CS248701B2 - Concentrated water solution of the pesticide - 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

The present invention relates to aqueous concentrates of liquid and / or solid pesticidally active substances which are stable in water but insoluble and which concentrates can be diluted by the user prior to practical application prior to spraying.

From the point of view of chemists involved in the preparation of active ingredients, many pesticide active substances can be considered to be insoluble in water. Their solubility in water is usually less than 1.0% (w / v), but this is not a limiting factor in the conditions of the present invention. Dissolution of these compounds in an aqueous medium into an aqueous concentrate is difficult and in many cases impossible. If dissolution is possible, the resulting substance may be present in too low a concentration and may have a short shelf life, low low temperature stability, and in general the end product may be commercially unacceptable. For such active substances, conventional methods of preparing non-aqueous compositions are used or aqueous suspensions are produced if the active ingredient has a melting point of at least 70 ° C.

These preparation methods depend on the physicochemical properties of the active ingredient, but can basically be classified according to the following three aspects:

(B)

1.

Emulsifiable concentrates (EC) - when the active ingredient is oil-soluble. In this type of formulation, an emulsifier or surfactant is required to form a homogeneous emulsion upon dilution with water. The main advantage of this type of formulation is that it is liquid. The disadvantages of this type of formulation are: firstly, a significant amount of potentially harmful and expensive solvents is needed; and secondly: for safety reasons, these devices are often packaged in expensive aluminum or tin containers.

2.

Wettable or dispersible powders (WP) - if the active ingredient is insoluble in oil. In this case, the addition of surfactants is required in order to achieve a perfect dispersion of the active ingredient in water upon final dilution with water. The main disadvantages of this type of formulation are that it is a powder and therefore there is a risk of dusting, and that the powder must be weighed in the field before application, rather than being metered in volume as in in the case of liquid formulations.

3.

Aqueous suspension suspensions (SC) - if the active substance is insoluble in water and oil and has a melting point of at least 70 ° C. For this type of composition, the addition of surfactants is required. to ensure ... .suspenr. dování. finely ground ingredients in water. The main advantage of this type of composition is that it is liquid. The main drawbacks lie in the effort to form a sediment which can no longer be dispersed again and in the fact that this type of composition cannot be used for. . ka-. even when added as excipients.

Accordingly, if the active ingredient is soluble in the oil, it can be processed to a liquid emulsifiable concentrate, but if it is not soluble in the oil, then the active ingredient is usually processed into a wettable powder or a suspension concentrate; if the melting point is high enough. All of these three types of formulations have a number of disadvantages, the wettable powder being less preferred than the other two. preparations.

It has been found that the numerous disadvantages associated with the processing of the active compounds mentioned in this application can be overcome by the new processing technique of the present invention.

It is an object of the present invention to provide concentrated aqueous solutions of practically water-stable but water-insoluble pesticides, which concentrates are storage-stable and which can be diluted with water to relatively stable emulsions or dispersions.

These objectives are achieved using a group of compounds known as aromatic sulfonic acids, and theirs. salts. . hydrotropes.

Subject. of the invention is that. concentrated. . · Aqueous pesticide solution; which. rests. In this case, the patient is -25.62 ..-. 5Q ...%. .· active substance, . which is stable in water and its solubility in water. water. Yippee . less than 1.0. · Percentage · (weight / volume), and ../3).· z / 15. to. · 50. percent .. (weight / volume); . aromattckérsul-. · phonic. . acids or,. salts thereof; of formula I

Z represents a direct bond or does not mean a straight or branched alkylene group containing 1 to 6 carbon atoms, wherein. preferably means a direct bond,

Rd represents hydrogen, an alkali metal, an ammonium group, a radical of a primary, secondary or tertiary amine containing in the alkyl moiety of 1 to 4 carbon atoms of the remainder of the ethanolamine residue of diethanolamine . or a moriolino group.

Concentrated aqueous solutions of the present invention can be prepared in a simple manner. By dissolving component () in an aqueous solution of compound (3).

The concentrated aqueous pesticide solution according to the invention preferably contains 5 to 50% (w / v) of the active ingredient [ingredient]

(w / v) of an aromatic sulfonic acid or a salt thereof.

