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WO2019052898A1 - New agrochemical formulations - Google Patents

New agrochemical formulations Download PDF

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Publication number
WO2019052898A1
WO2019052898A1 PCT/EP2018/074082 EP2018074082W WO2019052898A1 WO 2019052898 A1 WO2019052898 A1 WO 2019052898A1 EP 2018074082 W EP2018074082 W EP 2018074082W WO 2019052898 A1 WO2019052898 A1 WO 2019052898A1
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WO
WIPO (PCT)
Prior art keywords
absorber
organic solvent
pesticide
formulation
methyl
Prior art date
Application number
PCT/EP2018/074082
Other languages
French (fr)
Inventor
Natalia SHABELINA
Simon Nord
Dieter Strobel
Tobias SCHWABEN
Stefan Bechtel
Marcus Annawald
Reiner Weiler
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to EP18762533.0A priority Critical patent/EP3681291A1/en
Publication of WO2019052898A1 publication Critical patent/WO2019052898A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention is related to agrochemical formulations comprising a) a pesticide P1 , said pesticide P1 being 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.
  • the present invention is further related to methods for making agrochemical formulations comprising pesticide P1 and at least one UV absorber and to methods for controlling phytopatho- genic fungi using such formulations.
  • the efficiency of agrochemical formulations in controlling phytopathogenic fungi is one of the key properties of agrochemical formulations.
  • Formulations known in the art comprising 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-me- thyl-phenyl]-4-methyl-tetrazol-5-one (herein also referred to as "pesticide P1 ”) in the field show need for improvement with respect to the efficiency in controlling fungi.
  • pesticidal activity of pesticide P1 decreases over the time. Thus, if formulations of pesticide P1 are stored over longer periods of time, higher amounts of pesticide P1 have to be applied, or pesticide P1 has to be applied in shorter intervals.
  • the object of the present invention was to provide formulations comprising pesticide P1 , that show a high stability of the pesticide and that show little formation of unwanted degradation products, especially after the application of such formulations.
  • the object was solved by formulations comprising a) a pesticide P1 , said pesticide P1 being 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.
  • Formulations according to the invention normally comprise from 1 to 30 wt% of pesticide P1 , preferably 2 to 15 % by weight, in another embodiment, 2 to 10 wt%, in each case relative to the formulation.
  • Formulations according to the invention comprise at least one organic solvent S1.
  • formulations according to the invention comprise an organic solvent system in which pesticide P1 is solubilized, comprising at least one organic solvent S1 , which has a water solubility of less than 1 % by weight at 20°C and at least one organic solvent S2, which is wa- ter miscible at 20 °C.
  • water miscible shall mean that a solvent that is “miscible” with water has a solubility in water of at least 1 % by weight at 20°C.
  • Organic solvents S1 that have a water solubility of less than 1 % by weight at 20 °C, include: 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.
  • vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the afore-mentioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40°C and 250°C and a distillation range between 150°C and 450°C;
  • ketones e.g. acetophenone
  • carbonates e.g. dibutyl carbonate
  • esters e.g. benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate;
  • lactates e.g. 2-ethylhexyl lactate
  • pyrrolidones such as N-octylpyrrolidone, N-ethyl pyrrolidone, N-docedyl pyrrolidone;
  • fatty acid amides e.g. N,N-dimethyloctanamide, ⁇ , ⁇ -dimethylnonaneamide, N,N-dimethylde- canamide, ⁇ , ⁇ -Dimethyl 9-decenamide, lauryl ⁇ , ⁇ -dimethylamide, lauryl N,N-dimethylamide, and mixtures thereof.
  • C8 dimethylamide and “ ⁇ , ⁇ -dimethyl octaneamide” shall be understood to mean “C8 fatty acid ⁇ , ⁇ -dimethylamide” (analogously for other chain lengths).
  • Fatty acid herein shall denote a linear or branched carboxylic acid with a saturated or unsaturated aliphatic chain.
  • Preferred organic solvents S1 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, tetrahy- dronaphthalene, alkylated naphthalenes and C8 to C1 1 aromatic petroleum derivatives (aro- matic hydrocarbons) with a boiling point range from 130°C to 300°C;
  • vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the afore-mentioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40°C and 250°C and a distillation range between 150°C and 450°C;
  • acetophenone dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.
  • More preferred organic solvents S1 are:
  • acetophenone dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.
  • C8-C12 fatty acid dimethyl amides include and preferred C8-C12 fatty acid dimethyl amides are: C8 dimethyl amide ( ⁇ , ⁇ -dimethyloctanamide), C8/C10 dimethyl amide (mixture of N,N-dime- thyloctanamide and ⁇ , ⁇ -dimethyldecanamide), C9 dimethyl amide (N,N-dimethylnonaneamide or ⁇ , ⁇ -Dimethyl iso-nonaneamide), C10 dimethyl amide (N-Dimethyldecanamide or N,N-Dime- thyl 9-decenamide), C12 dimethyl amide (lauryl N,N-dimethylamide).
  • Especially preferred organic solvents S1 are benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbon or their mixtures.
  • Particularly preferred organic solvents S1 are benzylacetate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbon or their mixtures.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C8/C10 dimethylamide, aromatic hydrocarbons and benzylacetate. In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C8/C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
  • Formulations according to the invention normally comprise 10 to 70, preferably 10 to 60 % by weight of at least one organic solvent S1 , based on the formulation.
  • Organic solvents S2, that are miscible with water include:
  • alcohols for example ethanol, n-/i-propanol, n-/i-/sec-/tert-butanol, benzyl alcohol, cyclohexanol, benzyl alcohol, diacetone alcohol, for example 4-hydroxy-4-methyl-2-pentanone, n-octanol, 2- ethylhexanol; glycol and derivatives such as polyethylene glycol, glycerol, propylene glycol, pro- pylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monophenyl ether;
  • lactate esters such as n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate;
  • Carboxylic acid amides e.g. N,N-dimethyl-propanamide, ⁇ , ⁇ -dimethyl-lactatamide, N,N-dime- thyl-butylamide; ⁇ , ⁇ -dimethyl-pentylamide; methyl-5-(dimethylamino)-2-methyl-5-oxopentano- ate;
  • ketones e.g. gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone;
  • lactate esters such as n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate;
  • lactones e.g. N-methyl-pyrrolidone, N-propyl-pyrrolidone, N- butyl- pyrrolidone, N-octyl-pyrroli- done, 1 ,3-dimethyl-2-imidazolidinone, 1 ,3-diethyl-2-imidazolidinone, 1 ,3-diisopropyl imidazoli- dinone such as 2-imidazolidinone;
  • carbonates e.g. glycerin carbonate, pentylene carbonate, butylene carbonate, propylene carbonate;
  • Preferred organic solvents S2 that are miscible with water, are:
  • glycol and derivatives such as polyethylene glycol, glycerol, propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monophenyl ether;
  • N-Ethylmorpholine dimethyl sulfoxide, and mixtures thereof.
  • Especially preferred organic solvents S2 are ⁇ , ⁇ -dimethyllactamide, methyl-5-(dimethylamino)- 2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
  • a particularly preferred organic solvent S2 is N,N-dimethyllactamide.
  • Formulations according to the invention typically comprise 0 to 30 % by weight of organic solvents S2, based on the formulation.
  • said formulations according to the invention comprise 10 to 60 % by weight of at least one organic solvent S1 and 0 to 30 % by weight of at least one organic solvent S2, in each case based on the formulation.
