WO2017157678A1

WO2017157678A1 - Reduced photodegradation by co-dissolving pyraclostrobin and uv absorber

Info

Publication number: WO2017157678A1
Application number: PCT/EP2017/054864
Authority: WO
Inventors: Murat Mertoglu; Marcus Annawald; Rainer Berghaus
Original assignee: Basf Se
Priority date: 2016-03-17
Filing date: 2017-03-02
Publication date: 2017-09-21

Abstract

The present invention relates to a method of controlling phytopathogenic fungi, which comprises the steps of a) dissolving pyraclostrobin and a water-insoluble UV absorber in an organic solvent to provide a solution, b) converting the solution into an agrochemical formulation by optionally adding auxiliaries, c) dispersing the agrochemical formulation in water to provide a tank mix, and d) allowing the tank mix to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment. The invention further relates to an agrochemical formulation comprising a solution of pyraclostrobin and a water-insoluble UV absorber in an organic solvent; and to a method for preparing the tank mix which comprises the steps of a), b) and c).

Description

Reduced photodegradation by co-dissolving pyraclostrobin and UV absorber

The present invention relates to a method of controlling phytopathogenic fungi, which comprises the steps of

a) dissolving pyraclostrobin and a water-insoluble UV absorber in an organic solvent to provide a solution,

b) converting the solution into an agrochemical formulation by optionally adding auxiliaries, c) dispersing the agrochemical formulation in water to provide a tank mix, and

d) allowing the tank mix to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment.

The invention further relates to an agrochemical formulation comprising a solution of pyraclostrobin and a water-insoluble UV absorber in an organic solvent; and to a method for preparing the tank mix which comprises the steps of a), b) and c). The preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another.

Pyraclostrobin (CAS No 175013-18-0) might be sensitive to sunlight and decompose. The decomposition might already take place already during storage or even more after application to the environment. As a result, the pesticidal activity decreases, higher amounts of pyraclostrobin have to be applied, pyraclostrobin has to be applied in shorter intervals, or eventually toxic degradation products are produced.

Agrochemical formulations comprising pyraclostrobin and an organic UV absorbers are known.

The object of the invention was to provide an method which reduces the decomposition of pyraclostrobin due to sunlight, especially due to ultraviolet (UV) light. Another object was to increase the stability of agrochemical formulation of pyraclostrobin during storage and/or after application to the environment. Yet another object was to increase the pesticidal activity of pyraclostrobin formulations after application to the environment.

The objects were achieved by a method of controlling phytopathogenic fungi, which comprises the steps of

a) dissolving pyraclostrobin and a water-insoluble UV absorber in an organic solvent to pro- vide a solution,

d) allowing the tank mix to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment. The objects were also achieved by an agrochemical formulation comprising a solution of pyra- clostrobin and a water-insoluble UV absorber in an organic solvent. Preferably, the agrochemical formulation is obtainable by dissolving pyraclostrobin and the water-insoluble UV in the organic solvent to provide the solution.

The objects were also achieved by a method for preparing the tank mix which comprises the steps of a), b) and c).

The objects were also achieved by an agrochemical formulation comprising a solution of pyra- dostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones, benzotria- zoles, or triazines, preferably 2-hydroxy-4-octyloxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6- di-tert.-pentylphenol, or 2-(4-(4,6-bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester, in an organic solvent. Suitable UV absorbers are:

A) benzotriazoles, such as 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1 -phenylethyl)phenol (Tinuvin® 900, CIBA AG), [3-[3-(2H-benzotriazol-2-yl)-5-(1 ,1-dimethylethyl)-4-hydroxy- phenyl]-1-oxopropyl]-w-[3-[3-(2Hbenzotriazol-2-yl)-5-(1 ,1-dimethylethyl)-4-hydroxyphenyl]-1 - oxopropoxy]poly(oxy-1 ,2-ethanediyl) (Tinuvin® 1 130, CIBA AG), 6-tert.-butyl-2-(5-chloro-2H- benzotriazol-2-yl)-4-methylphenol, 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetra- methylbutyl)-phenol, 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4,6- bis(1-methyl-1-phenylethyl)phenol;

B) Cyanoacrylates, such as ethyl 2-cyano-3-phenylcinnamate (Uvinul^® 3035, BASF SE), 2-cy- ano-3,3-diphenylacrylic acid-2'-ethylhexyl ester or 2-ethylhexyl-2-cyano-3-phenylcinnamate

(octocrylene, Uvinul^® 539 T, Uvinul 3039, BASF SE);

