FI69235C - PESTICIDE CONCENTRATE WITH VAT - 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 69235

Aqueous pesticide concentrates -Vattenhaltiga pesticide concentrates

The invention relates to aqueous pesticide concentrates of liquid and / or solid active ingredients which, although stable in water, are insoluble in water, whereby the concentrates can be diluted for spraying by the final consumer. The invention also relates to a process for the preparation of such preparations.

10 From the point of view of manufacturer chemists, many pesticide active ingredients can be considered to be insoluble in water. Their water solubility is usually less than 1.0% w / v; however, this is not a limiting factor within the scope of this invention. Solubilization of these compounds in an aqueous medium to prepare an aqueous concentrate has been difficult and in many cases impossible. When possible, the final product may be too low in concentration and may have poor storage stability, too low temperature stability, and is generally commercially unusable. For this reason, classical non-aqueous preparation techniques have usually been used for these active ingredients, or aqueous suspensions have been prepared if the melting point of the active ingredient is at least 70 ° C.

25 These preparation techniques depend on the physico-chemical properties of the active ingredient used, but can be broadly classified into three categories: 1. Emulsifiable Concentrates (EC) - when the active ingredient is soluble in oils. An emulsifier or surfactant is required in this type of preparation to ensure that the product forms a homogeneous emulsion when diluted for use with water. The main advantage of this type of preparation is that it is a liquid. The disadvantages of this type of manufacture are: firstly, large quantities of potentially harmful and expensive solvents are required and, secondly, 2,69235, these preparations are often packaged in expensive aluminum or tin plate containers for safety reasons.

2. Wettable or dispersible powders (WP) -if the active ingredient is insoluble in oils. Surfactants are needed in this type of preparation to ensure complete dispersion of the product in the water into which it is diluted by the final consumer. The main disadvantages of this type of preparation are, firstly, that it is a powder and therefore a potential dust hazard, and secondly, that the consumer has to weigh the powder in the field instead of measuring it by volume, as can be done with liquids.

3. Aqueous suspension concentrates (SC) - if the active ingredient is insoluble in oils and water and has a melting point of at least 70 ° C. Surfactants are needed in this type of preparation to suspend the finely ground ingredient in water. The main advantage of this type of preparation is that it is a liquid; its main disadvantages are its tendency to form non-redispersible fines and the fact that this type of preparation cannot be used for liquid and low-melting active ingredients even when used as ingredients.

Thus, if the active ingredient is soluble in "oil-25", it may be prepared as a liquid emulsifiable concentrate, if it is insoluble in "oils", then the usual method of preparing it is as a wettable powder or suspension concentrate if the melting point is high enough. However, all three of these 30-30 formulations have major disadvantages, with more than two others being wettable powder.

We have now found that several disadvantages associated with the preparation of the active ingredient mentioned in this application can be eliminated by the new preparation technique according to the invention.

Il 3 6Γ235

The main object of the invention is to provide aqueous pesticide solution concentrates of substantially water-stable and water-insoluble pesticidal active ingredients which are storage-stable and water-dilutable for the preparation of relatively stable emulsions and dispersions.

It is also an object of the invention to provide a method for formulating an active pesticide ingredient of the above type together with a water-insoluble solid active ingredient which cannot be formulated by the method of the present application alone.

The objects of the present invention are solved by using as a hydrotrope a group of compounds known as aromatic sulfonic acids and their salt derivatives. Thus, the present invention comprises an aqueous solution concentrate comprising a) a pesticide which is stable in water but substantially insoluble in water, and β) an aromatic sulfonic acid or a salt thereof having the formula f'SO3R4 S \ R, - + - ii Cl) R 2 * 3 wherein R 1, R 2 and R 2 are the same or different and each is hydrogen or a straight or branched alkyl group containing 1-6 (preferably 1-3) carbon atoms; Z is a straight or branched alkylene group containing 1 to 6 carbon atoms, or preferably a direct bond; and R 1 is hydrogen, an alkali metal, an ammonium group, a primary, secondary or tertiary amine group, a hydroxyalkylamine group or a morpholine group. The aqueous solution concentrates of the present invention can be prepared simply by dissolving the compound (a) in the aqueous solution of the compound (4).

4,69235

Aqueous solution concentrates preferably contain 5-75 w / v of the active ingredient (component a), preferably 5-50 w / v and 15-70 w / v of pure hydrotrope (component β), more preferably 15 - 50 wt / 5 vol.%.

Typical useful examples of compounds of formula I include ammonium cumene sulfonate (commercially available as a 60% aqueous concentrate); potassium xylene sulfonate (commercially available in solid form up to 100% active and up to 40% aqueous solution); sodium cumene sulfonate (commercially available in solid form up to 100%); sodium toluene sulfonate (commercially available in solid form as a 100% active solution and up to 40% aqueous solution); and xylenesulfonic acid (commercially available up to 90% in liquid form easily dilutable with water).