  • formulations according to the invention comprise at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and at least one organic solvent S2 selected from N,N-dimethyllac- tamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
  • formulations according to the invention comprise 10 to 60 wt% of at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and 0 to 30 wt% of at least one organic solvent S2 selected from ⁇ , ⁇ -dimethyllactamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
  • solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures
  • organic solvent S2 selected from ⁇ , ⁇ -dimethyllactamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone,
  • formulations according to the invention comprise 10 to 60 wt% of benzylacetate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures as organic solvent S1 and 0 to 30 wt% of ⁇ , ⁇ -dimethyllactamide as organic solvent S2.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C8-C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C9 dimethylamide, aromatic hydrocarbons and benzylacetate. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C8-C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C9 dimethylamide, aro- matic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, ar- omatic hydrocarbons and methylbenzoate.
  • formulations according to the invention comprise 10 to 70 wt% of organic solvents S1 and S2.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyl- lactamide.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyl- lactamide.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyllactamide. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyllactamide.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone. In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of ⁇ , ⁇ -dimethyllactamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of ⁇ , ⁇ -dimethyllactamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of N,N-dimethyl- lactamide and acetophenone.
  • organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of N,N-dimethyl- lactamide and acetophenone.
  • the mass ratio of Pesticide P1 to organic solvents S1 is 1 :30 to 1 :2, preferably 1 :20 to 1 :3 and more preferably 1 :15 to 1 :4.
  • UV absorber is generally understood to mean substances that are able to absorb ultraviolet rays and emit the absorbed energy in the form of longer-wave radiation, e.g. heat.
  • UV absorbers absorb radiation of wavelengths between 200 and 400 nm.
  • suitable UV absorbers also referred to as UV absorbers A
  • UV absorbers A are especially substances that absorb UV radiation in the wavelength range of 300-340 nm.
  • UV absorbers A have an absorbance in the range of 300-340 nm of at least 0.2, preferably of at least 0.3, more preferably of at least 0.5.
  • the "absorbance” shall mean the common logarithm of the ratio of incident to transmitted radiation through a layer of a thickness of 10 mm of a 0.02 g/l solution of the respective UV absorber in acetonitrile.
  • UV absorbers A are essentially water-insoluble and may have a solubility in water of up to 1 g/l, more preferably 0.5 g/l and in particular up to 0.1 g/l, at 20 °C.
  • the solubility in water of UV ab- sorber may be determined at pH 7.
  • UV absorbers A are usually organic UV absorbers.
  • UV absorbers A have a solubility in organic solvents S at 20°C of at least 2 g/l and have a solubility in water of less than 1 % by weight at 20°C.
  • Suitable UV absorbers A include:
  • benzotriazoles such as alpha-3-(3-(2H-benzotriazol-2- yl)-5-tert-butyl-4- hydroxyphenyl)pro- pionyl- omega-hydroxypoly(oxyethylene), alpha-3-(3- (2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxy- phenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotria- zole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300 (Tinuvin® 213, BASF SE), 2-(2H- benzotriazol-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phenol (Tin
  • 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);
  • PABA para-aminobenzoic acid
  • 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;
  • 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;
  • 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);
  • 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, 2-hydroxy-4-oc- tyloxybenzophenone;
  • 2-hydroxy-4-methoxybenzophenone Uvinul®
  • 3-benzylidenecamphor and derivatives thereof such as 3-(4'-methylbenzylidene)o i -1 -camphor, benzylidiene camphor sulfonic acid (Mexoryl ® SO, Chimex);
  • esters of benzalmalonic acid such as 2-ethylhexyl 4-methoxybenzmalonate
  • 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, BASF SE), anisotriazine (Tinosorb® S, BASF SE), 2,4,6-tris(diisobutyl 4'-aminobenzalmalo- nate)-s-triazine;
  • dioctylbutamidotriazone Uvasorb® HEB, Sigma
  • UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazines, oxanilides or their mixtures.
  • suitable UV absorbers A are A) benzotriazoles, such as 2-(2H-benzotri- azole-2-yl)-4-methyl-6-(2-methyl-3- ((1 ,1 ,3,3-tetramethyl-1 -(trimethylsilyloxy)disiloxanyl)-pro- pyl)phenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxy- phenyl)benzotriazole, 2-(5'-tert.-butyl-2'- hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1 ,1 ,3,3- tetramethylbutyl)phenyl]benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxyphenyl)-5-chlorobenzotria- zole, 2-(3'-ter
  • UV absorbers A are selected from benzotriazoles A), cyanoacrylates B), benzophe- nones F), triazine I), oxanilide L) or their mixtures.
  • UV absorber A comprises a benzotriazole A), e.g.
  • UV absorber A comprises a cyanoacrylates B), such as ethyl 2-cyano-3- phenylcinnamate
  • UV absorber A comprises a benzophenones F), such as 2-hydroxy-4-oc- tylbenzophenone.
  • UV absorber A comprises a triazine I), such as 2-hydroxyphenyl-s-triazine derivative
  • UV absorber A comprises oxanilide L) N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide.
  • UV absorber A comprises alpha-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propi- onyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-bu- tyl-4-hydroxyphenyl) propionate/ PEG 300
  • UV absorber A comprises 2-hydroxy-4-octyloxybenzophenone.
  • UV absorber A comprises a benzophenone F).
  • UV absorber A comprises a triazine I), e.g. 2-(4-(4,6-bis((1 ,1 '-biphenyl)- 4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester.
  • UV absorbers A are benzophenones selected from 2-hydroxy-4-meth- oxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methox- ybenzophenone, 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexylester, and 2-hydroxy benzophenone derivatives (such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-do- decyloxy-, 4-benzyloxy-, 4,2', 4'- trihydroxy-, and 2'-hydroxy-4,4'-dimethoxy- 2-hydroxybenzo- phenone), or their mixtures.
  • 2-hydroxy benzophenone derivatives such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-do- decyloxy-, 4-benzyloxy-, 4,2', 4'-
  • UV absorbers A are benzophenones selected from 2,2'-dihydroxy-4- methoxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-octyloxybenzo- phenone; 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid, hexyl ester; 2,2' ,4,4'-tetrahy- droxybenzophenone, or their mixtures.
  • UV absorber A comprises a benzotriazole A), e.g. 2-(2H-benzotriazol-2-yl)- 4,6-di-tert.-pentylphenol).
  • UV absorber A comprises 2-cyano-3-phenylcinnamate (Uvinul® 3035, BASF SE)
  • UV absorber A comprises N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanedia- mide.
  • UV absorber A comprises alpha-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propi- onyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-bu- tyl-4-hydroxyphenyl) propionate/ PEG 300.
  • UV absorber A comprises 2-hydroxy-4-octyloxybenzophenone.
  • UV absorber A comprises a benzophenone F). In one preferred embodiment, no further UV absorber A beside UV absorber selected from ben- zotriazoles, cyanoacrylates, benzophenones, triazine, oxanilide derivatives, or their mixtures is comprised in formulations F.
  • no further UV absorber beside UV absorber selected from 2-hydroxy-4-octyloxybenzophenone, 2-cyano-3-phenylcinnamate, 2-(2H-benzotriazol-2-yl)- 4,6-di-tert.-pentylphenol), N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanediamide and the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300 is comprised in formulations F.
  • no further UV absorber beside UV absorber selected from 2-hydroxy-4-octyloxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol) and N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanediamide is comprised in formulations F.
  • formulations according to the invention comprise 0.5 to 20 % by weight of UV absorber A, relative to the formulation.
  • formulations according to the invention comprise 0.5 to 10 % by weight, more preferably 0.8 to 5 % by weight of UV absorber A, relative to the formulation.
  • the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1 , more preferably 20:1 to 1 :1 ; even more preferably 10:1 to 1 :1 .
  • the weight ratio of said at least one organic solvent S to UV absorber A is in the range from 100:1 to 3:1 , more preferably 50:1 to 3:1 , even more preferably 30:1 to 3:1 ; and especially preferably 10:1 to 5:1.
  • Formulations according to the invention may further comprise auxiliaries such as surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, com- patibilizers, 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 emulsifier, 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 include alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin 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 include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates 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.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
  • Suitable cationic surfactants include 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 pol- ymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, 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 pesticides like pesticide P1 on the target.