C) para-aminobenzoic acid (PABA) derivatives, especially esters, such as ethyl-PABA, ethox- ylated PABA, ethyl-dihydroxypropyl-PABA, Glycerol-PABA, 2-ethylhexyl 4-(dimethylamino)- benzoate (Uvinul^® MC 80), 2-octyl 4-(dimethylamino)benzoate, amyl 4-(dimethylamino)ben- zoate;

D) esters of salicylic acid, such as 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homo- menthyl salicylate, TEA salicylate (Neo Heliopan^® TS, Haarmann and Reimer), dipropyl- eneglycol salicylate;

E) esters of cinnamic acid, such as 2-ethylhexyl 4-methoxycinnamate (Uvinul® MC 80), octyl-p- methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, , conoxate, diisopropyl methylcinnamate, etocrylene (Uvinul® N 35, BASF SE);

F) benzophenones, such as 2-hydroxy-4-methoxybenzophenone (Uvinul® M 40, BASF SE), 2- hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-(4- diethylamino-2-hydroxybenzoyl)-benzoic acid hexylester (Uvinul® A Plus, BASF SE), 4-n- octyloxy-2-hydroxy-benzophenone (Uvinul® 3008, BASF SE), 2-hydroxybenophenone derivatives such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy- , 4, 2', 4'- trihydroxy-, 2'-hydroxy-4,4'-dimethoxy-2-hydroxybenzophenone;

G) 3-benzylidenecamphor and derivatives thereof, such as 3-(4'-methylbenzylidene) o -camphor, benzylidiene camphor sulfonic acid (Mexoryl^® SO, Chimex); H) esters of benzalmalonic acid, such as 2-ethylhexyl 4-methoxybenzmalonate;

I) triazines, such as dioctylbutamidotriazone (Uvasorb® HEB, Sigma), 2,4,6-trinanilino-p- (carbo-2'-ethyl-hexyl-1 '-oxy)-1 ,3,5-triazine (Uvinul® T 150, BASF SE), 2-[4-[(2-Hydroxy-3-(2'- ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6bis(2,4-dimethylphenyl)-1 ,3,5-triazine (Tinuvin® 405, CIBA AG), anisotriazine (Tinosorb® S, CIBA AG), 2,4,6-tris(diisobutyl 4'-aminobenzalmalo- nate)-s-triazine;

J) Propane-1 ,3-diones, such as, 1 -(4-tert-butylphenyl)-3-(4'-methoxyphenyl)propane-1 ,3-dione; K) benzoylmethanes, such as, 1 -(4'-tert-butylphenyl)-3-(4'-methoxyphenyl)propane-1 ,3-dione, 4- tert-butyl-4'-methoxydibenzoylmethane or 1-phenyl-3-(4'-isopropylphenyl)propane-1 ,3-dione.

In another form suitable UV absorbers are A) benzotriazoles, such as 2-(2H-benzotriazole-2-yl)- 4-methyl-6-(2-methyl-3- ((1 ,1 ,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)-propyl)phenol, 2- (2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert.-butyl-2'- hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phe- nyl]benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert.-butyl- 2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec.-butyl-5'-tert.-butyl- 2'-hydroxy- phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert.-amyl-2'-hy- droxyphenyl)benzotriazole, 2-[3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl]benzotriazole, 2- [3'-tert.-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert- butyl-5'-(2-(2-ethylhexyloxy)-carbonylethyl)-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2[3'-tert.- butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert.-butyl-2'- hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert.-butyl-2'-hydroxy-5'-(2-oc- tyloxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert.-butyl-5'-(2- (2-ethylhexyloxy)carbonylethyl)- 2'-hydroxyphenyl]benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'- tert.-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2'-methylen-bis[4- (1 ,1 ,3,3-tetramethylbutyl)-6- benzotriazol-2-yl-phenol], esterfied product of 2-[3'-tert.-butyl-5'-(2- methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethylenglycol 300, [R- CH₂CH2-COO(CH₂)3-]2 with R being 3'-tert.-butyl-4-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'- hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2'-hydroxy- 3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)phenyl]benzotriazole;

In another form suitable UV absorbers are I) triazines, such as 2,4,6-Tris-{N-[4-(2-ethylhex-1 - yl)oxycarbonylphenyl]amino}-1 ,3,5-triazine, 4,4'-((6- (((tert.-butyl)aminocarbonyl)phenylamino)- 1 ,3,5-triazin-2,4-diyl)imino)bis(benzoic acid-2'-ethylhexylester); 2,4,6-tris(2-hydroxy-4-octyloxy- phenyl)1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis-(2-hydroxy-4-propy- loxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dime- thylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis-(2,4-di- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-di- methylphenyl)-1 ,3,5-triazine, 2-[2-Hydroxy-4(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis- (2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-Hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)4,6-diphenyl-1 ,3,5-triazine, 2,4,6-Tris[2- hydroxy-4-(3-butoxy-2- hydroxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxy-phenyl)-4-(4-methoxyphenyl)-6-phenyl- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6- bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2-(4-(4,6-bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxy- phenoxy) propanoic acid isooctyl ester.

