# Patent

## Title
Agrochemical composition and method for preparing and using the same

## Abstract

An agrochemical composition comprises an azole active ingredient and an N,N-dialkyl long chain alkylamide. The N,N-dialkyl long chain alkylamide is present in sufficient amount to prevent or inhibit the crystallization of the azole derivative during the application of the composition to a locus. Preferred N,N-Dialkyl long chain alkylamide(s) comprised in the composition is/are selected from the group consisting of compounds of the formula (I): in which (a) R1 and R2 are independently normal alkyl radicals having 2 carbon atoms, and R represents an alkyl group having from 10 to 30 carbon atoms; or (b) R1 and R2 are independently normal alkyl radicals having 3 carbon atoms, and R represents an alkyl group having from 9 to 30 carbon atoms; or 20 (c) R1 and R2 are independently normal alkyl radicals having from 4 to 20 carbon atoms and R represents an alkyl group having from 6 to 30 carbon atoms. The composition is particularly advantageous when formulated with a fungicide, in particular one or more of tebuconazole, cyproconazole, difenoconazole, diniconazole, triticonazole, hexaconazole, triflumiazole, metconazole, tricylazole, flusilazole, flutriafol, and myclobutanil.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a 371 U.S. National Stage of International Application No. PCT/CN2008/071116, filed May 28, 2008. This application claims the benefit of Chinese Patent Application No. 200710022965.0, filed May 28, 2007. The disclosures of the above applications are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to an agrochemical composition. The invention is especially concerned with such compositions comprising one or more compounds active as a fungicide. The present invention further relates to a method of preparing the aforementioned compositions and their use in crop protection. The present invention is particularly concerned with the inhibition of crystal growth in aqueous spray liquors based on azole pesticidal compounds and to compositions exhibiting reduced crystal growth.
BACKGROUND OF THE INVENTION
Perhaps the most prevalent practice for applying pesticides to plants is by spraying aqueous liquors onto the plants to be treated. The spray equipment customarily used for the application of aqueous formulations of plant treatment agents is well known in the art and generally comprises one or more filters and/or nozzles. Some technical difficulties are associated with spraying practice when predominantly aqueous compositions of pesticides which are essentially water insoluble, are employed. In such cases, often the filters and nozzles are clogged as a result of crystal growth of the water insoluble active ingredients. Certain pesticidally active azole derivates show a particular tendency to crystallize in such situations.
A particular method for overcoming this problem is by inhibiting or preventing the crystal growth of the pesticide in the sprayer parts by employing a crystal growth inhibitor in the pesticidal composition. Thus, U.S. Pat. No. 5,206,225 describes the use of certain alkyl carboxylic acid dimethylamides as crystallization inhibitors of azole fungicides. Further, U.S. Pat. No. 5,369,118 describes the use of alkyl lactam as a crystal growth inhibitor of azole fungicides.
The crystal growth inhibitors disclosed in the prior publications do not offer a solution for all needs, practices and conditions employed in agriculture. Thus, there is an ongoing need to develop further crystal growth inhibitors applied in agriculture which overcome the shortcoming of the prior art and to provide formulations comprising such inhibitors.


