KR100349458B1 - Use of Phosphate Ester as Crystallization Agent - Google Patents

Abstract

The present invention relates to the application of A) certain azole derivatives with crystallization tendencies and B) suitable spraying aqueous compounds containing one or more other active compounds and additives, where appropriate, It relates to a phosphate ester of formula (I) which can be used to prevent crystallization.

In the above formula,

R ¹ represents alkyl having 2 to 18 carbon atoms,

R ² and R ³ independently of each other represent alkyl having 2 to 12 carbon atoms.

Description

Use of Phosphate Ester as Crystallization Inhibitor

The present invention relates to the novel use of certain phosphate esters to prevent crystallization when an aqueous mixture for spraying based on certain fungicidally active compounds is applied.

Spray devices commonly used to apply aqueous formulations of products for plant treatment have a number of filters and nozzles. For example, a vacuum filter is arranged between the tank and the tank pump, and a pressure filter is arranged below the pump in the pressure section. It is also possible to arrange the nozzle filter just before the spray nozzle. All such filters and nozzles can be somewhat consistently blocked by the active compound which crystallizes when an aqueous spray mixture based on a solid active compound is applied.

The azole derivatives mentioned below are fungicidally active and can be applied to plants and / or their habitats in the form of aqueous spray mixtures:

1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol,

1- (4-phenyl-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol,

1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol,

1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -hexan-2-ol,

1-([bis- (4-fluorophenyl) -methyl-silyl] -methyl) -1H- (1,2,4-triazole),

1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-en-3-ol,

1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-&-3-ol,

1- (4-chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol,

1- (4-chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) -butane and

1- [3- (2-Chlorophenyl) -2- (4-fluorophenyl) -oxirane-2-yl-methyl] -1 H- (1,2,4-triazole).

Reference example: EP-OS (European publication specification) 0 040 345, DE-PS (German patent specification) 2 201 063 DE-PS 2 324 010, EP-OS 0 015 756, US-PS (US patent specification) 4 551 469, EP-OS 0 068 813, DE-OS (DE-OS) 2 838 847, DE-OS 3 010 560, DE-OS 3 406 993, DE-OS 2 821 971 and EP-OS 0 196 038.

It is also known that N-alkyllactams and N, N-dimethylalkylcarboxamides can be used as crystallization inhibitors in the preparation and application of spray mixtures of the above-mentioned active compounds (see European Publication 0 0 391 168). And 0 453 899). For example, for spraying containing 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane-3- as active compound N-octylpyrrolidone and / or 5% N, N-dimethylhexanamide, 50% N, N-dimethyloctanamide, 40 to prevent crystallization of the active compound in the spraying device when an aqueous mixture is applied Mixtures having an average composition of% N, N-dimethyldecanamide and 5% N, N-dimethyldodecanamide can be used. However, the activity of the above-mentioned crystallization inhibitor is not always satisfactory when such a spray mixture is used for a long time.

Finally, tributyl phosphate is (±) -2-ethoxy-2,3-dihydro-3,3--dimethylbenzofuran-5-yl-methylsulfonate (= etofume) in the preparation of the herbicidally active compound. It is known that it can be used to inhibit the crystallization of (Sate) (European publication 0 328 217). However, the similar use of other agrochemically active compounds in the formulation is not yet known.

To the present invention

A) at least one azole derivative of formula (II) and / or at least one azole derivative of formula (III) and / or at least one azole derivative of formula (IV) and / or 1-([bis- (4-fluorophenyl) -methyl-silyl] -methyl) -1H- (1,2,4-triazole) of V) and / or 1- [3 of formula (VI) -(2-chlorophenyl) -2- (4-fluorophenyl) -oxirane-2-yl-methyl] -1 H-(1,2,4-triazole) and

B) Where appropriate, when using an aqueous spray mixture containing one or more other active compounds and additives, the following general formulas are used to prevent crystallization of the active compounds of the general formulas (II) to (VI) It was found that the phosphate ester of formula (I) can be used.