Typical examples of useful compounds of formula I include the ammonium salt of Rumenesulfonic acid (commercially used as .60%: scientific concentrate); . xylenesulfonic acid potassium salt (commercially available in solid form containing up to 100% active ingredient and up to 40% aqueous solution); cumensullonic acid sodium salt (marketed in solid form with up to 100% active ingredient); toluene sulphonic acid sodium salt (commercially available in solid form with up to 100% active ingredient and in aqueous solution containing up to 40% active ingredient); And - xylenesulfonic acid (commercially available in liquid form containing up to 90% of the active ingredient which can be easily diluted with water).

The ability of the pesticide to dissolve in the hydrophilic composition. Dependent: on. · The following three; properties:

1 .. · ^ хриз-ШоеТ; · pesticide ·. in water (or solubility, of a pesticide in water) as determined by indirect measurement as a so-called "Water · Number" (hereinafter referred to as "WN.") according to the method by which. described by Greenwald, Brown, and Fineman; Anal; Chom. 28, 1693 (1956);

2, - · chemical · structure · · hydrotropic. · folders;,

3. concentration = hydrotropic components of the composition to be formulated.

The general rules are liquid. pesticides: p. value. .WN less than · .10. · too much·. lipophilic and substantially soluble in the aromatic, sulfonic acid (salt) solutions. to any commercial degree. Pesticides with a WN value above 10 are possible. On the other hand, to be processed into commercial formulations and on an aqueous basis using suitable aromatic sulfonic acids (salts). S. by surprise, it was found that. · · once ; Is a pesticide soluble in this type of hydrotrope, it can be dispersed or dissolved in water to either form an emulsion or dispersion. Without the use of emulsifiers or surface-active agents, which are important in the case of conventional emulsifiable concentrates using hydrocarbon diluents.

in which

Ri, ·· Rž. and · Rs · are the same or. · Each other, different. · · A. . is hydrogen or. A straight or branched alkyl group. containing 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms. · 3 ·.

carbon atoms,

However, it may be beneficial to add to the aqueous concentrates of the present invention an adjuvant such as a surfactant or an auxiliary solvent (to improve leaf compatibility and to improve penetration and to prevent crystallization of solid pesticides in a dilute aqueous solution, i.e. a spray composition), adhesives and thickeners (to provide adhesion to the sheet and to control droplet dimensions) and antifoams to reduce foaming.

Examples of such aids are:

(a) surfactants and co-solvents: ethoxylated nonylphenol, for example the product used under the trade name ( ^R) Ethylan N; ethoxylated alcohols and fatty acids, for example the product known under the trade name ^(R ) Ethylan

C; and hydrocarbon solvents such as natural oils, petroleum, xylenols and polyglycol ethers;

(b) adhesives and thickeners: polyethylene glycols, polyacrylamide solutions and polyvinylpyrrolidone;

c) anti-foaming agents: silicone-based compounds and emulsions, fatty acids such as coconut fatty acid and block copolymers of ethylene oxide and propylene oxide, such as commercially available Pluronic polyols.

Examples of liquid and solid active ingredients which are particularly suitable for use as components · (a) in the concentrated aqueous solution of the invention are given in the following tables:

TABLE 1

Active ingredient Liquid active ingredients: New water-based product Type (derivative) Common product Metolachlor acetanilide EC (500 g A. S / ltr) ECW (300 g A.S.) /liter) Propiconazole triazole EG (250 g A.S / liter) ECW (250 g A.S.) WP (250 g A.S./kg) /liter) Imazalil diazol EC (500g A. ECW (500 g A.S.) /liter) Tridemorph morpholine EC (750 g A / liter) ECW (500 g A.S.) /liter) Chlorfenvinphos foslíát EC (300 g A.S / liter) ECW (300 g A.S.)