The extent to which a pesticide is soluble in hydrotropic silicon depends on three properties: 1) The water solubility of the pesticide (or an indirect measurement of its water solubility, e.g., as a Water Number), determined according to the method of Greenwald, Brown and Fineman (Anal. Chem. 2J8, 1693 (1956)); 2) the chemical structure of the hydrotrope; and 3) the concentration of hydrotrope in the manufactured product.

As a general rule, liquid pesticides with a water number of less than 10 are too lipophilic and insoluble in any commercial extent in aromatic sulfonic acid (salt) solutions; while pesticides with a water number greater than 30 10 can be prepared into commercial aqueous products using suitable aromatic sulfonic acids (salts). It is surprising to find that once a pesticide is dissolved in this type of hydrotrope, it disperses when diluted with water to form either an emulsion or a dispersion.

35 This phenomenon can occur without the use of emulsifiers or surfactants, which are essential for conventional

It 5 69235 emulsifiable concentrate using a hydrocarbon diluent.

However, it may be helpful to add functional excipients, such as surfactants and co-solvents, to the aqueous concentrates of the invention (to wet and permeate the leaves and to avoid crystallization of solid pesticides in dilute aqueous solutions, i.e. spray compositions), binders and preservatives. -10 for application) and antifoams to reduce foaming.

Examples of such functional excipients are: a) surfactants and co-solvents: nonyl-phenylethoxylates, e.g. of the commercially available N-type of thylan; alcohol and fatty acid ethoxylates, e.g. commercially available β-fetyl type C; and hydrocarbon solvents such as vegetable oils, naphthanes, xylenes or polyglycol ether; (B) fixing agents and thickeners: polyethylene glycols, polyacrylamide solutions and polyvinylpyrrolidone; and c) antifoams: silicone-based compounds and emulsions, fatty acids, e.g. coconut fatty acid, and ethylene oxide / propylene oxide block copolymers, such as commercially available luronic polyols.

6 69235 The common chemical names used in this specification correspond to the following chemical names: Name used_Chemical name__

Metolachlor 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide

Propiconazole 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole

Imazalil allyl [1- (2,4-dichlorophenyl) -2-imidazolyl- (1) -ethyl] ether

Tridemorph 2,6-dimethyl-4-tridecylmorpholine

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

Metalaxyl 2-methoxy-N- (2,6-dimethylphenyl) -N- (1-methoxycarbonyl-ethyl) -acetamide

Captan 3a, 4,7,7a-tetrahydro-2-1- (trichloromethyl) thio] -1H-isoindole-1,3 (2H) -dione

Carbendazim methyl 1H-benzimidazol-2-ylcarbamate

Atrazine 6-chloro-N-ethyl-N '- (1-methylethyl) -1,3,5-triazine-2,4-diamine

Thiabendazole 2- (4-thiazolyl) -1H-benzimidazole

Ziram (T-4) -bis- (dimethylcarbamodithioato- (S, S ') - zinc

Folpet 2 - [(trichloromethyl) thio] -1H-isoindole-1,3- (2H) -dione 7 69235

Examples of liquid and solid ingredients which are particularly suitable for use as component (a) of the new concentrates are given in the following tables:

Table 1:

Liquid active ingredients active type current new aqueous ingredient (derivative) preparation form metolachlor acetanilide EC (500g ai / 1) BCW (300g ai / 1) propiconazole triazole EC (250g ai / 1) ECW (250g ai / 1) WP ( 250g ai / kg) imazalil diazole EC (500g ai / l) ECW (500g ai / l) tridemorph morpholine EC (750g ai / l) ECW (500g ai / l) chlorfenvinphos phosphate EC (300g ai / l) ECW (300g ai / l) / 1)

Table 2:

Solid active ingredients active type current new aqueous ingredient (derivative) preparation form metalaxyl acylaniline WP (250g ai / 1) ECW (250g ai / 1) 2- (2,4-dithiazole EC (100g ai / 1) ECW (100g ai / 1) chlorophenyl) -1- (1H-1,2,4-triazolyl-1) pantane EC = emulsifiable concentrate WP = wettable powder ECW = emulsifiable concentrate in aqueous solution ai = active ingredient 69235

Although a few solid active ingredients are soluble in these hydrotropes, many water-insoluble solid active ingredients are not soluble to an acceptable degree. This phenomenon can be used to solve the second object of the present invention, i. to prepare a combination product comprising two or more active ingredients with a broader spectrum of biological activity, using aromatic sulfonic acid salt solutions as both suspending and solubilizing agents.

Thus, according to another embodiment of the present invention, there are provided aqueous concentrates comprising ingredients (a) and (β) as defined above and, as an additive (γ), a solid pesticide which is insoluble in the hydrotrope.

