentane Acyl alanine triazole WP (250 g AS / kg) EC (100 g AS / 1) ECW (2 50 g AS / 1) ECW (100 g AS / 1)

EC - Emulsifiable concentrate

WP = wettable spray powder

ECW = Emulsifiable concentrate as an aqueous solution

AS = active substance.

Many water-insoluble solid excipients are not soluble to any appreciable degree in these hydrotropes, although some water-insoluble solid actives are soluble in these hydrotropes. It is therefore also an object of the present invention

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to provide a combination product containing two or more active agents having a broader spectrum of activity, the aromatic sulfonic acid salt solution serving as both a suspending and dissolving reagent.

A further subject of the invention therefore comprises aqueous concentrates which, in addition to the already defined components (α) and (β), contain as further component (γ) a solid pesticide which is not soluble in the hydrotrope.

These novel aqueous three-component concentrates can be prepared by preparing a solution of component (α) in (β), preferably but not necessarily using a surfactant, and adding component (γ) to the resulting solution and optionally milling the mixture to the desired particle size solid component (γ) are produced.

The resulting formulation is:

i) a liquid

ii) based on water produced iii) physically and chemically at high and low temperatures

stable iv) diluted with water to a stable sprayable spray mixture

and v) non-dusting compared to the corresponding wettable powder.

The use of aromatic sulfonic acid salt solutions as a hydrotrope and / or suspending agent for solid pesticides has the following advantages: A suspension prepared using this hydrocrope may not require the addition of antifreeze or suspension aids; the commercially available solutions of these hydrotropes can give the end product all of these properties to lend.

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This technique can also be used successfully to combine other liquid or solid active ingredients with other solid pesticides that are not hydrotrope-soluble. Examples are given in the following tables

Table 3: Combinations of liquid and solid pesticides:

Feast

Captan Carbendazim Atrazine Thiabendazole

Propiconazole +

Propiconazole +

Metolachlor ♦

Imazalil +

Table 4: Hard ( $>) copper oxychloride Korabinations of two solid pesticides: Zi ram Festig) folpet Metalaxyl + copper oxychloride Metalaxyl + Working Example Metalaxyl + 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) -pentane +

The following examples serve to illustrate the present invention in more detail:

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Comparative Example A (Usual Formulation)

propiconazole 250 1.9 emulsifiers 100 g / i Hydrocarbon of f- / aromatic solutions medium to on Example 1:

Propiconazole 250 g / l

60% Amraoniumcumolsulfonat solution up to 100 % of

volume,

As can be seen from the above details, both formulations contain the same concentration of active ingredient; nevertheless, Example 1 has the following advantages over Comparative Example A:

i) it contains no potentially dangerous solvents ii) it has no flash point lii) it contains no emulsifier

iv) it can be packaged in polyethylene containers and v) it is less toxic "because it is made on the basis of water.

Example 2:

Propiconazole 125 g / l

^ Soprophor FL 40 g / l

40% Ammoniumxylolsulfonatlösung up to 100 % of

Volume.

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Example 3;

Metolachlor 300 g / l

^ Tween 85 10 g / l

60% ammonium lauracurolsulfonate solution up to 100 % of the volume,

Example 4: 300 g / l chlorfenvinphos 25 g / l * - 'Emuisogen EL ethylene oxide / propylene oxide 25 g / l Block Copolyraer

60% Amraoniumcumolsulfonatlösung up to 100 % of

volume,

Example 5:

2- (2,4-0ichlorphenyl) -l- (lH-l, 2 _# 4-triazol-l-yl) pentane 100 g / l

Cyclohexanone 50 g / l

Xylene 50 g / l

© Emuisogen EL 25 g / l

Nonylphenol polyglycol ether (8 to 12 mol Eo) 25 g / l 60% ammonium curesulfonate solution up to 100 % of the

Volume.

Examples 1 to 5 are prepared by dissolving the active and the auxiliary auxiliaries in the aqueous solution of the sulfonic acid salt to form a homogeneous solution.

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fen 1.9 AP A 01 N / 239 802/0 - 11 - 1.9 60 853/11 Mixtures of two active substances 250 g / i Example 6a: 200 g / i propiconazole 70 carbendazim 5 ^ Soprophor FL ^ - 'Silicone antifoam MlO

ι 60% ammonium cumenesulfonate solution up to 100 % of

volume,

Example 6b:

Propiconazole 125 g / l

Carbendazim 100 g / l

^ Soprophor FL 50 g / l

®Aerosil COK 84 15 g / l 60% ammonium cumenesulfonate solution up to 100 % of

volume,

All of the components of Examples 6a and 6b are mixed by dissolving the propiconazole and soprophor FL in the ammonium cumene sulphonate solution and then adding the silicone antifoam and the carbendazim. After the carbendazim has been suspended in a suitable mixer, the mixture is wet ground, with a In Example 6b, the thickener, Aerosil COK 84, is dispersed in the formulation after wet milling with a high shear mixer.