Preferred UV absorbers are selected from benzotriazoles A) (e.g. 2-(2H-benzotriazol-2-yl)-4,6- di-tert.-pentylphenol), benzophenones F), triazine I), or their mixtures. In a preferred form the UV absorber comprises a benzotriazole A), e.g. 2-(2H-benzotriazol-2-yl)- 4,6-di-tert.-pentylphenol).

In another preferred form the UV absorber comprises a benzophenone F). In another preferred form the UV absorber comprises a triazine I), e.g. 2-(4-(4,6-bis((1 ,1 '-bi- phenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester.

More preferred UV absorbers are benzophenones selected from 2-hydroxy-4-methoxybenzo- phenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophe- none, 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexylester, and 2-hydroxy benzophenone derivatives (such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4- benzyloxy-, 4, 2', 4'- trihydroxy-, and 2'-hydroxy-4,4'-dimethoxy- 2-hydroxybenzophenone), or their mixtures. Even more preferred UV absorbers are benzophenones selected from 2,2'-dihydroxy-4-methox- ybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-octyloxybenzophenone; 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid, hexyl ester; 2,2' ,4,4'-tetrahydroxybenzophe- none, or their mixtures. The UV absorber is in particular 2-hydroxy-4-octyloxybenzophenone.

Preferably, no further UV absorber beside the UV absorber selected from benzophenones is used in the method. More preferably, no further UV absorber beside the UV absorber selected from 2-hydroxy-4-octyloxybenzophenone is used in the method.

The UV absorber is water-insoluble and may have a solubility in water of up to 10 g/l, preferably up to 1 .0 g/l, more preferably 0.5 g/l and in particular up to 0.1 g/l, e.g. at 20 °C. The solubility in water of the UV absorber may be determined at pH 7. The UV absorbers are usually organic UV absorbers. Typically, inorganic UV absorbers do not dissolve in an organic solvent.

The term "UV absorber" may be understood as meaning organic substances which are able to absorb ultraviolet rays and give off the absorbed energy again in the form of longer-wave radiation, e.g. heat. Typically, UV absobers absorb light of wawelenghts between 200 and 600 nm. The weight ratio of the pyraclostrobin to the UV absorber is typically in the range from 50:1 to 1 :1 , preferably from 20:1 to 3:1 , and in particular from 15:1 to 5:1 . In another form the weight ratio of the pyraclostrobin to the UV absorber is typically in the range from 30:1 to 1 :2, preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1.

The agrochemical formulation may comprise from 0.5 to 20 wt%, preferably from 0.8 to 10 wt%, and in particular from 1.0 to 5.0 wt% of the UV absorber. In another form the agrochemical formulation may comprise up to 4.0 wt%, preferably up to 3.0 wt% and in particular up to 2.5 wt% of the UV absorber.

The agrochemical formulation may comprise further pesticides in addition to pyraclostrobin.

In a preferred form the invention relates to the method of controlling phytopathogenic fungi, which comprises the steps of

a) dissolving pyraclostrobin and a water-insoluble UV absorber (e.g. benzophenone derivatives selected from 2,2'-dihydroxy-4-methoxybenzophenone; 2-hydroxy-4-methoxybenzo- phenone; 2-hydroxy-4-n-octyloxybenzophenone; 2-(4-diethylamino-2-hydroxybenzoyl)- benzoic acid, hexyl ester; 2,2' ,4,4'-tetrahydroxybenzophenone, or their mixtures) in an organic solvent to provide a solution,

d) allowing the tank mix to act on the respective pests, their environment or the plants to be protected from the respective pest, and/or the crop plants and/or their environment. The organic solvent may be water-soluble (e.g. having a solubility in water of at least 1 wt%, preferably at least 5 wt%, and in particular at least 10 wt% at 20 °C) or water-insoluble (e.g. having a solubility in water of up to 10 wt%, preferably up to 5 wt%, and in particular up to 1 wt% at 20 °C). The solubility in water of the organic solvent may be determined at pH 7. Suitable organic solvents are mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propa- nol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

The agrochemical formulation may comprise 10 to 70 wt% of the organic solvent.