These three-component aqueous concentrates of the invention can be prepared by preparing a solution of component (a) in component (β), preferably, but not necessarily, using an additional surfactant; and then adding component (γ) to the resulting solution and optionally grinding the mixture to the desired particle size of solid component (γ).

The preparation obtained is: i) liquid ii) aqueous 25 iii) physically and chemically stable at high and low temperatures iv) dilutable with water to form a stable dilution suitable for spraying v) non-dusty compared to an equivalent wettable 30.

The use of an aromatic sulfonic acid salt solution as a hydrotrope and / or suspending medium for solid pesticides has the following advantages: a suspension prepared using these hydrotropes does not require any antifreeze or suspending additives, as commercial solutions of these hydrotropes can give all 11 9 69235 these properties into the final product.

This technique can also be used successfully to combine other liquid or solid active ingredients with other solid pesticides that are insoluble in the hydrotrope. The following tables provide examples:

Table 3:

Combination of liquid and solid pesticide: liquid (g) solid (γ) 10 propiconazole + captan propiconazole + carbendazim metolachlor + atrazine imazalil + thiabendazole

Table 4: Combining two solid pesticides: solid (a) solid (γ) metalaxyl + copper oxychloride metalaxyl + ziram metalaxyl + folpet 20 2- (2,4-dichloro + copper oxychloride phenyl) -1- (1H- 1,2,4-triatsolyy-1-yl) pentane

The following examples further illustrate the present invention:

Comparative Example A (current preparation) propiconazole 250 g / l emulsifiers 100 g / l hydrocarbon / aromatic 30 solvents 100% by volume 1 o 69235

Example 1: propiconazole 250 g / l of a 60% ammonium cumene sulfonate solution to form 100% by volume.

5 As can be seen from the above details, both preparations contain the same concentration of active ingredient, but Example 1 has the following advantages over Comparative Example A: i) it does not contain possible harmful solvents 10 ii) it has no flash point iii) it does not contain emulsifiers iv) it can be packaged in polyethylene containers and v) it is less toxic because it is water based.

Example 2: Propiconazole 125 g / l

®Soprophor FL

(Rhone Poulenc) 40 g / l 40% ammonium xylene sulfonate solution up to 100% v / v Example 3: metolachlor 300 g / l ®Tween 85 (Atlas Chemicals) 10 g / l 60% ammonium cumene sulfonate solution up to 100% v / v Example 4: chlorfenvinphos 300 g / l

® Emulsogen EL

(Hoechst AG) 25 g / l 30 ethylene oxide / propylene oxide block copolymer 25 g / l I) 1 692 35 60% ammonium cumene sulfonate solution up to 100% by volume Example 5: 2- (2,4-dichlorophenyl ) -1- (1H-1,2,4-5 thiazole-1) -pentane 100 g / l cyclohexanone 50 g / l xylene 50 g / l ®Emulsogen EL (Hoechst AG) 25 g / l nonylphenol polyglycol ether 10 (8- 12 moles eo) 25 g / l of a 60% ammonium cumene sulphonate solution up to 100% by volume

Examples 1-5 are prepared by diluting the active ingredient and any additives in the preparation into an aqueous solution of the sulfonic acid-15 salt to prepare a homogeneous solution.

Mixtures of the two active ingredients Example 6a: propiconazole 250 g / l 20 carbendazim 200 g / l ® Soprophor FL (Rhone Poulenc) 7 0 g / l ® Silicone antifoam M10 (Dow Corning) 5 g / l 60% ammonium cumene sulfonate solution up to 100 vol Example 6b; propiconazole 125 g / l carbendazim 100 g / l ®Soprophor FL (Rhone Poulenc) 50 g / l ®Aerosil COK 84 (Degussa) 15 g / l 30 60% ammonium cumene sulfonate solution up to 100% vol; ij_n 12 6 * 235

All of the ingredients of Examples 6a and 6b have been premixed by dissolving propiconazole and Soprophor FL in ammonium cumene sulfonate solution, followed by the addition of a silicone antifoam and carbendazim. After the carbendazim is suspended using a suitable mixer, the premix is ground wet to produce a fine suspension. In Example 6b, a thickener, Aerosil COK 84, is dispersed in the preparation after wet milling using a high shear mixer.

Example 7: metalaxyl 80 g / l copper oxychloride 690 g / l p

Soprophor FL (Rhone Poulenc) 30 g / l ®Mowiol 40-88 (Hoechst) 10 g / l 15% 60% ammonium cumene sulphonate solution up to 100% v / v

Metalaxyl, Soprophor FL and Mowiol 40-88 are dissolved in ammonium cumene sulfonate solution. The copper oxychloride is then suspended in this solution and ground in a suitable wet pressure mill to produce a fine suspension.