In the above formula,

R ¹ represents 2 to 18 carbon atoms, and

R ² and R ³ independently represent alkyl having 2 to 12 carbon atoms,

In general formula (II),

a) R ⁴ is Indicates,

R ⁵ represents t-butyl,

R ⁶ represents hydroxyl, or

b) R ⁴ represents 4-fluorophenyl,

R ⁵ represents 2-fluorophenyl,

R ⁶ represents hydroxyl, or

c) R ⁴ represents 2,4-dichlorophenyl,

R ⁵ represents n-butyl,

R ⁶ represents hydroxyl, or

d) R ⁴ is Indicates,

R ⁵ represents phenyl,

R ⁶ represents cyano, or

e) R ⁴ represents 4-chlorophenyl,

R ⁵ is Indicates

R ⁶ represents hydroxyl,

In general formula (III),

a) Y represents -CH (OH),

R ⁷ represents chlorine or phenyl,

b) Y represents CO,

R ⁷ represents chlorine,

R ⁸ represents hydrogen or chlorine.

It is surprising that the crystallization propensity of the azole derivatives of formulas (II) to (VI) was significantly reduced by using the phosphate esters of formula (I) according to the invention. In particular, it was not expected that the phosphate esters of general formula (I) would be more suitable for the presented purpose than N-alkyllactams and N, N-dimethylalkylcarboxamides.

The use of phosphate esters of formula (I) in aqueous formulations based on fungicidally active azole derivatives of formulas (II) to (VI) has a series of advantages. For example, the phosphate ester of general formula (I) is a substance which is easy to handle and can be used in large quantities. In addition, by using a substance of the general formula (I), when the aqueous formulation containing the active compounds of the general formulas (II) to (VI) is applied by spraying, it is possible to prevent the filter and the nozzle of the spraying apparatus from clogging. . Another advantage is that the phosphate esters of formula (I) do not cause any kind of unwanted side effects in plant protection.

Formula (I) provides a general definition of phosphate esters which may be used according to the invention.

R ¹ preferably represents straight or branched chain alkyl having 4 to 12 carbon atoms,

R ² preferably represents straight or branched alkyl having 2 to 8 carbon atoms,

R ³ preferably represents straight or branched chain alkyl having 2 to 8 carbon atoms.

R ¹ is particularly preferably n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octic, iso-octyl, n -Nonyl, iso-nonyl, n-decyl, n-dodecyl or iso-dodecyl,

R ² particularly preferably represents n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl or iso-octyl ,

R ³ particularly preferably represents n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl or iso-octyl .

Examples of phosphoric acid esters that may be used according to the invention include tri-n-butyl phosphate, tri-n-pentyl phosphate, tri-n-hexyl phosphate, tri-n-heptyl phosphate, tri-n-octyl phosphate and tri- (2 -Ethyl-hexyl) phosphate may be mentioned.

Phosphoric acid esters of general formula (I) are already known (see Organic Chemistry Reference).

Formulas (II) to (VI) provide definitions of azole derivatives contained in an aqueous spray mixture which can be used according to the invention. The following azole derivatives may be included alone or several.

1- (4-Chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol of formula (II-a)

1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol of formula (II-b)

1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -hexan-2-ol of formula (II-c)

1- (4-Chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) -butane of formula (II-d)

1- (4-Chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol of formula (II-e)

1- (4-Chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol of formula (III-a)

1- (4-phenyl-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol of formula (III-b)

1- (4-Chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one of formula (III-c)

1- (4-Chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-en-3-ol of formula (IV-a)

1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-ene-3- of the formula (IV-b) Come

1-([bis- (4-fluorophenyl) -methyl-silyl] -methyl) -1H- (1,2,4-triazole of formula (V)

1- [3- (2-Chlorophenyl) -2- (4-fluorophenyl) -oxirane-2-yl-methyl] -1 H- (1,2,4-triazole) of formula (VI)

Compounds of formulas (II) to (VI) and their use for controlling phytopathogens are known (EP-OS (European Publication) 0 040 345, US Patent Specification 4 551 469, EP-PS (European Patent Specification) ) 0 015 756, EP-OS 0 068 813, DE-OS (Declaration of Federal Republic of Germany) 3 406 993, DE-PS (Declaration of Federal Republic of Germany) 2 324 010, DE-PS 2 201 063, DE-OS 2 838 847, DE-OS 3 010 560, DE-OS 2 821 971 and EP-OS 0 196 038).