The weight ratio of the organic solvent to the UV absorber is usually in the range from 50:1 to 3:1 , preferably from 40:1 to 5:1 , and in particular from 30:1 to 10:1. In another form the weight ratio of the organic solvent to the UV absorber is usually in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 . In a preferred form the organic solvent comprises a water-insoluble organic solvent, and the ag- rochemical formulation is selected from emulsifiable concentrates (EC), suspoemulsion concentrates (SE), or microcapsules (CS). The agrochemical formulation selected from EC or CS may comprise 15 to 65 wt%, preferably 20 to 55 wt% and in particular 25 to 45 wt% of the water-in- soluble organic solvent. The agrochemical formulation selected from SE may comprise 5 to 50 wt%, preferably 10 to 40 wt% and in particular 15 to 30 wt% of the water-insoluble organic solvent. Suitable water-insoluble organic solvents are mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; and mixtures thereof.

Suitable microcapsules (CS) are polyurethane microcapsules. Typically, the polyurethane comprises polyfunctional isocyanate and polyfunctional amine in polymerized form. Preferred polyi- socyanates are isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, and toluene diiso- cyanates. In another preferred embodiment, the polyisocyanate comprises an aromatic polyiso- cyanate, such as toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphenyl- methene-4,4'-diisocyanate (MDI), preferably MDI. In another preferred embodiment, the polyisocyanate comprises an oligomeric isocyanate, which are described above. Preferred polyfunctional amines are aliphatic polyamines, such as α,ω-diamines of the formula hbNHChbJn-NI-b, wherein n is an integer from 2 to 6. Examples of such diamines are ethylenediamine, propylene- 1 ,3-diamine, tetramethylenediamine, pentamethylenediamine and hexame-thylenediamine. A preferred diamine is hexamethylenediamine. The average particle size of the microcapsules (z- average by means of light scattering; preferably a D4,3 average) is 0.5 to 50 μηη, preferably 0.5 to 8 μηη, more preferably 1 to 5 μηη, and especially 1 to 3 μηη. The CS agrochemical formulation may comprise 10 to 450 g/l encapsulated pyraclostrobin, 50 to 450 g/l water insoluble organic solvent, 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1 ,0 I. More preferably, said composition comprises 100 to 350 g/l encapsulated pyraclostrobin, 150 to 400 g/l water-insoluble organic solvent, 10 to 60 g/l surfactant, and water up to 1 ,0 I. In another preferred embodiment, the CS comprises 10 to 300 g/l polyisocyanate and 0,5 to 30 g/l polyamine. More preferably, the CS comprises 50 to 150 g/l polyisocyanate and 1 to 10 g/l polyamine.

In another preferred form the organic solvent comprises a water-soluble organic solvent and the agrochemical formulation is selected from dispersible concentrates (DC). The agrochemical formulation selected from DC may comprise 20 to 80 wt%, preferably 30 to 70 wt% and in particu- lar 35 to 65 wt% of the water-soluble organic solvent. Suitable water-soluble organic solvents are alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyro- lactone; amines; amides, e.g. N-methylpyrrolidone or Ν,Ν-dimethyllactamide, fatty acid dime- thylamides; and mixtures thereof.

In step a) the pyraclostrobin and the water-insoluble UV absorber are dissolved in an organic solvent to provide a solution. The dissolving may be achieved by stirring or mixing the components. The dissolving may be done at 0 to 150 °C, preferably at 10 to 100 °C, and in particular at 40 to 90 °C. The solution is usually a clear solution. The solution is usually a homogenous solution.

In step b) the solution is converted into an agrochemical formulation by optionally adding auxil- iaries. The converting of the solution into an agrochemical formulation may be achieved by adding auxiliaries, or by other known formulation process steps, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. In another form the converting of the solution into an agrochemical formulation may re- quire no additional adding of auxiliaries in step b), e.g. when the solution of step a) can be directly used for step c).

It is also possible to add auxiliaries in step a) and/or c), or in at least one of the steps of a), b) and c).