/liter)

TABLE 2

Solid active ingredients:

Active ingredient Type (derivative) Common remedy New water-based product Metalaxyl 2- (2,4-Dichlorophenyl) -1- (1H, 1,2,4-tri- acylalanine triazole WP (250 g A.S./kg) EC (100 g A.S / liter) ECW (250 g A.S. / / liter) ECW (100 g A.S. / / liter)

azol-1-yl) pentane

EC = emulsifiable concentrate

WP = wettable powder

ECW = emulsifiable concentrate in the form of an aqueous solution A.S. = active ingredient

Common names used in the previous as well as in the next section

The common name of the description corresponds to the following chemical names:

Chemical? name

Métolachlor

Propiconazole

Imazalil

Tridemor.ph

Chlorfenvinphos

Metalaxyl

Captan

Carbendazim

Atrazine

Thiabendazole

Copper oxychloride

Ziram

Folpet

2-chloro-N- (2-ethyl-6-methylphenyl) -N-

- (2-methoxy-1-methylethyl) acetamide

1- [2- (2,4-Dichlorophenyl) -4-propyl-1,3-

dioxolan-2-ylmethyl] -lH-l, 2,4-triazole allyl- _[4 l - (. 2, IL-dichlorophenyl) -2-imidazol-ylethyl] ether, 2,6-dimethyl-4.- tridecylmorpholine

2-chloro-1- (2,4-dichlorophenyl) ethenyl diethyl phosphate

2-methoxy-Nr (2,6-dimethylphenyl) -N-

(1-Methoxycarbonylethyl) acetamide 3a, 4,7,7a4-tetrahydro-2 - [. 6-chloro-N-ethyl-N '- (1-methylethyl) -1,3,5-triazine (trichloromethyl) thiol-1H-isoindole-1,3 (2Ή) -dione methyl-1H-benzimidazol-2-ylcarbamate -2,4-diamine Z-thiazolyl-1H-benzimidazole cupric oxychloride Cu (OH) 3 Cl zinc dimethyldithiocarbamic acid zinc salt

2 - [(trichloromethyl) thio] -1H-isoindole-1,3- (2H) -dione.

Although some solid active ingredients are soluble in these hydrotropic substances, there are many water-insoluble solid active ingredients that are not soluble in the hydrotropic material to a significant extent. This phenomenon can be used to realize the second object of the invention, i.e. to produce a combined a composition comprising two or more active ingredients having a broader spectrum of biological activity using aromatic salt solutions; sulfonic acids as suspending agents and solvents.

Accordingly, a further object of the present invention is an aqueous concentrate comprising the components (1) and (1) as defined above, and further as a further component (6), a solid pesticidal active substance that is not soluble in the hydrotreated component.

The three-component aqueous concentrate of the invention can be prepared by preparing a solution of component tt) in component (3), preferably but not necessarily, using a surfactant and then adding component y) to the resulting solution and optionally grinding the mixture to achieve the desired size. particles of solid component y).

The resulting resource is a resource with the following properties:

(i) it is liquid, (ii) is water-based (iii) is physically and chemically stable at both high and low temperatures, (iv) can be diluted with water to a stable solution suitable for spray application,

(v) compared to the equivalent wettable. powder-free.

The use of aromatic sulfonic acid salt solutions as a hydrotropic component and / or as a suspending medium for solid pesticides has the following advantages: a suspension prepared using these hydrotropic fractions may not contain antifreeze or suspending agents as commercial solutions of these hydrotropic components may transfer all of these properties to final means.

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

TABLE 3

Combinations of liquid and solid pesticides:

Liquid pesticide (a)

Propiconazole + Propiconazole + Métolachlor + Imazalil +

Solid pesticide (Г)

Captan Carbendazim Atrazine Thiabendazole

8 70’1

TABLE 4

Example 4

Combination of two solid pesticides:

Chlorfenvinphos

300 g / liter

Solid pesticide (s)

Solid pesticide (r)

Metalaxyl

Metalaxyl Metalaxyl 2- (2,4; -dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) pentane + copper oxychloride

-I- I gaze + Folpet + copper oxychloride

Emulsogen EL (manufactured by Hoechst AG) block polymer of ethylene oxide and propylene oxide cumene sulfonic acid ammonium salt solution g / liter g / liter up to 100% by volume.