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Example 7:

Metalaxyl copper oxychloride

80 g / l 690 g / l

30 g / l

Soprophor FL

Mowiol 40-88 10 g / l

60% ± ammonium chlorosulfonate solution up to 100 % of the

Volume.

The metalaxyl, soprophor FL and Mowiol 40-88 are dissolved in the ammonium curativesulfonate solution. Then the copper oxychloride is suspended in this solution and this suspension is ground to a fine suspension in a suitable wet grinding plant.

Example 8: 50 g / l metalaxyl 200 g / l Zi ram 15 g / i • 2 / Aerosil COK 84 200 s / i sodium cumene

Water up to 100 % of the volume «

Example 8 is prepared by dissolving the metalaxyl in the solution of sodium cumene sulfonate in water and suspending the ziram in this solution. After wet milling the suspension in a suitable mill, the Aerosil COK 84 is dispersed in the formulation with a high shear mixer.

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Claims (18)

23 98 0 2 0 ""> '' ·· * AP A Ol N / 239 802/0 - 13 - 60 853/11 claim for invention Aqueous pesticidal concentrate, characterized in that it contains ei) a liquid or solid, water-stable, substantially water-insoluble pesticide and β) an aromatic sulphonic acid or a salt of the formula Z-SO ₃ R ₄ R ₁ -I-II (i) 2. Concentrate according to item 1, characterized in that it contains up to 75% by weight / volume of the pesticide as component o * and up to 70% by weight / volume of the sulfonic acid of the formula I as component β * 2 ^R 3 in which R ₁ , R ₃ and R _{3 have} the same or different meaning and are hydrogen or straight-chain or branched C ₃ -Cg alkyl, Z is a direct bond or a straight-chain or branched C ₁ -C. Alkylene and R. hydrogen, an alkali metal, a Amtnoniumgruppe, a primary, secondary or tertiary amine group, a Hydroxyalkylamingruppe or a Morpholingruppe mean. Concentrate according to item 2, characterized in that it contains 5 to 50% by weight / volume of pesticide and 15 to 50% by weight / volume of sulfonic acid of formula I « 4. Concentrate according to one of the items 1 to 3, characterized in that the pesticide is liquid. 23 98 0 2 0 ι. «» AP A Ol N / 239 802/0 - 14 - 60 853/11 5. Concentrate according to one of the items 1 to 3 _f, characterized in that the pesticide is solid. Concentrate according to one of the above points, characterized in that Z is a direct bond * 7. Concentrate according to one of the above points, characterized in that R ₁ , R "and R 'have the same or different meaning and denote hydrogen or straight-chain or branched ^C i- ^C ₃ alkyl, 8. Concentrate according to one of the above points, characterized in that the compound of the formula I is ammoniumuracurol sulphonate, potassium xylene sulphonate, sodium toluene sulphonate, xylene sulphonic acid or sodium cumene sulphonate. Concentrate according to one of the preceding points, characterized in that a functional auxiliary agent is added, 10. A concentrate according to item 9, characterized in that the functional aid is one or more surfactants, an adhesive or thickener or an antifoam agent. 11. Concentrate according to item 9, characterized in that the formulation aid is one or more organic solvents, 12. Concentrate according to one of the items 4 or 6 to 11, characterized in that the liquid pesticide is chlorfenvinphos, metolachlor, propiconazole or imazalil. 2398 0 2 0 ¹ ^ ¹⁰ - ¹⁹⁸² AP A Ol N / 239 802/0 - 15 - 60 853/11 13. A concentrate according to any one of items 5 to 11, characterized in that the solid pesticide is 2- (2,4-oichlorophenyl) -I- (IH-I, 2, A- triazol-1-yl) -pentane or metalaxyl , 14. Concentrate according to one of the above points, characterized in that as a further component ( j *) a solid, not soluble in an aqueous solution of the compound of formula I pesticide is present. Concentrate according to item 14, characterized in that component (i) is propiconazole and component (c) is captan or carbendazirone or component (ot) is metolachlor and component (^) is atrazine or component (0) ) Imazalil and the component (E) is thiabendazole or that the component (s) is metalaxyl or 2- (2,4-dichlorophenyl) -1- (1H-l, 2,4-triazol-1-yl) -pentane and the component ( $ *) is copper oxychloride, ziram or folpet. 16. A process for preparing an aqueous solution concentrate according to item 1, characterized in that one dissolves component ( d ) in an aqueous solution of component (ß). 17. A process for the preparation of an aqueous concentrate according to item 14, characterized in that one prepares a solution of component (oC) in an aqueous solution of component (ß) and then the component ( f) is added and the mixture, if desired, to the desired Particle size of the solid components. 18. Aqueous concentrate, characterized in that it is prepared by a method according to one of the items 16 or.