Suitable auxiliaries are surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. The auxiliaries are preferably free of any UV absorber.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkox- ylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolygluco- sides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylal- cohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene ox- ide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines. Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazoli- nones. Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of the pyraclostrobin. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). In step c) the agrochemical formulation is dispersed in water to provide a tank mix. The dispersing may be achieved by adding, mixing, shaking or stirring, e.g. at ambient temperature. Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the tank mix. These agents can be admixed with the pesticide in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 . Typically, the tank mix contains at least 50 wt% water, preferably at least 65 wt%, more prefer-ably at least 80 wt% and in particular at least 90 wt%. The water is preferably untreated natural water, such as ground water, rain water collected in a water reservoir, river water, or lake water. For comparison, treated water relates to tap water, which has passed a sewage plant. In step d) the tank mix is allowed to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment. When employed in plant protection, the amounts of the pyra- clostrobin applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha. The user applies the tank mix usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricul- tural useful area. The tank mix is typically applied at a volume of 5 to 5000 l/ha, preferably of 50 to 500 l/ha. The tank mix is typically applied at a rate of 5 to 3000 g/ha pesticide, preferably 20 to 1500 g/ha.

The steps a), b), c), and d) are usually made in an alphabetical sequence one after the other.

Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avo- cados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested pro- duce of these plants.

The term crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues. In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, triazine derivatives, or their mixtures, and where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1.

In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, triazine derivatives, or their mixtures, and where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the UV absorber has a solubility in water of up to 1.0 g/l.

In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone deriva- tives, triazine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1. In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, triazine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 , and where the UV absorber has a solubility in water of up to 1.0 g/l.

In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, triazine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the tank mix contains at least 50 wt%, preferably at least 65 wt%, more preferably at least 80 wt% and in particular at least 90 wt% water.

In another preferred form the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, triazine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 , and where the UV absorber has a solubility in water of up to 1 .0 g/l, and where the tank mix contains at least 80 wt% water.

In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, and where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1. In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, and where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the UV absorber has a solubility in water of up to 1 .0 g/l.

In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1.

In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 , and where the UV absorber has a solubility in water of up to 1.0 g/l. In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the tank mix contains at least 50 wt%, preferably at least 65 wt%, more prefera- bly at least 80 wt% and in particular at least 90 wt% water.

In another preferred form the method for preparing the tank mix comprises the steps of a), b) and c), where the UV absorber is selected from benzotriazoles, benzophenone derivatives, tria- zine derivatives, or their mixtures, where the weight ratio of the pyraclostrobin to the UV ab- sorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 , and where the UV absorber has a solubility in water of up to 1.0 g/l, and where the tank mix contains at least 80 wt% water. In a preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones, preferably 2-hydroxy-4- octyloxybenzophenone, in an organic solvent. In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from benzotriazoles, preferably 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol, in an organic solvent. In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy triazine derivatives, preferably 2-(4-(4,6-bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid iso- octyl ester, in an organic solvent.

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones, preferably 2-hy- droxy-4-octyloxybenzophenone, in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 .

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones, preferably 2-hy- droxy-4-octyloxybenzophenone, in an organic solvent, where the weight ratio of the pyra- dostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1.

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the UV absorber has a solubility in water of up to 1.0 g/l. In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from benzotriazoles, preferably 2-(2H-benzotriazol- 2-yl)-4,6-di-tert.-pentylphenol, in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1.

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from benzotriazoles, preferably 2-(2H-benzotriazol- 2-yl)-4,6-di-tert.-pentylphenol, in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 .

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from benzotriazoles in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the UV absorber has a solubility in water of up to 1.0 g/l. In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from triazine derivatives, preferably 2-(4-(4,6- bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester, in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 .

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from triazine derivatives, preferably 2-(4-(4,6- bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester, in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to 3:1 , and in particular from 40:1 to 5:1 .

In another preferred form the agrochemical formulation comprises a solution of pyraclostrobin and a water-insoluble UV absorber selected from triazine derivatives in an organic solvent, where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 , and where the UV absorber has a solubility in water of up to 1.0 g/l.

The invention offers various advantages: the decomposition of the pyraclostrobin due to sunlight is reduced, especially due to ultraviolet (UV) light; the stability of agrochemical formulation during storage and/or after application to the environment is increased; the pesticidal activity of agrochemical formulations after application to the environment is increased.

The examples below give further illustration of the invention, which is not, however, restricted to these examples.

Examples

Auxiliary A Dodecylbenzene sulfonate, calcium salt, 60 wt% in organic solvent.

Auxiliary B liquid, water-soluble nonionic surfactant ethoxylated castor oil.

Auxiliary C nonionic surfactant, liquid ethoxylated polyalkylarylphenol, HLB 12-13.