DETAILED DESCRIPTION OF THE INVENTION
In the present invention it is surprisingly found that certain N,N-dialkyl long chain alkylamides are useful for preventing the crystallization during the application of aqueous spray liquors having azole derivatives as the active agrochemical ingredient.
U.S. Pat. No. 5,206,225 discloses the use of varieties of alkylcarboxylic acid dimethylamide of the formula R—CO—N(CH3)2 as crystallization inhibitors of azole fungicides. Although U.S. Pat. No. 5,206,225 describes the R group may represent alkyl having 5 to 19 carbon atoms, the amide group is exclusively dimethylamide. Thus, U.S. Pat. No. 5,206,225 teaches away from developing other dialkylamide derivatives for using as a crystallization inhibitor in agrochemical composition comprising azole derivatives as active ingredients.
DE 4,341,986 is concerned with the use of carboxylic acid amides having the general formula R—CO—N(R1R2) as crystallization inhibitors, in particular for fungicidally active compounds. DE 4,341,986 discloses a very wide range of compounds having the aforementioned formula and suggests that compounds of the aforementioned formula in which R is hydrogen, alkyl having from 1 to 16 carbon atoms, hydroxy alkyl having from 1 to 10 carbon atoms, alkenyl having from 2 to 16 carbon atoms, cycloalkyl having from 5 to 7 carbon atoms, cycloalkyl having from 5 to 7 carbon atoms, aralkyl having from 6 to 10 carbon atoms in the aryl group and from 1 to 4 carbon atoms in the alkyl chain, aralkenyl having from 6 to 10 carbon atoms in the alkyl group and from 2 to 4 carbon atoms in the alkenyl chain, phenoxyalkyl having from 1 to 4 carbon atoms in the alkyl or a wide range of amide groups, and in which R1 is hydrogen, alkyl having from 1 to 12 carbon atoms, hydroxyalkyl having from 1 to 8 carbon atoms, alkenyl having from 2 to 12 carbon atoms, optionally substituted cycloalkyl having from 5 to 7 carbon atoms, phenyl, benzyl or phenethyl, and R2 is alkyl having from 2 to 12 carbon atoms, hydroxyalkyl having from 1 to 8 carbon atoms, alkenyl having from 2 to 12 carbon atoms, optionally substituted cycloalkyl having from 5 to 7 carbon atoms, phenyl, benzyl or phenethyl may inhibit the crystallization of a wide range of azole derivatives.
DE 4,341,986 indicates a very large number of carboxylic acid amides and prefers to have R, R1 and R2 different classes of groups, in particular mixing saturated groups, such as alkyl and cycloalkyl, with unsaturated group, such as alkenyl, phenyl-containing groups, and amide groups. DE 4,341,986 discloses within the very broad range of carboxylic acid amides indicated a range of alkyl amides. However, DE 4,341,986 favours the use of carboxylic acid amides in which lower alkyl groups are present, that is in which the length of the alkyl chain and/or the total number of alkyl carbon atoms is low. In particular, of the alkyl amides specifically exemplified in table 2 of DE 4,341,986, representing a minority of the carboxylic amides exemplified in table 2 of 986', R is an alkyl group having 11 carbon atoms or fewer, with an emphasis being placed on R being a lower alkyl group. Further, of the alkyl amides specifically exemplified, the total number of carbon atoms in the alkyl groups of R, R1 and R2 does not exceed 16.
In the present invention, the surprising finding is that alkyl amides of the general formula of DE 4,341,986 in which R is a higher alkyl group, in particular, depending upon the nature of R1 and R2 in the formula having at least 6 carbon atoms, and/or the total number of carbon atoms in the alkyl groups of R, R1 and R2 exceeds 16, exhibit a markedly superior activity to inhibiting crystallization of a specific class of azole derivatives.
Based on the above surprising finding, the present invention relates to a use of certain N,N-dialkyl long chain alkylamides for preventing the crystallization during the application of aqueous spray liquors having azole derivatives as the active agrochemical ingredient. It has been found that such N,N-Dialkyl long chain alkylamides are particularly effective as crystal growth inhibitor in spray liquors comprising azole derivatives as active ingredients.
Accordingly, in a first aspect, the present invention provides an agrochemical composition comprising an azole active ingredient and a N,N-dialkyl long chain alkylamide.
More particularly, in the first aspect, the present invention provides an agrochemical composition comprising an N,N-dialkyl long chain alkylamide of the formula (I)




in which:
(a) R1 and R2 are independently normal alkyl radicals having 2 carbon atoms, and R represents an alkyl group having from 10 to 30 carbon atoms; or
(b) R1 and R2 are independently normal alkyl radicals having 3 carbon atoms, and R represents an alkyl group having from 9 to 30 carbon atoms; or
(c) R1 and R2 are independently normal alkyl radicals having from 4 to 20 carbon atoms and R represents an alkyl group having from 6 to 30 carbon atoms;
and at least one azole active ingredient having the general formula (II)