The active compounds of general formulas (II) to (VI) can be used in conventional formulations. They may preferably be applied in the form of an aqueous mixture for spraying,

Spray mixtures which can be used according to the invention may also contain one or more other active compounds in addition to the active compounds of general formulas (II) to (VI), which preferably comprises compounds which exhibit fungicidal activity. Suitable. Examples of the active compounds which may be further used

N, N-dimethyl-N'-phenyl- (N'-fluorodichloromethylthio) -sulfamide (diclofluanide),

N, N-dimethyl- (N'-fluorodichloromethylthio) -N '-(4-methyl-phenyl) -sulfamide (tolylfluanide),

N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide (captan),

N- (1,1,2,2-tetrachloroethyl-sulphenyl) -cis-4-cyclohexene-1,2-dicarboxamide (captapol),

N-trichloromethylthio-phthalimide (polpet),

N-dodecyl-guanidine-acetate (dodine),

Tetrachloro-isophthalo-dinitrile (chlorotalonyl),

4,5,6,7-tetrachlorophthalide,

Zinc ethylene-bis-dithiocarbamate (Geneb),

Manganese ethylene-bis-dithiocarbamate (maneb),

Zinc ethylene-bis-dithiocarbamate / manganese ethylene-bis-dithiocarbamate (mancozeb),

Zinc propylene-1,2-bis-dithiocarbamate (propineb),

1- [3- (4- (1,1-dimethylethyl) -phenyl) -2-methylpropyl] -piperidine (phenpropidine),

N-tridecyl-2,6-dimethyl-morpholine (tridemorph),

N-dodecyl-2,6-dimethyl-morpholine (Aldimorph),

Cis-4- [3- (4-t-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine (phenpropimorph),

2- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) -ethyl] -imidazole (imazaryl),

N- [2- (2,4,6-trichlorophenoxy) -ethyl] -N-propyl-1H-imidazole (prochloraz),

1- [2- (2,4-Dichlorophenyl) -4-propyl- (1,3-dioxolan-2-yl) -methyl] -1H- (1,2,4-triazole) (propicozazole ),

N- (3,5-dichlorophenyl) -1,2-dimethyl-cyclopropane-1,2-dicarboximide (procymidone),

2-methoxycarbamoyl-benzimidazole (carbendazim),

1- (butylcarbamoyl) -2-benzimidazole-methylcarbamate (benomyl),

2,4-dichloro-6- (2'-chlorophenyl-amino) -1,3,4-triazine (anilaazine),

Bis- (8-guanidine-O-octyl) -amine-triacetate (guazatin),

Mention may be made of 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenyl-urea (pensaicuron).

Suitable additives which may be present in the spraying mixtures usable according to the invention are surfactants, organic diluents, acids, low temperature stabilizers, tackifiers and other crystallization inhibitors.

Suitable surfactant materials are nonionic, anionic, cationic and zwitte-r emulsifiers. Such materials include the reaction products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkyl phenols or alkylarylphenols with ethylene oxide and / or propylene oxide, and sulfuric acid esters, phosphate mono-esters and phosphate di-esters, also ethylene Reaction products of oxides with propylene oxide, alkylsulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl-ammonium halides, trialkyl-aryl-ammonium halides and alkylamine sulfonates. Emulsifiers can be used alone or in the form of mixtures. These preferably include a reaction product of castor oil in a molar ratio of 1:20 to 1:60 and an ethylene oxide, a reaction product of C ₆ -C ₂₀ fatty alcohol in an ethylene oxide ratio of 1: 5 to 1:50, and 1: Reaction product of 2 to 1:20 molar ratio of fatty amine and ethylene oxide, 1 mole of phenol and 2 to 3 moles of styrol and 10 to 50 moles of ethylene oxide, 1 water of phenol and 2 to 3 moles of vinyl Reaction product of toluene and ethylene oxide of 10 to 50 water, reaction product of C ₈ -C _l2 alkylphenol and ethylene oxide in a 1: 5 to 1:30 molar ratio, alkyl glycosides, and C ₈ -C ₁₆ alkyl-benzene sulfonic acid Salts such as calcium, monoethanolammonium, di-ethanolammonium and triethanol ammonium salts may be mentioned.