Auxiliary D Phenolsulfonic acid formaldehyde urea condensate, sodium salt

Auxiliary E nonionic surfactant, liquid ethoxylated and propoxylated alcohol, solidifaction point about -7 °C, dynamic viscosity (23 °C) about 120 mPas

Auxiliary F: Copolymer prepared by radical polymerization, comprising a monomer mixture of

38 wt% vinylpyrrolidone, 29 wt% methyl methacrylate, 20 wt% tert-butyl acrylate, 3 wt% methacrylic acid, and 10 wt% C16/18 alkyl terminated polyethylene glycol (25 EO) methacrylate.

Auxiliary G: Graft polymer of polyethylene glycol and vinylacetate, obtainable as "Polymeric

Additive A" in WO201 1/1 10481.

Auxiliary H: EO-PO-EO Block polymer (50% EO).

Auxiliary I: nonionic surfactant, liquid ethoxylated and propoxylated C16/18 alcohol, solidifaction point about 5°C. Auxiliary J: nonionic surfactant, liquid ethoxylated and propoxylated isoC13 alcohol, soluble in alcohols, dynamic viscosity (23 °C) about 60 mPas.

Auxiliary K: solid, non-ionic surfactant, polyalkoxylated butyl ether.

Auxiliary L: Sodium lignosulphonate

Auxiliary M: Water soluble ethoxylated castor oil.

Auxiliary N: Ethoxylated tristyrylphenol, HLB about 13.

Aromatic Hydrocarbon: Water-insoluble aromatic hydrocarbon solvent, boiling range 240- 300 °C.

Fungicide A: An inert, synthetic fungicide, water-solubility below 3 g/l at 20 °C.

Fungicide B: An inert, synthetic fungicide, water-solubility below 1 g/l at 20 °C, solid at room temperature

Polyisocyanate A: solvent free polyisocyanate based on 4,4'-diphenylmethane diisocy-anate

(MDI) with an average functionality of 2,5 - 2,8, NCO content 30-35 g/100 g (determined by ASTM D 5155-96 A).

Example 1 - Emulsifiable concentrates (EC)

Emulsifiable concentrates were prepared by mixing pyraclostrobin and the UV absorber 2-hy- droxy-4-n-octyloxybenzophenone as listed in Table 1 , and stirring at 60 °C. A homogenous, clear solution was formed. All EC comprised 75 g/l N,N-dimethyllactamide, 50 g/l Aromatic Hy- drocarbon, 150 g/l Auxiliary E, 30 g/l Auxiliary C, 10 g/l Auxiliary A, 40 g/l Auxiliary B, 84 g/l Fungicide A, 50 g/l Auxiliary J, 150 g/l Auxiliary F, and rest up to 1 ,0 L lauryl N,N-dimethylamid. "Comp-1 " denotes a comparative example without UV absorber.

Table 1 : Composition of EC

Example 2 - UV stability of EC with/without UV absorber or UV absorber added in tank mix A) Test Procedure

The UV stability of the pyraclostrobin was tested with the following test procedure:

As measuring equipment the light tester "SUNTEST XLS+" from Atlas was used. This equipment imitates the natural sun light using a Xenon lamp (1700 watt) in the range of 300 - 800 nm.

The EC formulations as prepared in Example 1 (each 1.2 liter) were diluted in 200 liter CIPAC water D (standard hard water) to typical tank mix concentrations, wherein the EC formed an oil in water emulsion. Then the spray liquids were applied with a Hamilton syringe on leaves or on glass slides. For each measurement three replicates with 3 μΙ were made. After drying, the samples were placed in the irradiation chamber. Control samples were located below the test samples in a paper box protected by a thick aluminum foil. After different time intervals samples were analyzed with HPLC-MS-MS to quantify the amount of remaining pyraclostrobin. B) Comparative tank mix Adjuvant A

A typical tank mix Adjuvant A comprising the UV absorber was prepared by mixing all components as listed in Table 2, and stirring at 60 °C. A homogenous, clear solution was formed. Table 2: Composition of Adjuvant A (comparative)

C) Test Results

The samples in Table 3 were prepared as described in the Test Procedure A). The sample " Comp-1 , tank mixed with Adjuvant A" was prepared as follows: The Adjuvant A (0.047 liter) was added to a tank mix of 1.2 liter of Comp-1 in 200 liter water. The results of the Test Procedure are summarized in Table 3.

The comparison between the tank mix prepared from the sample without UV absorber (Comp-1 ) and the sample with the UV absorber (1 -A) demonstrated that the pesticide degradation by UV light was clearly reduced.

The sample without UV absorber (Comp-1 ) was supplemented in the tank mix with UV absorber by addition of Adjuvant A. Although a UV absorber was now present in the tank mix the pesticide degradation by UV light was NOT reduced.