  • Examples are surfactants, mineral or vegetable oils, and other auxiliaries. 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, carboxymethyl- cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • 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
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hex- acyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, poly- acrylates, biological or synthetic waxes, and cellulose ethers.
  • formulations according to the invention comprise one or more further pesticide P2.
  • Pesticide P2 is preferably selected from fungicides, herbicides, insecticides, growth regulators, nematicides or safeners.
  • pesticide P2 is a fungicide.
  • further pesticides P2 are selected from fluxapyroxad, pyraclostrobin and mefentrifluconazol.
  • further pesticides P2 are selected from fluxapyroxad and mefentrifluconazol.
  • formulations according to the invention are selected from emulsifiable concentrates (EC), suspoemulsion concentrates (SE), oil-in-water emulsions (EW), microemulsion (ME) or microcapsules (CS).
  • formulations according to the invention are selected from emulsifiable con- centrates (EC), emulsion (EW) or microemulsion (ME).
  • formulations according to the invention are emulsifiable concentrates (EC). In one embodiment, formulations according to the invention are oil-in-water emulsions (EW). In one embodiment, formulations according to the invention are microemulsions.
  • formulations F are EC formulations, they normally comprise 15 to 65 wt%, preferably 20 to 55 wt% and in particular 25 to 45 wt% of the water-insoluble organic solvent S1 .
  • formulations F are SE or CS formulations, they normally comprise 5 to 50 wt%, preferably 10 to 40 wt% and in particular 15 to 30 wt% of the water-insoluble organic solvent S1 .
  • Suitable microcapsules include polyurethane microcapsules.
  • the polyurethane comprises polyfunctional isocyanate and polyfunctional amine in polymerized form.
  • Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, and toluene diisocyanates.
  • the polyisocyanate comprises an aromatic pol- yisocyanate, such as toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphe- nylmethene-4,4'-diisocyanate (MDI), preferably MDI.
  • TTI toluene diisocyanates
  • MDI diphe- nylmethene-4,4'-diisocyanate
  • the polyisocyanate comprises an oligomeric isocyanate, which are described above.
  • Preferred polyfunctional amines are aliphatic polyamines, such as ⁇ , ⁇ -diamines of the formula H2N-(CH2)n-NH2, wherein n is an integer from 2 to 6. Examples of such diamines are ethylenediamine, propylene- 1 ,3-diamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine. 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 ⁇ , preferably 0.5 to 8 ⁇ , more preferably 1 to 5 ⁇ , and especially 1 to 3 ⁇ .
  • the CS agrochemical formulation F normally comprises 10 to 100 g/l encapsulated pesticide P1 , 50 to 450 g/l water insoluble or- ganic solvent S1 , 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1 .0 I.
  • such CS formulation F comprises 10 to 50 g/l encapsulated pesticide P1 , 150 to 400 g/l water-insoluble organic solvent S1 , 10 to 60 g/l surfactant, and water up to 1.0 I.
  • 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.
  • Another aspect of the present invention are methods for preparing formulations F that includes dissolving pesticide P1 and at least one UV absorber A in at least one organic solvent S1 and optionally S2 to provide a solution.
  • Another aspect of the present invention are methods for controlling phytopathogenic fungi, wherein the fungi, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material are treated with an effective amount of formulations according to the invention.
  • methods for controlling phytopathogenic fungi according to the invention involve application of formulations F in an amount such that 20 to 100 grams per hectar of pesticide P1 and 10 to 50 g/ha of at least one UV absorber A are applied.
  • methods for controlling phytopathogenic fungi according to the invention involve application of formulations F in an amount such that 30 to 80 grams per hectar of pesticide P1 and 15 to30 g/ha of at least one UV absorber A are applied.
  • formulations F show excellent biological effects even at very low concentrations of UV absorber A in formulations F and on the field. It turned out that formulations F are very effective in controlling fungi even if formulations F are applied in amounts that result in very thin layers of pesticide and UV absorber, for example with a thickness of 0.002 ⁇ to 0.09 ⁇ with respect to UV absorber A. Normally, the skilled person would expect from the extinction coefficient and the layer thickness that the UV stabilizer does not have a significant effect if applied in such low amounts.
  • the present invention relates to a method of controlling phyto- pathogenic fungi, which comprises the steps of
  • said spray solution is a tank mix.
  • step a) pesticide P1 and the at least one UV absorber A are dissolved in at least one organic solvent S1 to provide a solution.
  • pesticide P1 is dissolved in a mixture of at least one organic solvent S1 and of at least one organic solvent S2.
  • 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 20 to 90 °C.
  • the solution is usually a clear solution.
  • the solution is usually a homogenous solution.
  • step b) the solution is converted into an agrochemical formulation by optionally adding auxiliaries.
  • 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 develop- ments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • the converting of the solution into an agrochemical formulation may require 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). Examples of suitable auxiliaries are given above.
  • step c) the agrochemical formulation obtained in step b) is dispersed in water to provide a spray solution.
  • 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
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with pesticide P1 in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 .
  • the spray solution 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.
  • treated water relates to tap water, which has passed a sewage plant.
  • step d) the spray solution obtained in step c) 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 unde- sired plants and/or the crop plants and/or their environment.
  • the amounts of pesticide P1 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 spray solution usually from a predos- age device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the spray solution is typically applied at a volume of 5 to 5000 l/ha, preferably of 50 to 500 l/ha.
  • the spray solution is typically applied at a rate of 5 to 3000 g/ha pesticide, preferably 20 to 1500 g/ha.
  • steps a), b), c), and d) are usually made in an alphabetical sequence one after the other.
  • the efficiency of formulations F is increased, if UV absorber A is added prior to step c).
  • UV absorber is added in step a).
  • 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 ex- ample 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 avocados, cinnamon or camphor; energy
  • 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 ma- terial).
  • 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.
  • the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where UV absorber is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, and where the weight ratio of pesticide P1 to UV absorber A 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 of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where UV absorber is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to 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 .
  • the method of controlling phytopathogenic fungi comprises the steps a), b), c), and d), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particu- lar from 15:1 to 1 :1 , and where the spray solution contains at least 50 wt%, preferably at least 65 wt%, more preferably at least 80 wt% and in particular at least 90 wt% water.
  • the method of controlling phytopathogenic fungi comprises the steps a) , b), c), and d), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide
  • P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 spray solution contains at least 80 wt% water.
  • the method for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, and where the weight ratio of pesticide P1 to UV absorber A 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 for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 .
  • the method for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A 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 spray solution contains at least 50 wt%, preferably at least 65 wt%, more preferably at least 80 wt% and in particular at least 90 wt% water.
  • UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures
  • the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1 , preferably from 20:1
  • the method for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 spray solution contains at least 80 wt% water.
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzophe- none, in at least one organic solvent S1 .
  • the agrochemical formulation comprises a solution of pesticide P1 and a water-insoluble UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-ben- zotriazol-2- yl)-5-tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene), alpha- 3-(3- (2H-benzotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotria- zol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 .
  • a water-insoluble UV absorber A selected
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy triazine, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy cyanoacrylates, preferably ethyl 2-cyano-3-phenylcin- namate, in at least one organic solvent S1 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octylbenzophe- none, in at least one organic solvent S1 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilide, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzo- phenone, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV ab- sorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzo- phenone, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 .
  • the agrochemical formulation comprises a solution of pesticide P1 and a UV absorber A selected from hydroxy benzophenones in at least one organic solvent, where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-benzotriazol-2- yl)-5- tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene), alpha-3-(3- (2H-ben- zotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert- butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3- (2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 in at least one organic solvent S1 , where the weight ratio of pesticide P1 to
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-benzotriazol-2- yl)-5- tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene) and alpha-3-(3- (2H- benzotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3- (3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 , in at least one organic solvent S1 , where the weight ratio of pesticide P1 to
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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.