    
    
        in which R1 represents phenyl, 4-chlorophenyl, 4-chlorophenylethyl, 4-fluorophenyl, 2,4-dicholorophenyl, or 4-chlorophenyloxy;
    
    


R2 represents n-butyl, tert-butyl, phenyl, 2-fluorophenyl or a group of the general formula (III):




    
    
        and
        R3 represents hydroxyl, oxygen or cyano,
    
    


and optionally at least one member selected from the group consisting of a surface-active agent, organic diluent and low temperature stabilizer.
The azole active ingredients are water insoluble compounds and such compounds are prone to crystallizing in aqueous compositions. However, the compositions are generally applied in the form of an aqueous liquor, prepared by the dilution of a concentrate with water. The N,N-dialkyl long chain alkylamide is present in the composition in an amount sufficient to reduce and/or inhibit crystal growth formation of the azole active ingredient. It has been found that the N,N-dialkyl long chain alkylamides are effective in reducing and/or inhibiting crystal growth of azole active compounds. Thus, the inclusion of one or more N,N-dialkyl long chain alkylamides in the aqueous composition prevents the spray equipment and the like from being blocked and makes the spray liquor free of any crystals. This in turn maintains the composition in a more homogeneous condition. In addition, it has been found that the use of the N,N-dialkyl long chain alkylamides to prevent crystal formation and growth improves the efficiency and efficacy of the active ingredient.
The N,N-dialkyl long chain alkylamides are present in an amount sufficient to reduce and/or inhibit crystal growth of the azole compounds. The amount of the N,N-dialkyl long chain alkylamide present may depend upon the concentration of the azole active ingredient and may be determined by routine experimentation. The N,N-dialkyl long chain alkylamides are preferably present in an amount such as to give a weight ratio of the azole active ingredient to the N,N-dialkyl long chain alkylamide of from 1:0.1 to 1:5, more preferably from 1:1 to 1:4.
The composition may comprise a single N,N-dialkyl long chain alkylamide or a combination of two or more N,N-dialkyl long chain alkylamides.
The N,N-Dialkyl long chain alkylamide(s) comprised in the composition of the present invention is/are selected from the group consisting of compounds of the formula I:




in which,
(a) R1 and R2 are normal alkyl radicals having 2 carbon atoms, and R represents an alkyl group having 10 to 30 carbon atoms, more preferably from 11 to 18 carbon atoms;
(b) R1 and R2 are normal alkyl radicals having 3 carbon atoms, then R represents an alkyl group having 9 to 30 carbon atoms, more preferably from 9 to 18 carbon atoms; and
(c) R1 and R2 are normal alkyl radicals having 4 to 20 carbon atoms, more preferably from 4 to 8 carbon atoms, R represents an alkyl group having 6 to 30 carbon atoms, more preferably from 6 to 18 carbon atoms.
Alkyl groups present as R in the compounds of formula (I) may be straight chain or branched.
In one embodiment of the present invention, it is preferred that the alkyl groups R, R1 and R2 contain, in total, greater than 16 carbon atoms, more preferably greater than 18 carbon atoms, especially greater than 20 carbon atoms.
According to a preferred embodiment of the present invention, the preferred N,N-dialkyl long chain alkylamides are selected from the group consisting of diethyldodecanamide, diethyltridecanamide, N,N-diethyltetradecanamide, N,N-diethylhexadecanamide, N,N-diethylheptadecanamide, N,N-diethyloctadecanamide, N,N-diethylnonadecanamide, N,N-dipropyldecanamide, N,N-dipropyldodecanamide, N,N-dipropyltridecanamide, N,N-dipropyltetradecanamide, N,N-diethylhexadecanamide, N,N-dipropylheptadecanamide, N,N-dipropyl octadecanamide, N,N-dipropylnonadecanamide, N,N-dibutylheptamide, N,N-dibutyloctanamide, N,N-dibutylnonamide, N,N-dibutyldecanamide, N,N-dibutyldodecanamide, N,N-dibutyltridecanamide, N,N-dibutyltetradecanamide, N,N-dibutylhexadecanamide, N,N-dibutylheptadecanamide, N,N-dibutyloctadecanamide, N,N-dibutylnonadecanamide, N,N-dipentyloctanamide, N,N-dipentyldecanamide, N,N-dipentyldodecanamide, N,N-dipentyltetradecanamide, N,N-dipentylhexadecanamide, N,N-dipentyloctadecanamide, or any mixture thereof.
The composition of the present invention may be a concentrate, which is diluted with water prior to application on the plants to be treated. In this case, the one or more N,N-dialkyl long chain alkylamides are preferably present in an amount of from 5% to 80% by weight, more preferably from 20% to 60% by weight.
As noted above, it has been found that N,N-dialkyl long chain alkylamides are effective in reducing or inhibiting the crystal formation of certain azole derivatives active as agrochemicals, in particular pesticides. The composition may comprise one or more azole derivative active ingredients.
The N,N-dialkyl long chain alkylamides are particularly effective in preventing the crystallization of azole derivatives that are active as fungicides. In particular, the N,N-dialkyl long chain alkylamides have been found to be effective as inhibiting crystal growth in aqueous formulations of azole derivatives of the general formula (II):