Example 8: metalaxyl 50 g / l ziram 200 g / l ®Aerosil COK 84 (Degussa) 15 g / l 25 sodium cumene sulfonate 200 g / l water up to 100% v / v

Example 8 is carried out by dissolving metalaxyl in a solution of sodium cumene sulfonate in water, and then dispersing the ziram in the solution. This suspension is then ground wet in a suitable mill to produce a fine suspension. Finally, Aerosil COK 84 is dispersed in the product using a high shear mixer.

Il

Claims (15)

65235 Claims; Aqueous solution concentrate, characterized in that it comprises a) 5-75 w / v% of a liquid or solid pesticide which is stable in water but substantially insoluble in water, and β) 15-70 w / v. an aromatic sulfonic acid or a salt thereof having the formula? -SO 3 R 4 ✓ \ R 1 -tryl -, λ \ wherein R 1, R 2 and R 3 are the same or different and each represents hydrogen or a straight-chain or branched alkyl group containing 1 -6 carbon atoms; Z is a direct bond or a straight-chain or branched alkylene group containing 1 to 6 carbon atoms; and R 4 is hydrogen, an early metal, an ammonium group, a primary, secondary or tertiary amine group, a hydroxyalkylamine group or a morpholine group. Concentrate according to Claim 1, characterized in that the pesticide is a liquid. Concentrate according to Claim 1, characterized in that the pesticide is solid. Concentrate according to one of the preceding claims, characterized in that Z is a direct bond. Concentrate according to one of the preceding claims, characterized in that R 1, R 2 and R 3 are the same or different and each represents hydrogen or a straight-chain or branched alkyl group containing 1 to 3 carbon atoms. Concentrate according to one of the preceding claims, characterized in that the compound of the formula I is ammonium cumene sulfonate, potassium xylene sulfonate, sodium toluenesulfonate, xylenesulfonic acid or 69235 sodium cumene sulfonate. Concentrate according to one of the preceding claims, characterized in that a functional additive is added. Concentrate according to Claim 7, characterized in that the functional additive is one or more surfactants, adhesives or thickeners and antifoams. Concentrate according to Claim 8, characterized in that the additive in the preparation is one or more organic solvents. Concentrate according to one of Claims 2 or 4 to 9, characterized in that the liquid pesticide is chlorfenvinphos (2-chloro-1- (2,4-dichlorophenyl) ethenyl diethyl phosphate), metolachlor (2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide), propiconazole (1- [2- (2,4-dichlorophenyl) -4-propyl-1, 3-dioxolan-2-ylmethyl-1H-1,2,4-triazole) or imazalil (allyl- [1- (2,4-dichlorophenyl) -2-imidazolyl- (1) -ethyl] -ether). Concentrate according to one of Claims 3 to 9, characterized in that the solid pesticide is 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazolyl-1) pentane or metalaxyl (2 methoxy-N- (2,6-dimethylphenyl) -N- (1-methoxycarbonyl-ethyl) -acetamide). Concentrate according to one of the preceding claims, characterized in that a solid pesticide which is insoluble in an aqueous solution of the compound of the formula I is also present as additive (γ). Concentrate according to Claim 12, characterized in that component (a) is propiconazole (1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1 , 2,4-triazole) and the component (γ) captan (3a, 4, 7,7a-tetrahydro-2 - [(trichloromethyl) thio] -1H-isoindole-1,3 (2H) -dione) or carbendazim ( methyl 1H-benzimidazol-2-yl carbamate); or as component (a) metolachlor (2-chloro- (I 15 69235 r1-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide) and as component (γ) atrazine (6-chloro-N-ethyl-N '- (1-methylethyl) -1,3,5-triazine-2,4-diamine) or as component (a) imazalil (allyl-11- (2, 4-dichlorophenyl) -2-imidazolyl- (1) -ethyl] -ether) and component (γ) thiabenzazole (2- (4-thiazolyl) -1H-benzimidazole) or component (a) is metalaxyl (2- methoxy-N- (2,6-dimethylphenyl) -N- (1-methoxycarbonylethyl) acetamide) or 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazolyl- (l) -pentane and the component (γ) copper oxychloride, ziram ((T-4) -bis- (dimethylcarbamethioate- (S, S ') - zinc) or folpet (2 - [(trichloromethyl) thio] - H-isoindole-lr3- (2H) -dione). A process for preparing an aqueous solution concentrate as defined in claim 1, characterized in that component (a) is dissolved in an aqueous solution of component (6). A process for preparing an aqueous concentrate as defined in claim 12, characterized in that a solution of component (a) is prepared in an aqueous solution of component (β) and then component (γ) is added to the resulting solution, and optionally grinding the mixture to the desired particle size.