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates, preferably ethyl 2-cyano-3-phenylcinnamate, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates, preferably ethyl 2-cyano-3-phenylcinnamate, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 , where the weight ratio of pesti- cide P1 to UV absorber A 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 agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 .
  • the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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.
  • Formulations F are easy and economical to prepare and show high activity and effectiveness and efficiency in controlling fungi.
  • Formulations F are very stable with respect to the storage stability and the chemical stability of its components, especially pesticide P1. Only little decomposition due to light or heat is ob- served in formulations F. The stability of the pesticides in formulations F during storage and/or after application to the environment is increased; the pesticidal activity of formulations F after application to the environment is increased. The formation of side products due to UV irradiation, especially after application, is decreased.
  • Methods according to the invention for controlling fungi are easy and economical to carry out and result in high stability of formulations F during storage and/or after application to the environment is increased and in high pesticidal activity of formulations F after application to the environment. They are very effective also with low dosages of UV absorbers.
  • 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 nonionic surfactant, liquid ethoxylated and propoxylated C16/18 alcohol, solidifica- tion point about 5°C.
  • Auxiliary E nonionic surfactant, liquid ethoxylated and propoxylated isoC13 alcohol, soluble in alcohols, dynamic viscosity (23 °C) about 60 mPas.
  • Auxiliary D Phenolsulfonic acid formaldehyde urea condensate, sodium salt
  • Pesticide P1 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-te- trazol-5-one
  • Pesticide P2A fluxapyroxat
  • Pesticide P2B mefentrifluconazol Preparation of emulsifiable concentrates (EC)
  • Emulsifiable concentrates were prepared by mixing P1 and the UV absorbers with solvents and stirring and other formulants until complete dissolution.
  • the EC formulations 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 ⁇ 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 P1 .
  • Table 1 EC composition and P1 stability - with different UV absorbers and without UV absorber
  • UV Absorber 2-Hydroxy- 19 9.5
  • UV Absorber Reaction 19 9.5
  • UV Absorber N-(2- 19 9.5
  • UV Absorber ethyl 2-cy- 19 9.5 ano-3-phenylcinnamate
  • Auxiliary D 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • UV Absorber 2-Hydroxy-4-n-oc- 19 9.5
  • UV Absorber Reaction product of 19 9.5
  • UV Absorber ethyl 2-cyano-3-phe- 19 9.5 nylcinnamate
  • Table 4 EC composition and P1 stability - with different UV absorbers and without UV absorber
  • UV Absorber 2-Hydroxy-4-n-octyloxybenzophenone 19 15
  • UV Absorber N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) 15 ethanediamide
  • UV Absorber ethyl 2-cyano-3-phenylcinnamate 15

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Abstract

Agrochemical formulations comprising a) a pesticide P1, said pesticide P1 being 1-[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.

Description

New Agrochemical Formulations
The present invention is related to agrochemical formulations comprising a) a pesticide P1 , said pesticide P1 being 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.
The present invention is further related to methods for making agrochemical formulations comprising pesticide P1 and at least one UV absorber and to methods for controlling phytopatho- genic fungi using such formulations.
The efficiency of agrochemical formulations in controlling phytopathogenic fungi is one of the key properties of agrochemical formulations.
Formulations known in the art comprising 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-me- thyl-phenyl]-4-methyl-tetrazol-5-one (herein also referred to as "pesticide P1 ") in the field show need for improvement with respect to the efficiency in controlling fungi.
It was found that the pesticidal activity of pesticide P1 decreases over the time. Thus, if formulations of pesticide P1 are stored over longer periods of time, higher amounts of pesticide P1 have to be applied, or pesticide P1 has to be applied in shorter intervals.
Furthermore, formation of degradation products occurs upon storage or after application in the field.
Thus, the object of the present invention was to provide formulations comprising pesticide P1 , that show a high stability of the pesticide and that show little formation of unwanted degradation products, especially after the application of such formulations.
The object was solved by formulations comprising a) a pesticide P1 , said pesticide P1 being 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.
Such formulations and embodiments thereof described hereafter are also referred to herein as formulations F. Formulations according to the invention normally comprise from 1 to 30 wt% of pesticide P1 , preferably 2 to 15 % by weight, in another embodiment, 2 to 10 wt%, in each case relative to the formulation.
Formulations according to the invention comprise at least one organic solvent S1.
In one embodiment, formulations according to the invention comprise an organic solvent system in which pesticide P1 is solubilized, comprising at least one organic solvent S1 , which has a water solubility of less than 1 % by weight at 20°C and at least one organic solvent S2, which is wa- ter miscible at 20 °C.
In the context of the miscibility of solvents, "water miscible" shall mean that a solvent that is "miscible" with water has a solubility in water of at least 1 % by weight at 20°C. Organic solvents S1 , that have a water solubility of less than 1 % by weight at 20 °C, include: 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, tetrahy- dronaphthalene, alkylated naphthalenes and C8 to C1 1 aromatic petroleum derivatives (aromatic hydrocarbons) with a boiling point range from 130°C to 300°C;
vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the afore-mentioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40°C and 250°C and a distillation range between 150°C and 450°C;
ketones, e.g. acetophenone;
carbonates, e.g. dibutyl carbonate;
esters, e.g. benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate;
lactates, e.g. 2-ethylhexyl lactate;
fatty acid esters,
fatty acids;
phosphonates;
fatty acid amines;
pyrrolidones, such as N-octylpyrrolidone, N-ethyl pyrrolidone, N-docedyl pyrrolidone;
fatty acid amides, e.g. N,N-dimethyloctanamide, Ν,Ν-dimethylnonaneamide, N,N-dimethylde- canamide, Ν,Ν-Dimethyl 9-decenamide, lauryl Ν,Ν-dimethylamide, lauryl N,N-dimethylamide, and mixtures thereof.
Herein, "C8 dimethylamide" and "Ν,Ν-dimethyl octaneamide" shall be understood to mean "C8 fatty acid Ν,Ν-dimethylamide" (analogously for other chain lengths).
"Fatty acid" herein shall denote a linear or branched carboxylic acid with a saturated or unsaturated aliphatic chain. Preferred organic solvents S1 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, tetrahy- dronaphthalene, alkylated naphthalenes and C8 to C1 1 aromatic petroleum derivatives (aro- matic hydrocarbons) with a boiling point range from 130°C to 300°C;
vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the afore-mentioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40°C and 250°C and a distillation range between 150°C and 450°C;
acetophenone; dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.
More preferred organic solvents S1 are:
acetophenone; dibutyl carbonate; benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; 2-Ethylhexyl lactate; fatty acid esters; fatty acids; C8-C12 fatty acid dimethyl amides; and mixtures thereof.
C8-C12 fatty acid dimethyl amides include and preferred C8-C12 fatty acid dimethyl amides are: C8 dimethyl amide (Ν,Ν-dimethyloctanamide), C8/C10 dimethyl amide (mixture of N,N-dime- thyloctanamide and Ν,Ν-dimethyldecanamide), C9 dimethyl amide (N,N-dimethylnonaneamide or Ν,Ν-Dimethyl iso-nonaneamide), C10 dimethyl amide (N-Dimethyldecanamide or N,N-Dime- thyl 9-decenamide), C12 dimethyl amide (lauryl N,N-dimethylamide). Especially preferred organic solvents S1 are benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbon or their mixtures.
Particularly preferred organic solvents S1 are benzylacetate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbon or their mixtures.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8/C10 dimethylamide, aromatic hydrocarbons and benzylacetate. In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8/C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
Formulations according to the invention normally comprise 10 to 70, preferably 10 to 60 % by weight of at least one organic solvent S1 , based on the formulation.