in which R1 represents phenyl, 4-chlorophenyl, 4-chlorophenylethyl, 4-fluorophenyl, 2,4-dicholorophenyl, or 4-chlorophenyloxy;
R2 represents n-butyl, tert-butyl, phenyl, 2-fluorophenyl or a group of the general formula (III):




and
R3 represents hydroxyl, oxygen or cyano.
Preferred compounds of the general formula (II) are those in which R1 represents 4-chlorophenyl. Compounds of the general formula (II) in which R2 represents tert-butyl are also preferred. In addition, compounds in which R3 is a hydroxyl group are also preferred.
A particularly preferred compound for use in the composition of the present invention is tebuconazole, which is the compound of general formula (II) in which R1 is 4-chlorophenyl, R2 is tert-butyl and R3 is hydroxyl. The concentrate of the present invention has been found to be particularly stable when used to formulate tebuconazole, without any reduction in the fungicidal activity of the compound when applied to a locus. Tebuconazole is a well known compound in the art and is available commercially.
A further preferred compound for use in the composition of the present invention is hexaconazole, which is the compound of general formula (II) in which R1 is 2,4-dichlorophenyl, R2 is n-butyl and R3 is hydroxyl. The concentrate of the present invention has been found to be particularly stable when used to formulate hexaconazole, without any reduction in the fungicidal activity of the compound when applied to a locus. Again, hexaconazole is a well known compound in the art and is available commercially.
A further preferred compound for use in the composition of the present invention is cyproconazole, that is the compound of general formula (II) in which R1 is 4-chlorophenyl, R2 is a group of general formula (III) and R3 is hydroxyl. The concentrate of the present invention has been found to be particularly stable when used to formulate cyproconazole, without any reduction in the fungicidal activity of the compound when applied to a locus. Cyproconazole is a well known compound in the art and is available commercially.
A further preferred compound for use in the composition of the present invention is myclobutanil, that is the compound of general formula (II) in which R1 is 4-chlorophenyl, R2 is n-butyl and R3 is cyano. The concentrate of the present invention has been found to be particularly stable when used to formulate myclobutanil, without any reduction in the fungicidal activity of the compound when applied to a locus. Myclobutanil is a well known compound in the art and is available commercially.
A further preferred compound for use in the composition of the present invention is flutriafol, that is the compound of general formula (II) in which R1 is 4-fluorophenyl, R2 is 2-fluorophenyl and R3 is hydroxyl. The concentrate of the present invention has been found to be particularly stable when used to formulate flutriafol, without any reduction in the fungicidal activity of the compound when applied to a locus. Flutriafol is a well known compound in the art and is available commercially.
The compositions of the present invention have also been found to be effective in preventing the crystallization of triadimefon, that is a compound of general formula (II) in which R1 is 4-chlorophenyloxy, R2 is tert-butyl and R3 is oxygen. Triadimefon is a commercially available fungicide.
In other embodiments, the composition of the present invention comprises one or more of difenoconazole, diniconazole, propiconazole, tricyclazole, triticonazole, triflumizole, flusilazole, metconazole.
In one embodiment, the formulation contains azole derivatives as active ingredients selected from the group consisting of tebuconazole, cyproconazole, difenoconazole, diniconazole, triticonazole, hexaconazole, triflumiazole, metconazole, tricylazole, flusilazole, flutriafol, myclobutanil and mixtures thereof.
The composition to be applied to the plants to be treated, in particular by spraying, may contain the active azole derivative in any suitable concentration. As noted above, the spray liquors are typically prepared by the dilution with water of a concentrate. Typically, the spray liquor contains azole active ingredients from 0.0001 to 3%, more preferably 0.002 to 2%, by weight.
In addition to one or more N,N-dialkyl long chain alkylamides and one or more azole derivative active ingredients, the compositions of the present invention may comprise other components, including one or more of organic diluents or solvents, water and emulsifiers. Suitable components are known in the art.
Organic diluents or solvents that may be included in the composition include both polar and non-polar organic solvents, for example ketones, amides, such as dimethyl formamide, and aromatic hydrocarbons, such as xylene. Other suitable solvents will be known to the person skilled in the art.
Suitable emulsifiers comprised in the compositions of the present invention are also known in the art and commercially available. Suitable emulsifiers include both ionic and non-ionic emulsifiers, such as fatty acid esters, fatty alcohol esters, ethers, alkyl sulphonates and aryl sulphonates. Other suitable surface active components will also be known to the person skilled in the art.