The pesticide degradation by UV light was only reduced when the UV absorber and the pesticide were dissolved in an organic solvent to provide a solution as described in Example 1 (Sample 1 -A). Table 3: Percentage of pyraclostrobin remaining after UV stability test

Example 3 - Dispersible concentrates (DC)

The dispersible concentrates were prepared by mixing pyraclostrobin, the UV absorber 2-hy- droxy-4-n-octyloxybenzophenone as listed in Table 4, and stirring at 60 °C. Both DC contained 50 g/l Auxiliary A, 50 g/l Auxiliary B, 300 g/l Auxiliary G, and were filled up to 1 ,0 I with N,N-di- methyllactamide. A homogenous, clear solution was formed. "Comp-3" denotes a comparative example without UV absorber. Table 4: Composition of DC

Example 4 - UV stability of DC with/without UV absorber or UV absorber added in tank mix A) Test Procedure

The Test Procedure of Example 2 A) was used. The DC formulations as prepared in Example 2 (each 1.2 liter) were diluted in 200 liter CIPAC water D (standard hard water) to typical tank mix concentrations, wherein the DC formed an aqueous suspension of the pyraclostrobin. B) Comparative tank mix Adjuvant A

The tank mix Adjuvant A from Example 2 B) was used.

C) Test Results

The samples in Table 5 were prepared as described in the Test Procedure A). The sample " Comp-3, tank mixed with Adjuvant A" was prepared as follows: The Adjuvant A (0.047 liter) was added to a tank mix of 1.2 liter of Comp-3 in 200 liter water. The results of the Test Procedure are summarized in Table 5.

The comparison between the tank mix prepared from the sample without UV absorber (Comp-3) and the sample with the UV absorber (3-A) demonstrated that the pesticide degradation by UV light was clearly reduced.

The sample without UV absorber (Comp-3) was supplemented in the tank mix with UV absorber by addition of Adjuvant A. Although a UV absorber was now present in the tank mix the pesti- cide degradation by UV light was NOT reduced.

The pesticide degradation by UV light was only reduced when the UV absorber and the pesticide were dissolved in an organic solvent to provide a solution as described in Example 3 (Sample 3-A).

Table 5: Percentage of pyraclostrobin remaining after UV stability test

Example 5 - UV stability of EC at varying concentration of UV absorber A) Test Procedure

The Test Procedure of Example 2 A) was followed. B) Test Results

The samples in Table 6 were prepared as described in the Test Procedure A). The results of the Test Procedure are summarized in Table 6.

The comparison between the tank mix prepared from the sample without UV absorber (Comp-1 ) and the sample with the UV absorber (1 -A) demonstrated that the pesticide degradation by UV light was clearly reduced. The sample without UV absorber (Comp-1 ) was supplemented in the tank mix with UV absorber by addition of Adjuvant A. Although a UV absorber was now present in the tank mix the pesticide degradation by UV light was NOT reduced.

The pesticide degradation by UV light was only reduced when the UV absorber and the pesti- cide were dissolved in an organic solvent to provide a solution as described in Example 1 (Sample 1 -A).

Table 6: Percentage of pyraclostrobin remaining after UV stability test

Example 6 - Suspoemulsion (SE)

The organic phase was prepared by mixing Aromatic Hydrocarbon (200 g/l final concentration), Auxiliary I (133 g/l), pyraclostrobin (133 g/l) and the UV absorber 2-hydroxy-4-n- octyloxybenzo- phenone (20 g/l) until a homogeneous solution was obtained.

In the the organic phase was added an SC premix (50 g/l Fungicide B, 40 g/l Auxiliary D, 10 g/L1 ,2-propylene glycol, 20 g/l Auxiliary H, 0,6 g/l Silicon Defoamer and 100 g of water; mixtures was milled down with the help of a bead mill to less than 2 μηη particle size) containing a thickener premix (1 ,5 g/l xanthan gum, silicon defoamer in 38 g of water). Finally, water was added until the composition reaches the volume of 1.0 I. Example 7 - Microcapsules (CS)

The organic phase was made by dissolving the pyraclostrobin, Auxilary K, Polyisocyanate A, Aromatic Hydrocarbon and 2-hydroxy-4-n-octyloxybenzophenone by mixing until a homogeneous solution was obtained. The aqueous phase was prepared by mixing the Auxiliary L, 20 g of 1 ,2- propylene glycol, and 358,25 g of deionized water. Finally, the organic phase was added into the aqueous phase while stirring with a colloid mill. Then the hexamethylendiamin was added while heating the mixture up to 60 °C, and stir at this temperature for 2 h. Finally the thickener premix (premade of xanthan gum, Silicon defoamer, 1 ,2-propylene glycol and 50 g of water) was added while stirring. Thus, an aqueous suspension of microcapsules was obtained which contained in the core a solution of pesticide and UV absorber in Aromatic Hydrocarbon. Table 8: Receipies for Capsules (concentration