The emulsifier obtained from the alkylaryl-polyglycol-ether group actually used is a mixture of one or more compounds. In particular, they are mixtures of substances having different degrees of substitution on the phenyl ring bound to the number of oxyethylene units and oxyethylene units, which explains why the average value for calculating the number of substituents on the phenyl ring contains fractional values. May be mentioned substances having the following average composition:

Organic diluents which may be present in the spraying mixtures which can be used according to the invention are all polar and nonpolar organic solvents which can be customarily used for this purpose. These are preferably ketones such as methyl isobutyl ketone and cyclohexanone, amides such as dimethylformamide, N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N Octyl-caprolactam, N-dodecyl-caprolactam and Cyclic compounds such as butyrolactone, strong polar solvents such as dimethyl sulfoxide, aromatic hydrocarbons such as xylene, and propyleneglycol monomethyl ether acetate, dibutyl adipate, hexyl acetate, heptyl acetate, tri-n- Esters such as butyl citrate and di-n-butyl phthalate, and also ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and 1-methoxy-2- Alcohols such as propanol are preferred.

Acids which may be present in the spraying mixtures which can be used according to the invention are all inorganic and organic acids which can conventionally be used for this purpose. As these, aliphatic and aromatic hydroxycarboxylic acids such as citric acid, salicylic acid and ascorbic acid are suitable.

Low temperature stabilizers which may be present in the spray mixtures usable in accordance with the invention are all materials customarily usable for this purpose. Among these, urea, glycerin and propylene glycol are suitable.

Tackifiers which may be present in the spray mixtures usable in accordance with the invention are all materials customarily usable for this purpose. These are preferably suitable for natural and synthetic phospholipids, such as carboxymethyl cellulose and gum arabic, polyvinyl alcohol and polyvinyl acetate, natural and synthetic polymers in the form of granules or emulsions, and cephalins and lecithins. As other additives, mineral oil and vegetable oil may be used.

In addition to the phosphate esters of general formula (I), crystallization inhibitors may also be included in the spray mixtures which can be used according to the invention. In the present invention, a mixture containing an average of 5% N, N-dimethylhexaneamide, 50% N, N-dimethyloctanamide, 40% N, N-dimethyldecanamide and 5% NN-dimethyldodecanamide This is suitable.

The spray mixtures which can be used according to the invention also contain water in each case.

The concentration of the active compound in the spray mixtures which can be used according to the invention can be varied within a certain range. In general, the concentration of the active compound is from 0.003 to 5% by weight, preferably from 0.003 to 3% by weight.

The ratio of the active compound of general formulas (II) to (VI) to the phosphate ester of general formula (I) can also be varied within certain ranges. In general, the weight ratio of active compound from group (A) to the phosphate ester of general formula (I) is from 1: 0.2 to 1: 5, preferably from 1: 0.6 to 1: 2.

The amount of other active compounds or additives in the spray mixtures that can be used according to the invention can be varied within a wide range. In this case, the amount used is usually the amount found in the aqueous spray mixture.

Spray mixtures which can be used according to the invention can be prepared by conventional methods. Generally, the necessary ingredients are first formulated in the desired order at a temperature of 10 ° C. to 30 ° C., the batches are mixed until uniform, and then the resulting mixture is filtered as necessary to produce the concentrate first. In order to prepare a spray mixture for immediate use, the concentrated formulation is mixed with the required amount of water in each case while stirring and / or pumping, where appropriate, to distribute the formulation uniformly and microdispersed in water.

All mixing devices and spraying devices which are normally suitable for this purpose can be used to prepare and apply spray mixtures which can be used according to the invention, and to prepare concentrated formulations.

By using the phosphate ester of formula (I) in an aqueous sprayable mixture based on the active compound of general formulas (II) to (VI), in the readily available concentrated formulations and during the application of the sprayed aqueous mixtures made from such formulations Crystallization of the active compound at the filter and outlet of the spraying device is inhibited or completely prevented so that the application of the spraying mixture is not adversely affected.