Further components comprised in the composition are well known in the art and include, for example stabilizers and thickeners. Such components are commercially available and their use will be recognized and understood by the person skilled in the art.
In a further aspect, the present invention provides an aqueous spray composition comprising an azole active ingredient and an N,N-dialkyl long chain alkylamide, as hereinbefore defined, and water.
Other components that may be included in the aqueous spray composition are as hereinbefore described. Details of the components of the aqueous spray composition are as given hereinbefore.
In a further aspect, the present invention provides the use of N,N-dialkyl long chain alkylamides, in particular the N,N-dialkyl long chain alkylamides as hereinbefore defined, to inhibit the crystal growth of pesticidally active azole derivatives.
The compositions of the present invention may be prepared using techniques known in the art. A particularly preferred method of preparing the composition is as follows:
Each component is added according to the weight fraction required in the final composition. First, the solvent, and one or more N,N-dialkyl long chain alkylamide crystallization inhibitors are charged to a suitable mixing vessel, for example a blending tank equipped with a hot water circulation. The resulting mixture is agitated. The one or more azole derivatives are added to the mixture and the agitation continued until all azole derivatives are dissolved completely in the solvent. An agitation time of about 30 minutes is typical. Thereafter, further components, such as emulsifiers, if present, are added and the mixture further agitated to ensure homogeneity. A further agitation time of about 1 hour is typical.
When the composition is to be sprayed, the formulation is diluted with water to the desired concentration of active ingredient, for example by adding the concentrated formulation to water in a vessel with stirring.
In a further aspect, the present invention comprises a method of preventing crystallization of pesticidal liquid formulations comprising azole derivatives during application, the method comprising adding a N,N-dialkyl long chain alkylamide as hereinbefore defined to the formulation in an amount sufficient to reduce crystallization of the azole derivative.
In still a further aspect, the present invention provides a method of treating pests at a locus comprising applying to the locus a composition as hereinbefore described. The composition is preferably applied in the form of a diluted aqueous formulation. The method is particularly suitable for the application of fungicides to treat fungal infestations of plants in the locus.
Embodiments of the present invention will now be described, by way of example only.
EXAMPLES
In each of the following examples, a composition was prepared according to the following general methodology:
Charge every component based on the recipe composition into a vessel in the following manner. First, add the solvent and crystallization inhibitor to a blending tank equipped with a hot water circulation; agitate the solution; add one or more azole active ingredients into the blending tank; continue agitating for 30 minutes until all azole active ingredients are dissolved completely; add the emulsifiers to the tank; continue agitating for one hour until the mixture is uniform; stop agitating.
Samples of each composition prepared were taken from the tank and analysed in accordance with the international testing methods CIPAC (Collaborative International Pesticides Analytical Council).
To test the crystallization properties, in each case 20 L of an aqueous spray liquor, prepared by dilution of the composition prepared with water to a concentrate content of 0.5% by weight, were pumped in circulation through a fine-meshed sieve for 1 hour in a flow-through apparatus with the aid of a pump. The solution after preparation was analyzed in a chromatograph to measure the concentration of the azole derivative active ingredient in PPM. The gauge pressure of the liquid being circulated was recorded every one hour. An increase in the pressure is an indication the nozzles and the fine-meshed sieve are being blocked by crystals. Every hour, a sample of the circulating liquid was taken and analyzed in the chromatograph to determine the concentration of the azole derivative active ingredient.
The preparation and the crystallization behavior of various spray liquors according to the present invention, prepared and tested as described above, are described in the following examples, taken in conjunction with comparative test results given in the respective table.
Example 1
The liquid formulation described in Table 1 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole and N,N-dialkyl long chain alkylamides was approx 1:1.8. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 1 contained N,N-dialkyl long chain alkylamides in an amount of 45% wt. Table 1 describes the liquid formulation of Example 1 and the comparison formulation, Comparison A.