Organic solvents S2, that are miscible with water, include:
alcohols, for example ethanol, n-/i-propanol, n-/i-/sec-/tert-butanol, benzyl alcohol, cyclohexanol, benzyl alcohol, diacetone alcohol, for example 4-hydroxy-4-methyl-2-pentanone, n-octanol, 2- ethylhexanol; glycol and derivatives such as polyethylene glycol, glycerol, propylene glycol, pro- pylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monophenyl ether;
lactate esters such as n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate;
Carboxylic acid amides, e.g. N,N-dimethyl-propanamide, Ν,Ν-dimethyl-lactatamide, N,N-dime- thyl-butylamide; Ν,Ν-dimethyl-pentylamide; methyl-5-(dimethylamino)-2-methyl-5-oxopentano- ate;
ketones, e.g. gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone;
lactate esters such as n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate;
lactones, e.g. N-methyl-pyrrolidone, N-propyl-pyrrolidone, N- butyl- pyrrolidone, N-octyl-pyrroli- done, 1 ,3-dimethyl-2-imidazolidinone, 1 ,3-diethyl-2-imidazolidinone, 1 ,3-diisopropyl imidazoli- dinone such as 2-imidazolidinone;
carbonates, e.g. glycerin carbonate, pentylene carbonate, butylene carbonate, propylene carbonate;
N-ethylmorpholine, dimethyl sulfoxide, and mixtures thereof. Preferred organic solvents S2, that are miscible with water, are:
ethanol, n-/i-propanol, n-/i-/sec-/tert-butanol, benzyl alcohol, cyclohexanol, benzyl alcohol, diacetone alcohol, for example 4-hydroxy-4-methyl-2-pentanone, n-octanol, 2-ethylhexanol; glycol and derivatives such as polyethylene glycol, glycerol, propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monophenyl ether;
n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate; N,N-dimethyl-pro- panamide, Ν,Ν-dimethyl-lactatamide, N,N-dimethyl-butylamide; Ν,Ν-dimethyl-pentylamide; me- thyl-5-(dimethylamino)-2-methyl-5-oxopentanoate;
gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone;
n-propyl lactate, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate; N-methyl-pyrrolidone, N-propyl-pyrrolidone, N- butyl- pyrrolidone, N-octyl-pyrrolidone, 1 ,3-dime- thyl-2-imidazolidinone, 1 ,3-diethyl-2-imidazolidinone, 1 ,3-diisopropyl imidazolidinone such as 2- imidazolidinone;
glycerin carbonate, butylene carbonate, propylene carbonate;
N-Ethylmorpholine, dimethyl sulfoxide, and mixtures thereof.
Especially preferred organic solvents S2 are Ν,Ν-dimethyllactamide, methyl-5-(dimethylamino)- 2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
A particularly preferred organic solvent S2 is N,N-dimethyllactamide.
Formulations according to the invention typically comprise 0 to 30 % by weight of organic solvents S2, based on the formulation.
In one embodiment, said formulations according to the invention comprise 10 to 60 % by weight of at least one organic solvent S1 and 0 to 30 % by weight of at least one organic solvent S2, in each case based on the formulation. In one embodiment, formulations according to the invention comprise at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and at least one organic solvent S2 selected from N,N-dimethyllac- tamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
In one embodiment, formulations according to the invention comprise 10 to 60 wt% of at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and 0 to 30 wt% of at least one organic solvent S2 selected from Ν,Ν-dimethyllactamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
In one embodiment, formulations according to the invention comprise 10 to 60 wt% of benzylacetate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures as organic solvent S1 and 0 to 30 wt% of Ν,Ν-dimethyllactamide as organic solvent S2.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C9 dimethylamide, aromatic hydrocarbons and benzylacetate. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C10 dimethylamide, aromatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C9 dimethylamide, aro- matic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, ar- omatic hydrocarbons and methylbenzoate.
Normally, formulations according to the invention comprise 10 to 70 wt% of organic solvents S1 and S2. In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyl- lactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyl- lactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is N,N-dimethyllactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyllactamide. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate and organic solvent S2 is N,N-dimethyllactamide.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone. In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dime- thylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone. In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and methylbenzoate and organic solvent S2 is acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of Ν,Ν-dimethyllactamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C8-C12 fatty acid dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of Ν,Ν-dimethyllactamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, ar- omatic hydrocarbons and benzylacetate and organic solvent S2 is a mixture of N,N-dimethyllac- tamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C12 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of N,N-dimethyl- lactamide and acetophenone.
In one embodiment, organic solvent S1 comprises a mixture comprising C10 dimethylamide, aromatic hydrocarbons and methylbenzoate and organic solvent S2 is a mixture of N,N-dimethyl- lactamide and acetophenone.
Normally, the mass ratio of Pesticide P1 to organic solvents S1 is 1 :30 to 1 :2, preferably 1 :20 to 1 :3 and more preferably 1 :15 to 1 :4.
The term "UV absorber" is generally understood to mean substances that are able to absorb ultraviolet rays and emit the absorbed energy in the form of longer-wave radiation, e.g. heat. Typically, UV absorbers absorb radiation of wavelengths between 200 and 400 nm. As it was found, suitable UV absorbers, also referred to as UV absorbers A, are especially substances that absorb UV radiation in the wavelength range of 300-340 nm. Preferably, UV absorbers A have an absorbance in the range of 300-340 nm of at least 0.2, preferably of at least 0.3, more preferably of at least 0.5. The "absorbance" shall mean the common logarithm of the ratio of incident to transmitted radiation through a layer of a thickness of 10 mm of a 0.02 g/l solution of the respective UV absorber in acetonitrile.
UV absorbers A are essentially water-insoluble and may have a solubility in water of up to 1 g/l, more preferably 0.5 g/l and in particular up to 0.1 g/l, at 20 °C. The solubility in water of UV ab- sorber may be determined at pH 7. UV absorbers A are usually organic UV absorbers.
UV absorbers A have a solubility in organic solvents S at 20°C of at least 2 g/l and have a solubility in water of less than 1 % by weight at 20°C. Suitable UV absorbers A include:
A) benzotriazoles, such as alpha-3-(3-(2H-benzotriazol-2- yl)-5-tert-butyl-4- hydroxyphenyl)pro- pionyl- omega-hydroxypoly(oxyethylene), alpha-3-(3- (2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxy- phenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotria- zole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300 (Tinuvin® 213, BASF SE), 2-(2H- benzotriazol-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phenol (Tinuvin® 900, BASF SE), [3-[3- (2H-benzotriazol-2-yl)-5-(1 ,1 -dimethylethyl)-4-hydroxyphenyl]-1 -oxopropyl]-w-[3-[3-(2Hben- zotriazol-2-yl)-5-(1 ,1 -dimethylethyl)-4-hydroxyphenyl]-1 -oxopropoxy]poly(oxy-1 ,2-ethanediyl) (Tinuvin® 1 130, BASF SE), 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-tetramethylbutyl)-phenol, 2-(2H-benzotria- zol-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, 2-hydroxy-4-oc- tyloxybenzophenone;
G) 3-benzylidenecamphor and derivatives thereof, such as 3-(4'-methylbenzylidene)oi-1 -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, BASF SE), anisotriazine (Tinosorb® S, BASF SE), 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. L) Oxanilides, such as N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanediamide (Tinuvin® 312)
In one embodiment, UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazines, oxanilides or their mixtures.