Example 8 - Emulsifiable concentrates (EC)

The emulsifiable concentrates in Table 9 were prepared by mixing pyraclostrobin, the "Triazin UV Absorber" (2-(4-(4,6-bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester), 67 g/l Fungicide A, 50 g/l Auxiliary J, 25 g/l Auxiliary M, 25 g/l Auxiliary N, 200 g/l decyl-N,N-dimethylamide solvent, and further organic solvents up to 1 .0 I, and stirring at 60 °C. A homogenous, clear solution was formed. "Comp-8" denotes a comparative example without UV absorber.

Table 9: Composition of EC

The UV stability of the pyraclostrobin was tested according to the Test Procedure of Example A and the results are summarized in Table 10.

Table 10: Percentage of pyraclostrobin remaining after UV stability test

Example 10 - Emulsifiable concentrates (EC)

The emulsifiable concentrates in Table 1 1 were prepared by mixing pyraclostrobin,

the "Benzotriazol UV Absorber" (2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol), 67 g/l Fungicide A, 50 g/l Auxiliary J, 25 g/l Auxiliary M, 25 g/l Auxiliary N, 200 g/l decyl-N,N-dimethylamide solvent, and further organic solvents up to 1 .0 I, and stirring at 60 °C. A homogenous, clear solution was formed. "Comp-9" denotes a comparative example without UV absorber. Table 1 1 : Composition of EC

The UV stability of the pyraclostrobin was tested according to the Test Procedure of Example A and the results are summarized in Table 12.

Table 12: Percentage of pyraclostrobin remaining after UV stability test

2h 4h 24h 48h

Comp-9 (without UV absorber) 100 95 86 70

9 (with UV absorber) 100 103 104 104

Claims

1. A method of controlling phytopathogenic fungi, which comprises the steps of a) dissolving pyraclostrobin and a water-insoluble UV absorber in an organic solvent to provide a solution, b) converting the solution into an agrochemical formulation by optionally adding auxiliaries, c) dispersing the agrochemical formulation in water to provide a tank mix, and d) allowing the tank mix to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment.

The method according to claim 1 where the weight ratio of the pyraclostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1 .

The method according to claims 1 or 2 where the weight ratio of the organic solvent to the UV absorber is in the range from 50:1 to 3:1 .

The method according to any of claims 1 to 3 where the UV absorber is selected from ben- zotriazoles, benzophenones, triazines, or their mixtures.

The method according to any of claims 1 to 4 where the agrochemical formulation com prises 0.5 to 20 wt% of the UV absorber.

The method according to any of claims 1 to 5 where the agrochemical formulation com prises 10 to 70 wt% of the organic solvent.

7. The method according to any of claims 1 to 6 where the organic solvent comprises a water- insoluble organic solvent, and the agrochemical formulation is selected from emulsifiable concentrates (EC), suspoemulsion concentrates (SE), or microcapsules (CS).

8. The method according to any of claims 1 to 7 where the organic solvent comprises a water- soluble organic solvent and the agrochemical formulation is selected from dispersible concentrates (DC).

9. The method according to any of claims 1 to 8 where the UV absorber has a solubility in water of up to 1.0 g/l.

10. An agrochemical formulation comprising a solution of pyraclostrobin and a water-insoluble UV absorber selected from hydroxy benzophenones, benzotriazoles, or triazines, preferably 2-hydroxy-4-octyloxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol, or 2- (4-(4,6-bis((1 ,1 '-biphenyl)-4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester, in an organic solvent.

1 1. The agrochemical formulations according to claim 10, where the weight ratio of the pyra- clostrobin to the UV absorber is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particular from 15:1 to 1 :1.

12. The agrochemical formulation according to claims 10 or 1 1 , where the weight ratio of the organic solvent to the UV absorber is in the range from 80:1 to 3:1 , preferably from 50:1 to

3:1 , and in particular from 40:1 to 5:1 .

13. The agrochemical formulation according to any of claims 10 to 12, where the UV absorber has a solubility in water of up to 1 .0 g/l.

14. The agrochemical formulation according to any of claims 10 to 13 where the agrochemical formulation comprises 10 to 70 wt% of the organic solvent.

15. A method for preparing a tank mix which comprises the steps of a), b) and c) as defined in any of claims 1 to 9.