TABLE 1







EXAMPLE 1:
COMPARISON A:



Tebuconazole EC (with
Tebuconazole EC (without



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark














Tebuconazole
250 kg
Tebuconazole
250 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Calcium
100 kg
Calcium
100 kg
Emulsifier


dodecylphenyl-

dodecylphenyl-




sulfonate

sulfonate




TWEEN 80
100 kg
TWEEN 80
100 kg
Emulsifier


Sorbitan

Sorbitan




monooleate

monooleate




ethoxylate

ethoxylate




Cyclohexanone
100 kg
Cyclohexanone
550 kg
Solvent


N,N-diethyl
450 kg


Crystal-


dodecanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example I
The experimental results are set forth in the following table.














Example I
Comparison A














Press.


Press.





(PSI)


(PSI)



200
Tebuconazole
Tebuconazole
200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1059
0
38
1141
0


solution


After
40
1043
−1.51
Nozzles


1 h



100%






blocked


After
40
1028
−2.93
Nozzles


2 h



100%






blocked


After
41
1002
−5.38


3 h


After
41
988
−6.70


4 h









Example 2
The liquid formulation was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of diniconazole and N,N-dialkyl long chain alkylamides was approx 1:5. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 2 contained N,N-dialkyl long chain alkylamides in an amount of 80% wt. Table 2 describes the liquid formulation of Example 2 and the comparison formulation, Comparison B.









TABLE 2







EXAMPLE 2:
COMPARISON B:



Diniconazole EC (with
Diniconazole EC (without



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark





Diniconazole
160 kg 
Diniconazole
160 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Rhodocal 70
 10 kg
Rhodocal 70
 10 kg
Emulsifier


Calcium

Calcium




dodecylphenyl-

dodecylphenyl-




sulphonate

sulphonate




Tween 80
 10 kg
Tween 80
 10 kg
Emulsifier


Sorbitan

Sorbitan




monooleate

monooleate




ethoxylate

ethoxylate




N-methyl
 20 kg
N-methyl
820 kg
Solvent


pyrrolidone

pyrrolidone




N,N-
800 kg


Crystal-


diethylnona-



lization


decanamide



inhibitors


Total
1000 kg 
Total
1000 kg 









Use Example II
The experimental results are set forth in the following table.