In another embodiment, suitable UV absorbers A are A) benzotriazoles, such as 2-(2H-benzotri- azole-2-yl)-4-methyl-6-(2-methyl-3- ((1 ,1 ,3,3-tetramethyl-1 -(trimethylsilyloxy)disiloxanyl)-pro- pyl)phenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxy- phenyl)benzotriazole, 2-(5'-tert.-butyl-2'- hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1 ,1 ,3,3- tetramethylbutyl)phenyl]benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxyphenyl)-5-chlorobenzotria- zole, 2-(3'-tert.-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec.-butyl-5'-tert.- butyl- 2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di- tert.-amyl-2'-hydroxyphenyl)benzotriazole, 2-[3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxy- phenyl]benzotriazole, 2-[3'-tert.-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl]-5-chloro- benzotriazole, 2-[3'-tert.-butyl-5'-(2-(2-ethylhexyloxy)-carbonylethyl)-2'-hydroxyphenyl]-5-chloro- benzotriazole, 2[3'-tert.-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotria- zole, 2-[3'-tert.-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert.-bu- tyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)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)phe- nyl]benzotriazole, 2,2'-methylen-bis[4-(1 ,1 ,3,3-tetramethylbutyl)-6- benzotriazol-2-yl-phenol], es- terified product of 2-[3'-tert.-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotria- zole and polyethyleneglycol 300, [R-CH2CH2-COO(CH2)3-]2 with R being 3'-tert.-butyl-4-hy- droxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetra- methylbutyl)phenyl]benzotriazole, 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(a,a-dime- thylbenzyl)phenyl]benzotriazole; In another form suitable UV absorbers A 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, oxanilides such as N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide.
Preferred UV absorbers A are selected from benzotriazoles A), cyanoacrylates B), benzophe- nones F), triazine I), oxanilide L) or their mixtures. In one preferred form UV absorber A comprises a benzotriazole A), e.g. alpha-3-(3-(2H-ben- zotriazol-2- yl)-5-tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene) and alpha-3-(3- (2H-benzotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-ben- zotriazol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300.
In one preferred form UV absorber A comprises a cyanoacrylates B), such as ethyl 2-cyano-3- phenylcinnamate
In one preferred form UV absorber A comprises a benzophenones F), such as 2-hydroxy-4-oc- tylbenzophenone.
In one preferred form UV absorber A comprises a triazine I), such as 2-hydroxyphenyl-s-triazine derivative In one preferred form UV absorber A comprises oxanilide L) N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide. In one preferred form UV absorber A comprises alpha-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propi- onyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-bu- tyl-4-hydroxyphenyl) propionate/ PEG 300
In one embodiment, UV absorber A comprises 2-hydroxy-4-octyloxybenzophenone.
In another embodiment, UV absorber A comprises a benzophenone F). In another embodiment, UV absorber A comprises a triazine I), e.g. 2-(4-(4,6-bis((1 ,1 '-biphenyl)- 4-yl)-1 ,3,5-triazin-2-yl)-3-hydroxyphenoxy) propanoic acid isooctyl ester.
In another embodiment, UV absorbers A are benzophenones selected from 2-hydroxy-4-meth- oxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methox- ybenzophenone, 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexylester, and 2-hydroxy benzophenone derivatives (such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-do- decyloxy-, 4-benzyloxy-, 4,2', 4'- trihydroxy-, and 2'-hydroxy-4,4'-dimethoxy- 2-hydroxybenzo- phenone), or their mixtures. In another embodiment UV absorbers A are benzophenones selected from 2,2'-dihydroxy-4- methoxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-n-octyloxybenzo- phenone; 2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid, hexyl ester; 2,2' ,4,4'-tetrahy- droxybenzophenone, or their mixtures. n one embodiment UV absorber A comprises a benzotriazole A), e.g. 2-(2H-benzotriazol-2-yl)- 4,6-di-tert.-pentylphenol).
In one embodiment UV absorber A comprises 2-cyano-3-phenylcinnamate (Uvinul® 3035, BASF SE)
In one embodiment UV absorber A comprises N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanedia- mide.
In one embodiment UV absorber A comprises alpha-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propi- onyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-bu- tyl-4-hydroxyphenyl) propionate/ PEG 300.
In one embodiment UV absorber A comprises 2-hydroxy-4-octyloxybenzophenone.
In another embodiment, UV absorber A comprises a benzophenone F). In one preferred embodiment, no further UV absorber A beside UV absorber selected from ben- zotriazoles, cyanoacrylates, benzophenones, triazine, oxanilide derivatives, or their mixtures is comprised in formulations F.
In one especially preferred embodiment, no further UV absorber beside UV absorber selected from 2-hydroxy-4-octyloxybenzophenone, 2-cyano-3-phenylcinnamate, 2-(2H-benzotriazol-2-yl)- 4,6-di-tert.-pentylphenol), N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanediamide and the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300 is comprised in formulations F.
In one especially preferred embodiment, no further UV absorber beside UV absorber selected from 2-hydroxy-4-octyloxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol) and N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) ethanediamide is comprised in formulations F.
Normally, formulations according to the invention comprise 0.5 to 20 % by weight of UV absorber A, relative to the formulation.
Preferably, formulations according to the invention comprise 0.5 to 10 % by weight, more preferably 0.8 to 5 % by weight of UV absorber A, relative to the formulation.
In one preferred embodiment, the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1 , more preferably 20:1 to 1 :1 ; even more preferably 10:1 to 1 :1 .
In one preferred embodiment, the weight ratio of said at least one organic solvent S to UV absorber A is in the range from 100:1 to 3:1 , more preferably 50:1 to 3:1 , even more preferably 30:1 to 3:1 ; and especially preferably 10:1 to 5:1. Formulations according to the invention may further comprise auxiliaries such as surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, com- patibilizers, 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 emulsifier, 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 include alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin 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 include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates 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-substituted 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 alkylpoly- glucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
Suitable cationic surfactants include 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 pol- ymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, 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 pesticides like pesticide P1 on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. 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, carboxymethyl- cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. 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 hex- acyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, poly- acrylates, biological or synthetic waxes, and cellulose ethers. In one embodiment, formulations according to the invention comprise one or more further pesticide P2. Pesticide P2 is preferably selected from fungicides, herbicides, insecticides, growth regulators, nematicides or safeners. Preferably, pesticide P2 is a fungicide. In one embodiment, further pesticides P2 are selected from fluxapyroxad, pyraclostrobin and mefentrifluconazol.
In one embodiment, further pesticides P2 are selected from fluxapyroxad and mefentrifluconazol. In one embodiment, formulations according to the invention are selected from emulsifiable concentrates (EC), suspoemulsion concentrates (SE), oil-in-water emulsions (EW), microemulsion (ME) or microcapsules (CS).
In one embodiment, formulations according to the invention are selected from emulsifiable con- centrates (EC), emulsion (EW) or microemulsion (ME).
In one embodiment, formulations according to the invention are emulsifiable concentrates (EC). In one embodiment, formulations according to the invention are oil-in-water emulsions (EW). In one embodiment, formulations according to the invention are microemulsions.
When formulations F are EC formulations, they normally comprise 15 to 65 wt%, preferably 20 to 55 wt% and in particular 25 to 45 wt% of the water-insoluble organic solvent S1 .
When formulations F are SE or CS formulations, they normally comprise 5 to 50 wt%, preferably 10 to 40 wt% and in particular 15 to 30 wt% of the water-insoluble organic solvent S1 .
Suitable microcapsules (CS) include polyurethane microcapsules. Typically, the polyurethane comprises polyfunctional isocyanate and polyfunctional amine in polymerized form. Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, and toluene diisocyanates. In another preferred embodiment, the polyisocyanate comprises an aromatic pol- yisocyanate, such as toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphe- nylmethene-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 H2N-(CH2)n-NH2, wherein n is an integer from 2 to 6. Examples of such diamines are ethylenediamine, propylene- 1 ,3-diamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine. 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 F normally comprises 10 to 100 g/l encapsulated pesticide P1 , 50 to 450 g/l water insoluble or- ganic solvent S1 , 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1 .0 I. More preferably, such CS formulation F comprises 10 to 50 g/l encapsulated pesticide P1 , 150 to 400 g/l water-insoluble organic solvent S1 , 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.