Examples of preparation and crystallization tendencies of spray mixtures which can be used according to the invention will be described in detail in the examples which follow.

Manufacturing Example

Example 1

To prepare the preparation, 1- (4-chlorophenyl) -4,4-dimethyl 3- (1,2,4-triazol-1-yl-methyl) -pentane-3 of formula (II-a) 25.0 parts by weight of -ol, 40.0 parts by weight of tri-n-butyl phosphate, 6.5 parts by weight of (2-hydroxyethyl) -ammonium 4- (n-dodecyl) -benzene-sulfonate, structural formula

6.5 parts by weight of an emulsifier of average composition of 2 parts by weight of N-methyl-pyrrolidone and 2.0 parts by weight of water were mixed and stirred at room temperature to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of the strength defined below (CIPAC-C water) to prepare a spray mixture containing 0.5% by weight of the concentrate.

CIPAC-C water = 1 water containing 4 mmol of calcium chloride and 1 mmol of magnesium chloride per 1.

Example 2

To prepare the formulation, 1- (4-chlorophenyl) -4.4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane-3- of formula (II-a) 25.0 parts by weight, 20.0 parts by weight of tri-n-butyl phosphate, 6.5 parts by weight of (2-hydroxyethyl) -ammonium 4- (n-dodecyl) -benzene-sulfonate, structural formula

6.5 parts by weight of an emulsifier of average composition, 5.0 parts by weight of N-methyl-pyrrolidone, 2.0 parts by weight of water, and 5% of N, N-dimethylhexanamide, 50% of N, N-dimethyloctanamide, 40% 35.0 parts by weight of a mixture having an average composition of N, N-dimethyldecanamide and 5% N, N-dimethyldodecaneamide at room temperature were mixed and stirred to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of defined intensity (CIPAC-C water; see Example 1) to prepare a spray mixture containing 0.5% by weight of concentrate.

Example 3

To prepare the preparation, 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane- of the following structural formula (II-a) 25.0 parts by weight of 3-ol, 20.0 parts by weight of tri-n-butyl phosphate, 5% of N, N-dimethylhexanamide, 50% of N, N-dimethyloctanamide, 40% of N, N-dimethyldecanamide and 35.0 parts by weight of a mixture having an average composition of 5% N, N-dimethyldodecanamide, and 20.0 parts by weight of a reaction product of castor oil and ethylene oxide in a 1:30 molar ratio were mixed and stirred at room temperature to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of defined intensity (CIPAC-C water; see Example 1) to prepare a spray mixture containing 0.5% by weight of the concentrate.

Example 4

To prepare the preparation, 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane- of the following structural formula (II-a) 25.0 parts by weight of 3-ol, 20.0 parts by weight of tri- (2-ethyl-hexyl) phosphate, 5% of N, N-dimethylhexanamide, 50% of N, N-dimethyloctanamide, 40% of N, N- 35.0 parts by weight of a mixture having an average composition of dimethyldecanamide and 5% of N, N-dimethyldodecanamide, structural formula

6.5 parts by weight of an emulsifier having an average composition of 6.5 parts by weight of 4- (n-dodecyl) -benzene-sulfonic acid (2-hydroxyethyl) ammonium salt, 5.0 parts by weight of N-methyl-pyrrolidone, and 2.0 parts by weight of water. Mix and stir at room temperature to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of defined intensity (CIPAC-C water; see Example 1) to prepare a spray mixture containing 0.5% by weight of the concentrate.

Example 5

To prepare the preparation, 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane- of the following structural formula (II-a) 25.0 parts by weight of 3-ol, 30.0 parts by weight of tri-n-butyl phosphate, 20.0 parts by weight of N-octylcaprolactam, 9.0 parts by weight of N-methyl-pyrrolidone, structural formula

8.0 parts by weight of an emulsifier of average composition and 8.0 parts by weight of 4- (n-dodecyl) -benzene-sulfonic acid (2-hydroxyethyl) ammonium salt were mixed and stirred at room temperature to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of defined intensity (CIPAC-C water; see Example 1) to prepare a spray mixture containing 0.5% by weight of the concentrate.