Example 2
Comparison B














Pressure


Pressure





(PSI)


(PSI)



200
Diniconazole
Diniconazole
200
Diniconazole
Diniconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
39
755
0
38
780
0


solution


After 1 h
39
746
−1.19
40
532
−31.75


After 2 h
39
732
−3.05
42
440
−43.70


After 3 h
40
728
−3.58
46
369
−52.74


After 4 h
40
699
−7.42
49
335
−57.12









Example 3
The liquid formulation was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of difenconazole and N,N-dialkyl long chain alkylamides was approx 1:3.33. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 3 contained N,N-dialkyl long chain alkylamides in an amount of 50% wt. Table 3 describes the liquid formulation of Example 3 and the comparison formulation, Comparison C.









TABLE 3







EXAMPLE 3:
COMPARISON C:



Difenoconazole EC (with
Difenoconazole EC (without



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark





Difenoconazole
150 kg
Difenoconazole
150 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Rhodocal 70
100 kg
Rhodocal 70
100 kg
Emulsifier


Sodium

Sodium




dodecylphenyl-

dodecylphenyl-




sulphonate

sulphonate




IGEPAL BC/9
100 kg
IGEPAL BC/9
100 kg
Emulsifier


Nonylphenol

Nonylphenol




ethoxylate

ethoxylate




Dimethyl
150 kg
Dimethyl
650 kg
Solvent


formamide

formamide




N,N-dipropyl-
200 kg


Crystal-


decanamide



lization






inhibitor


N,N-diethyl-
300 kg


Crystal-


dodecanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example III
The experimental results are set forth in the following table.














Example 3
Comparison C














Press.


Press.





(PSI) 200
Difenoconazole
Difenoconazole
(PSI) 200
Difenoconazole
Difenoconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
660
0
38
664
0


solution


After
40
655
−0.70
40
459
−30.97


1 h


After
40
647
−1.84
42
373
−43.81


2 h


After
40
643
−2.54
44
313
−52.82


3 h


After
41
611
−7.44
44
282
−57.55


4 h









Example 4
The formulation of Example 4 was prepared with a combination of tebuconazole and triadimefon. The liquid formulation was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole and triadimefon to N,N-dialkyl long chain alkylamides was approximately 1:0.1. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 4 contained N,N-dialkyl long chain alkylamides in an amount of 5% wt. Table 4 describes the liquid formulation of Example 4 and the comparison formulation, Comparison D.









TABLE 4







EXAMPLE 4:
COMPARISON D:



Tebuconazole•Triadimefon
Tebuconazole•Triadimefon



EC (Containing
EC (Not containing



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
Composition
Remark





Tebuconazole
100 kg
Tebuconazole
100 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Triadimefon
400 kg
Triadimefon
400 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Rhodocal 70
100 kg
Rhodocal 70
100 kg
Emulsifier


Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 540

EL 540




Castor oil

Castor oil




ethoxylate

ethoxylate




Dimethyl
250 kg
Dimethyl
300 kg
Solvent


formamide

formamide




N,N-dipropyl-
 25 kg


Crystal-


nonadecan-



lization


amide



inhibitor


N,N-dipropyl-
 25 kg


Crystal-


decanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example IV
The experimental results are set forth in the following table.














Example 4
Comparison D


















Press.




Press.







(PSI)
Tebuconazole
Triadimefon

TRI
(PSI)
Tebuconazole
Triadimefon
TB
TRI



200
(TB)
(TRI)
TB
Decrease
200
(TB)
(TRI)
decrease
decrease



mesh
(ppm)
(ppm)
decrease %
%
mesh
(ppm)
(ppm)
%
%





















Initial
40
448
1765
0
0
38
445
1760
0
0


Solution


After
40
432
1756
−3.57
−0.51
Nozzles


1 h





100%








blocked


After
40
426
1743
−4.91
−1.25
Nozzles


2 h





100%








blocked


After
41
410
1735
−8.48
−1.70


3 h


After
42
402
1720
−10.26
−2.55


4 h









Example 5
The liquid formulation was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of propiconazole and N,N-dialkyl long chain alkylamides was approx 1:2. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 5 contained N,N-dialkyl long chain alkylamides in an amount of 40% wt. Table 5 describes the liquid formulation of Example 5 and the comparison formulation, Comparison E.