Another aspect of the present invention are methods for preparing formulations F that includes dissolving pesticide P1 and at least one UV absorber A in at least one organic solvent S1 and optionally S2 to provide a solution. Another aspect of the present invention are methods for controlling phytopathogenic fungi, wherein the fungi, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material are treated with an effective amount of formulations according to the invention. In one embodiment, methods for controlling phytopathogenic fungi according to the invention involve application of formulations F in an amount such that 20 to 100 grams per hectar of pesticide P1 and 10 to 50 g/ha of at least one UV absorber A are applied. In another embodiment, methods for controlling phytopathogenic fungi according to the invention involve application of formulations F in an amount such that 30 to 80 grams per hectar of pesticide P1 and 15 to30 g/ha of at least one UV absorber A are applied.
It is a surprising result of the present invention, that formulations F show excellent biological effects even at very low concentrations of UV absorber A in formulations F and on the field. It turned out that formulations F are very effective in controlling fungi even if formulations F are applied in amounts that result in very thin layers of pesticide and UV absorber, for example with a thickness of 0.002 μηη to 0.09 μηη with respect to UV absorber A. Normally, the skilled person would expect from the extinction coefficient and the layer thickness that the UV stabilizer does not have a significant effect if applied in such low amounts.
In one preferred embodiment, the present invention relates to a method of controlling phyto- pathogenic fungi, which comprises the steps of
a) dissolving pesticide P1 and at least one UV absorber A in at least one organic solvent S1 and optionally at least one organic solvent S2 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 spray solution, and d) allowing the spray solution 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.
In one especially preferred embodiment, said spray solution is a tank mix.
In step a) pesticide P1 and the at least one UV absorber A are dissolved in at least one organic solvent S1 to provide a solution. In one embodiment pesticide P1 is dissolved in a mixture of at least one organic solvent S1 and of at least one organic solvent S2. 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 20 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 auxiliaries. 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 develop- ments 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 require 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). Examples of suitable auxiliaries are given above.
In step c) the agrochemical formulation obtained in step b) is dispersed in water to provide a spray solution. 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 spray solution. These agents can be admixed with pesticide P1 in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 . Typically, the spray solution 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 spray solution obtained in step c) 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 unde- sired plants and/or the crop plants and/or their environment. When employed in plant protection, the amounts of pesticide P1 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 spray solution usually from a predos- age 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 agricultural useful area. The spray solution is typically applied at a volume of 5 to 5000 l/ha, preferably of 50 to 500 l/ha. The spray solution 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. As it turned out unexpectedly, the efficiency of formulations F is increased, if UV absorber A is added prior to step c). Preferably, UV absorber is added in step a).
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 ex- ample 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 avocados, 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; bana- nas; 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 produce 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 ma- terial). 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 UV absorber is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, and where the weight ratio of pesticide P1 to UV absorber A 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 UV absorber is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to 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 UV absorber A is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , and in particu- lar from 15:1 to 1 :1 , and where the spray solution 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 UV absorber A is selected from benzotriazoles, cyanoacrylates, benzo- phenones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide
P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 spray solution contains at least 80 wt% water. In another preferred form the method for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, and where the weight ratio of pesticide P1 to UV absorber A 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 spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A 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 spray solution 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 for preparing the spray solution comprises the steps of a), b) and c), where UV absorber A is selected from benzotriazoles, cyanoacrylates, benzophe- nones, triazine, oxanilide derivatives, or their mixtures, where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S to UV absorber A 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 spray solution contains at least 80 wt% water. In one embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzophe- none, in at least one organic solvent S1 .
In one embodiment, the agrochemical formulation comprises a solution of pesticide P1 and a water-insoluble UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-ben- zotriazol-2- yl)-5-tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene), alpha- 3-(3- (2H-benzotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotria- zol-2-yl)-5-tert-butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 .
In another preferred form the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy triazine, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 .
In another preferred form the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy cyanoacrylates, preferably ethyl 2-cyano-3-phenylcin- namate, in at least one organic solvent S1 .
In another preferred form the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octylbenzophe- none, in at least one organic solvent S1 .
In another preferred form the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilide, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 .
In another embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzo- phenone, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV ab- sorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy benzophenones, preferably 2-hydroxy-4-octyloxybenzo- phenone, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and a UV absorber A selected from hydroxy benzophenones in at least one organic solvent, where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-benzotriazol-2- yl)-5- tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene), alpha-3-(3- (2H-ben- zotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5-tert- butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3-(3- (2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles, preferably alpha-3-(3-(2H-benzotriazol-2- yl)-5- tert-butyl-4- hydroxyphenyl)propionyl- omega-hydroxypoly(oxyethylene) and alpha-3-(3- (2H- benzotriazol-2-yl)-5- tert-butyl-4-hydroxyphenyl)propionyl-omega-3-(3-(2H-benzotriazol-2-yl)-5- tert-butyl-4- hydroxyphenyl)propionyloxypoly(oxyethylene), or the reaction product of methyl 3- (3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl) propionate/ PEG 300, in at least one organic solvent S1 , in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent to 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from benzotriazoles in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives, preferably 2-hydroxyphenyl-s-triazine derivative, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from triazine derivatives in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates, preferably ethyl 2-cyano-3-phenylcinnamate, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates, preferably ethyl 2-cyano-3-phenylcinnamate, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from cyanoacrylates in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 , where the weight ratio of pesti- cide P1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides, preferably N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) ethanediamide, in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A is in the range from 20:1 to 1 :1 , and where the weight ratio of organic solvent S1 to UV absorber A 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 embodiment, the agrochemical formulation comprises a solution of pesticide P1 and UV absorber A selected from hydroxy oxanilides in at least one organic solvent S1 , where the weight ratio of pesticide P1 to UV absorber A 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 invention offers various advantages:
Formulations F are easy and economical to prepare and show high activity and effectiveness and efficiency in controlling fungi.
Formulations F are very stable with respect to the storage stability and the chemical stability of its components, especially pesticide P1. Only little decomposition due to light or heat is ob- served in formulations F. The stability of the pesticides in formulations F during storage and/or after application to the environment is increased; the pesticidal activity of formulations F after application to the environment is increased. The formation of side products due to UV irradiation, especially after application, is decreased.
Methods according to the invention for controlling fungi are easy and economical to carry out and result in high stability of formulations F during storage and/or after application to the environment is increased and in high pesticidal activity of formulations F after application to the environment. They are very effective also with low dosages of UV absorbers.
The examples below give further illustration of the invention, which is not, however, restricted to these examples.
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: nonionic surfactant, liquid ethoxylated and propoxylated C16/18 alcohol, solidifica- tion point about 5°C.
Auxiliary E: nonionic surfactant, liquid ethoxylated and propoxylated isoC13 alcohol, soluble in alcohols, dynamic viscosity (23 °C) about 60 mPas. Auxiliary D: Phenolsulfonic acid formaldehyde urea condensate, sodium salt
Pesticide P1 : 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-te- trazol-5-one
Pesticide P2A: fluxapyroxat
Pesticide P2B: mefentrifluconazol Preparation of emulsifiable concentrates (EC)
Emulsifiable concentrates were prepared by mixing P1 and the UV absorbers with solvents and stirring and other formulants until complete dissolution.
UV stability of P1 : test procedure
The UV stability of the pesticide 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 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 P1 .