The following examples illustrate the invention but do not limit it:

Comparative Example A (conventional means)

Propiconazole hydrocarbon / aromatic emulsifier as solvent

250 g / liter

100 g / liter up to 100% vol

2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) -pentane 100 g / liter cyclohexanone 50 g / liter xylene 50 g / liter

Emulsogen EL (manufactured by Hoechst AG) 25 g / liter nonylphenol polyglycol ether up to 12 moles ethylene oxide) 25 g / liter

60% solution of cumene sulphonic acid ammonium salt up to 100% vol.

Example 1

Propiconazole

60% solution of cumene sulfonic acid ammonium salt

250 g / liter up to 100% vol.

It follows from the above that both compositions contain the same concentration of active ingredient, however, the composition of Example 1 has. over the composition described in Comparative Example A, the following advantages:

The compositions described in Examples 1-5 are prepared by dissolving the active ingredient and the adjuvants in an aqueous solution of the succinic acid salt to form a homogeneous solution.

Mixtures containing two active ingredients:

Example 6 a

Propiconazole Carbendazim

250 g / liter

200 g / liter

(i) contains no potentially dangerous solvents; (ii) is not flammable; (iii) contains no emulsifier; (iv) can be packaged in polyethylene containers; and

(v) it is less toxic because it is water-based.

Example 2

Propiconazole 125 g / liter

Soprophor FL (manufactured by Rhone Poulenc) 40 g / liter

40% solution of ammonium salt of xylene sulphonic acid up to 100% by volume.

Example 3

Metolachlor 300 g / liter / Sv

Tween 85 (product of company

Atlas Chemicals) 10 g / liter

60% solution of cumene sulphonic acid ammonium salt up to 100% vol.

& Soprophor FL (manufactured by Rhone Poulenc) (§)

Silicone antifoam M10 (manufactured by Dow Corning) 5 g / liter 60% solution of cumene sulfonic acid ammonium salt up to 100% by volume.

Example 6b

Propiconazole 125 g / liter Carbendazim 100 ALIGN! g / liter Soprophor FL (product Rhone Poulenc) 50 g / liter Aerosil ® COK 84 (product Degussa) 15 Dec g / liter

60% solution of ammonium salt, cumene sulphonic acid up to 100% by volume.

All ingredients listed in Example 6a and

6b are processed by preparing a premix by dissolving Propiconazole and Soprophor. FL. in a solution of the ammonium salt of cumene48701 sulfonic acid. Then copper oxychloride is suspended in this solution and the suspension is wet ground in a suitable mill to a fine suspension.

Example 8 sulfonic acid. Silicone antifoam and Carbendazim are then added. This mixture is stirred using a suitable stirrer. When the Carbendazim is suspended, the premix is ground to a fine suspension. In the case of Example 6b, the thickener, Aerosil COK 84, is dispersed in the formulation only after wet grinding using a shear mixer.

Metalaxyl Ziram

Example 7

Aerosil COK 84 (product g / lltr

200 g / liter

Copper metalaxyl oxychloride

Soprophor FL (manufactured by Rhone Poulenc)

Mowiol 40-88 (manufactured by Hoechst)

60% solution of cumene sulfonic acid ammonium salt

690 g / liter g / liter g / liter g / liter up to 100% vol.

Metalaxyl, Soprophor FL and are dissolved in a solution of the ammonium salt of cumene (Mowiol 40-88 from Degussa) sodium cumene sulfonic acid water g / liter

200 g / liter up to 100% vol.

Metalaxyl is dissolved in a solution of cumene sulfonic acid sodium salt in water and then Ziram is dispersed in the solution. The suspension obtained is then wet milled on a suitable mill to form a fine suspension. Finally, Aerosil COK 84 is dispersed in this suspension by means of a high shear mixer.