Example A (comparative example)

EP-OS (European Publication) 0 453 899 is known.

To prepare the preparation, 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane- of the following structural formula (II-a) 25.0 parts by weight of 3-ol, 5% of N, N-dimethylhexanamide, 50% of N, N-dimethyloctanamide, 40% of N, N-dimethyldecanamide and 5% of N, N-dimethyldodecane 35.0 parts by weight of a mixture having an average composition of amide, structural formula

6.5 parts by weight of an emulsifier of average composition, 20.0 parts by weight of N-octylpyrrolidone, 5.0 parts by weight of N-methylpyrrolidone and (2-hydroxyethyl) ammonium 4- (n-dodecyl) -benzene-sulfonate 6.5 parts by weight and 2.0 parts by weight of water are mixed at room temperature and stirred to obtain a homogeneous liquid.

Using the resulting concentrate, the concentrate was mixed with water of defined intensity (CIPAC-C water; see Example 1) to prepare a spray mixture containing 0.5% by weight of the concentrate.

Example of use

To test the crystallization propensity, 250 ml of sprayed aqueous mixture containing in each case 0.5% by weight of the concentrate is continuously circulated by pumping through the micromesh in a flow apparatus at a temperature of 5 ° C. The differential pressure on the sieve is measured to indirectly examine the crystal deposited on the sieve. A significant increase in pressure means that the sieve's mesh was blocked to a significant extent by the deposition of crystals.

The formulations used and test results are shown in the table below.

Claims (6)

Azole derivatives of formula (II), azole derivatives of formula (III), azole derivatives of formula (IV), 1-([bis- (4-fluorophenyl) -methyl-silyl] of formula (V) -Methyl) -1H- (1,2,4-triazole) and 1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) -oxirane-2-yl of formula (VI) Aqueous solution, characterized in that it contains a phosphate ester of formula (I) together with an aqueous spray mixture comprising at least one active compound selected from the group consisting of -methyl] -1H- (1,2,4-triazole) Or a composition that does not crystallize when sprayed with an emulsion. In the above formula, R ¹ represents alkyl having 2 to 18 carbon atoms, R ² and R ³ independently of each other represent alkyl having 2 to 12 carbon atoms, In general formula (II), a) R ⁴ is Indicates, R ⁵ represents t-butyl, R ⁶ represents hydroxyl, or b) R ⁴ represents 4-fluorophenyl, R ⁵ represents 2-fluorophenyl, R ⁶ represents hydroxyl; or c) R ⁴ represents 2,4-dichlorophenyl, R ⁵ represents n-butyl, R ⁶ represents hydroxyl, or d) R ₄ is Indicates, R ⁵ represents phenyl, R ⁶ represents cyano, or c) R ⁴ represents 4-chlorophenyl, R ⁵ is Indicates R ⁶ represents hydroxyl, In general formula (III), a) Y represents -CH (OH), R ⁷ represents chlorine or phenyl, b) Y represents CO, R ⁷ represents chlorine, R ⁸ represents hydrogen or chlorine. The method of claim 1, R ¹ represents straight or branched chain alkyl having 4 to 12 carbon atoms, R ² represents straight or branched chain alkyl of 2 to 8 carbon atoms, R ³ is a composition characterized in that a phosphate ester of the general formula (I) which represents straight or branched alkyl having 2 to 8 carbon atoms is used. The method of claim 1, R ¹ is n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, iso Nonyl, n-decyl, n-dodecyl or iso-dodecyl, R ² represents ethyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl or iso-octyl, R ³ is a general formula representing ethyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl or iso-octyl A composition characterized in that the phosphate ester of (I) is used. The composition of claim 1 wherein tri-n-butyl phosphate is used. The compound of claim 1, wherein 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentane-3 of formula II-a Tri-n-butyl phosphate is used in the spray mixture containing the -ol. At least one phosphate ester of general formula (I) according to claim 1 and at least one activity selected from the group consisting of general formulas (II), (III), (IV), (V) and (VI) Adding to the sprayable aqueous mixture containing the compound, thereby preventing crystallization of the compounds of the general formulas (II) to (VI) when the spraying aqueous mixture is applied.