Table 1 : EC composition and P1 stability - with different UV absorbers and without UV absorber
Examples 1 2 3 4 5 6 7 8 9
Composition of EC [g/L]
Pesticide P1 50 50 50 50 50 50 50 50 50
UV Absorber: 2-Hydroxy- 19 9.5
4-n-octyloxybenzophe- none
UV Absorber: Reaction 19 9.5
products of methyl 3-(3- (2H-benzotriazole-2-yl)- 5-t-butyl-4- hydroxy- phenyl) propionate / PEG
300
UV Absorber: N-(2- 19 9.5
ethoxyphenyl)-N'-(2- ethylphenyl) ethanedia- mide
UV Absorber: ethyl 2-cy- 19 9.5 ano-3-phenylcinnamate
S2: N,N-dimethyllactam- 75 75 75 75 75 75 75 75 75 ide
S1 : aromatic hydrocar80 80 80 80 80 80 80 80 80 bons
S1 : N,N-Dimethyldecan- 100 100 100 100 100 100 100 100 100 1 -amide
S1 : methylbenzoate 485 466 475.5 466 475.5 466 475.5 466 475.5
Auxiliary A 25 25 25 25 25 25 25 25 25
Auxiliary B 15 15 15 15 15 15 15 15 15
Auxiliary C 50 50 50 50 50 50 50 50 50
Auxiliary D 100 100 100 100 100 100 100 100 100
Auxiliary E 50 50 50 50 50 50 50 50 50
Percentage of P1 remaining after UV irradiation
0 h 100 100 100 100 100 100 100 100 100
6 h 77 97 95 98 89 97 94 98 97
24 h 60 95 85 91 78 95 87 93 88
48 h 31 92 74 85 71 88 79 88 78 Table 2: EC composition and P1 stability - with and without UV absorber:
Figure imgf000025_0001
Table 3: EC composition and P1 stability - comparison of different UV Absorbers:
Examples 1 1 12 17 18 19 20 21 22
Composition of EC [g/L]
Pesticide P1 40 40 40 40 40 40 40 40
Pesticide P2A 40 40 40 40 40 40 40 40
UV Absorber: 2-Hydroxy-4-n-oc- 19 9.5
tyloxybenzophenone
UV Absorber: Reaction product of 19 9.5
methyl 3-(3-(2H-benzotriazole-2- yl)-5-t-butyl-4- hydroxyphenyl) propionate / PEG 300 UV Absorber: N-(2-ethoxyphenyl)- 19 9.5
N'-(2-ethylphenyl) ethanediamide
UV Absorber: ethyl 2-cyano-3-phe- 19 9.5 nylcinnamate
S2: N,N-dimethyllactamide 75 75 75 75 75 75 75 75
S1 : aromatic hydrocarbons 80 80 80 80 80 80 80 80
S1 : N,N-Dimethyldecan-1 -amide 200 200 200 200 200 200 200 200
S1 : benzylacetate 376 385.5 376 385.5 376 385.5 376 385.5
Auxiliary A 25 25 25 25 25 25 25 25
Auxiliary B 15 15 15 15 15 15 15 15
Auxiliary C 50 50 50 50 50 50 50 50
Auxiliary D 75 75 75 75 75 75 75 75
Auxiliary E 25 25 25 25 25 25 25 25
Percentage of P1 remaining after UV irradiation
0 h 100 100 100 100 100 100 100 100
6 h 94 94 98 88 97 93 98 95
24 h 94 84 90 78 91 86 90 87
48 h 91 77 84 69 85 79 87 78
Table 4: EC composition and P1 stability - with different UV absorbers and without UV absorber
Examples 23 24 25 26 27 28
Composition of EC [g/L]
Pesticide P1 50 50 40 40 40 30
Pesticide P2B 50 50 50 50 50 50
UV Absorber: 2-Hydroxy-4-n-octyloxybenzophenone 19 15
UV Absorber: N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) 15 ethanediamide
UV Absorber: ethyl 2-cyano-3-phenylcinnamate 15
S2 N,N-dimethyllactamide 200 200 100 100 75 75
S2 acetophenone 75 75
S1 aromatic hydrocarbons 35 35 35 50 80 80
S1 N,N-Dimethyldecan-1 -amide 100 100 150 200
S1 N,N-Dimethyldodecyl-1 -amide 100 100
S1 benzylacetate 385 366 520 495 340
S1 methyl benzoate 440
Auxiliary A 20 20 20 25 20 25
Auxiliary B 25 25 20 15 20 15
Auxiliary C 50 50 50
Auxiliary D 75 75 75 75 1 12.5 100
Auxiliary E 25 25 25 25 37.5 50
Percentage of P1 remaining after UV irradiation h 100 100 100 100 100 100 h 77 96 60 98 96 98 h 58 92 44 93 94 88 h 57 88 23 88 92 85 h 55 84 18 84 90 83 h 41 82 16 83 85 82

Claims

Claims
1 . Agrochemical formulations comprising a) a pesticide P1 , said pesticide P1 being 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]- 3-methyl-phenyl]-4-methyl-tetrazol-5-one; b) At least one organic solvent S1 having a water solubility of less than 1 % at 20°C; and c) at least one UV absorber A, said at least one UV absorber A being water insoluble.
2. Formulation according to claim 1 , further comprising at least one organic solvent S2, which is water miscible at 20 °C.
3. Formulation according to any of claims 1 to 2, wherein said formulation comprises at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and at least one organic solvent S2 selected from Ν,Ν-dimethyllactamide, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
4. Formulation according to any of claims 1 to 3, wherein said formulation comprises 10 to 60 wt% of at least one solvent S1 and 0 to 30 wt% of at least one organic solvent S2.
5. Formulation according to any of claims 1 to 4, wherein said formulation comprises 10 to 60 wt% of at least one solvent S1 selected from benzylacetate, methylbenzoate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures and 0 to 30 wt% of at least one organic solvent S2 selected from Ν,Ν-dimethyllactamide, methyl-5-(dimethylamino)-2- methyl-5-oxopentanoate, acetophenone, DMSO, cyclohexanone, gamma-butyrolactone, benzyl alcohol or their mixtures.
6. Formulation according to any of claims 1 to 5, wherein said formulation comprises 10 to 60 wt% of benzylacetate, C8-C12 fatty acid dimethyl amide, aromatic hydrocarbons or their mixtures as organic solvent S1 and 0 to 30 wt% of N,N-dimethyllactamide.
7. Formulation according to any of claims 1 to 6, wherein said UV absorber A has an absorb- ance in the range of 300-340 nm of at least 0.2.
8. Formulation according to any of claims 1 to 7, wherein the weight ratio of pesticide P1 to UV absorber A is in the range from 50:1 to 1 :1.
9. Formulation according to any of claims 1 to 8, where the weight ratio of the at least one organic solvent S1 to UV absorber A is in the range from 100:1 to 3:1 .
10. Formulation according to any of claims 1 to 9 where UV absorber A is selected from ben- zotriazoles, benzophenones, triazines, oxanilides or their mixtures.
1 1 . Formulation according to any of claims 1 to 10 where the agrochemical formulation comprises 0.5 to 20 wt% of UV absorber A.
12. Formulation according to any of claims 1 to 1 1 , where the formulation comprises from 1 to 30 wt% of pesticide P1.
13. Formulation according to any of claims 1 to 12, wherein the agrochemical formulation is se- lected from emulsifiable concentrates (EC), suspoemulsion concentrates (SE), emulsions
(EW), microemulsions (ME) or microcapsules (CS).
14. Formulation according to any of claims 1 to 13 wherein the agrochemical formulation is an emulsifiable concentrate (EC).
15. Formulation according to any of claims 1 to 14, further comprising a further pesticide P2.
16. A method for controlling phytopathogenic fungi, wherein the fungi, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propa- gation material are treated with an effective amount of a formulation as defined in any of claims 1 to 15.
17. Method according to claim 16, wherein said formulation is applied in an amount such that 20 to 100 grams per hectar of pesticide P1 and 10 to 50 g/ha of at least one UV absorber A are applied.
18. A method according to claim 16 to 17, which comprises the steps of a) dissolving pesticide P1 and at least one UV absorber A in at least one organic solvent S1 and optionally organic solvent S2 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 spray solution, e.g. a tank mix, and allowing the spray solution to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on unde- sired plants and/or the crop plants and/or their environment.
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