Claims (14)

A concentrated aqueous solution, characterized in that it consists of 50% (w / v) of a liquid pesticidal active substance which is stable and has a water solubility of less than 1.0% (w / v a / 3) of 15 to 20% by weight. 50% (w / v) of an aromatic sulfonic acid or a salt of the general formula I in which: R 1, R a and R 3 are the same or different from each other and are hydrogen or a straight or branched (C 1 -C 6) alkyl radical, Z represents a direct bond or a straight or branched alkylene chain of 1 to 6 carbon atoms, R a represents hydrogen, an alkali metal, an ammonium group, a primary radical, an alkali metal, an ammonium group, a radical of a primary radical. a secondary or tertiary amine containing in the alkyl moiety a (C 1 -C 4) alkyl, an ethanolamine residue, a diethanolamine residue or a mono-amino group. 2. A concentrated aqueous solution according to claim 1, wherein the pesticide is a pesticide in the form of a liquid. OF THE INVENTION 3. Concentrated aqueous solution according to claim 1 or 2, characterized in that the pesticide is a solid pesticide. A concentrated aqueous solution according to any one of the preceding claims, characterized in that it comprises, as component (3), a sulfonic acid or its salts of the general formula I, wherein Z represents a direct bond and R 1 to R 4 have the meaning given in point 1. A concentrated aqueous solution according to any one of Claims 1 to 3, characterized in that it comprises as component (R) a sulfonic acid or a salt thereof of the general formula I, wherein R 1, R a and R 3 are the same or different from each other and are hydrogen or straight or branched (C až-C alky) alkyl and R R and Z are as defined in 1. 6. A concentrated aqueous solution according to claim 4, characterized in that it comprises as component (3 ') a sulfonic acid or a salt thereof of the general formula I, wherein R1, R2 and R3 are the same or different from each other and are hydrogen or. straight or branched (C 1 -C 3) alkyl, Z is a direct bond and R 4 is as defined in (1). Concentrated aqueous solution according to any one of the preceding claims, characterized in that it contains, as a compound of formula I, the ammonium salt of cumenesulfonic acid. xylene sulfonic acid potassium salt, toluene sulfonic acid sodium salt, xylenesulfonic acid sodium or cumene sulfonic acid sodium salt. A concentrated aqueous solution according to any one of the preceding claims, characterized in that it comprises an adjuvant. 9. A concentrated aqueous solution according to claim 8, characterized in that it contains at least one surfactant, adhesive or thickener and an antifoaming agent as adjuvant. A concentrated aqueous solution according to claim 8, characterized in that it contains at least one organic solvent as auxiliary. A concentrated aqueous solution according to any one of Claims 2 or 4 to 10, characterized in that the liquid pesticidal active ingredient is 2-chloro-1- (2,4-dichlorophenyl) ethenyldiethylphosphate, 2-chloro N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide, 1- (2- (2,4-dichlorophenyl) -4-propyl-1,3 -dioxolan-2-ylmethyl] -1H-1,2,4-triazole or ally 1- [1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl] ether. Concentrated aqueous solution according to one of Claims 3 to 10, characterized in that it contains 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) as a solid pesticidal active substance. pentane or 2-methoxy-N- (2,6-dimethylphenyl) -N- (1-methoxycarbonylethyl) acetamide. A concentrated aqueous solution according to any one of the preceding claims, characterized in that it comprises a further component (y) represented by a solid pesticide which is not soluble in the aqueous solution of the compound of formula I. 14. A concentrated aqueous solution according to claim 13, wherein the component comprises 1- [2- (2,4-dichlorophenyl-4-propyl-1,3-dioxolan-2-ylmethyl) -1H-1,2. 4-triazole and as component y] contains 3a, 4,7,7a-etahydro-2 - [(trichloromethyl) thio] -1H-isoindole-1,3 (2H) -dione or methyl-1H-benzimidazole-2 -ylcarbamate, or as component ()) contains 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide and as component χ) contains 6-chloro-N-ethyl-N '- [1-phenyl] ethyl] -1,3,5-triazine-2,4-diamine, or as component a) contains allyl-1- [2,4-dichlorophenyl] -24-imidazol-1-yl-ethyl] ether and as component χ) contains 2- (4-thiazolyl) -1H-benzimidazole or contains as component 2) 2-methoxy-N- (2,6- (4-thiophen-1-yl) phenyl) -N- (1- methoxycarbonylethyl] acetamide or 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) pentane and as component y] contains copper oxychloride of formula Cu (OH) 3Cl, zinc dimethyldithiocarbamic acid zinc salt or 2 - [(trichloromethyl] thio] -1H-isoindole-1,3- (2H) - dion.