TABLE 5







EXAMPLE 5:
COMPARISON E:



Propiconazole EC
Propiconazole EC



(Containing 
(Not Containing



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
composition
Remark





Propiconazole
200 kg
Propiconazole
200 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


70 C

70 C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 540

EL 540




Castor oil

Castor oil




ethoxylate

ethoxylate




Dimethyl
200 kg
Dimethyl
600 kg
Solvent


formamide

formamide




N,N-diethyl
300 kg


Crystal-


dodecanamide



lization






inhibitor


N,N-dibutyl-
100 kg


Crystal-


heptamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example V
The experimental results are set forth in the following table.














Example 5
Comparison E














Pressure


Pressure





(PSI) 200
Propiconazole
Propiconazole
(PSI) 200
Propiconazole
Propiconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
39
878
0
38
884
0


solution


After 1 h
39
862
−1.82
40
624
−29.41


After 2 h
39
850
−3.19
Nozzles 100%






blocked


After 3 h
40
838
−4.56
Nozzles 100%






blocked


After 4 h
40
820
−6.61









Example 6
The formulation of Example 6 was prepared with a combination of hexaconazole and myclobutanil as active ingredients. The liquid formulation was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of hexaconazole and myclobutanil to N,N-dialkyl long chain alkylamides was approx 1:1.8. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 6 contained N,N-dialkyl long chain alkylamides in an amount of 45% wt. Table 6 describes the liquid formulation of Example 6 and the comparison formulation, Comparison F.









TABLE 6







EXAMPLE 6:
COMPARISON F:



Hexaconazole•Myclobutanil
Hexaconazole•Myclobutanil



EC (Containing
EC (without



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
Composition
Remark





Hexaconazole
100 kg
Hexaconazole
100 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Myclobutanil
150 kg
Myclobutanil
150 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


70 C

70 C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Alkamuls
100 kg
Alkamuls
100 kg
Emulsifier


OR/36

OR/36




Castor oil

Castor oil




ethoxylate

ethoxylate




Dimethyl
100 kg
Dimethyl
550 kg
Solvent


formamide

formamide




N,N-diethyl
450 kg


Crystal-


dodecanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example VI
The experimental results are set forth in the following table.














Example 6
Comparison F


















Press.




Press.







(PSI)
Hexaconazole
Myclobutanil

MYC
(PSI)
Hexaconazole
Myclobutanil
HEX
MYC



200
(HEX)
(MYC)
HEX
decrease
200
(HEX)
(MYC)
decrease
Decrease



mesh
(ppm)
(ppm)
decrease %
%
mesh
(ppm)
(ppm)
%
%





















Initial
40
450
657
0
0
38
445
664
0
0


solution


After
40
438
648
2.67
−1.37
Nozzles


1 h





100%








blocked


After
40
430
633
4.44
−3.65
Nozzles


2 h





100%








blocked


After
41
422
625
6.22
−4.88


3 h


After
42
408
614
9.33
−6.55


4 h









Example 7
The formulation of Example 7 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole to N,N-dialkyl long chain alkylamides was approx 1:1. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 7 contained N,N-dialkyl long chain alkylamides in an amount of 30% wt. Table 7 describes the liquid formulation of Example 7 and the comparison formulation, Comparison G.









TABLE 7







EXAMPLE 7:
COMPARISON G:



Tebuconazole EC (with
Tebuconazole EC (without



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
Composition
Remark





Tebuconazole
300 kg
Tebuconazole
300 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


70 C

70 C




Calcium 

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Alkamuls
100 kg
Alkamuls
100 kg
Emulsifier


OR/36

OR/36




Castor oil

Castor oil




ethoxylate

ethoxylate




Butanole
200 kg
Butanole
500 kg
Solvent


N,N-dibutyl-
150 kg


Crystal-


nona-



lization


decanamide



inhibitor


N,N-dibutyl-
150 kg


Crystal-


decanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example VII
The experimental results are set forth in the following table.














Example 7
Comparison G














Pressure


Pressure





(PSI) 200
Tebuconazole
Tebuconazole
(PSI) 200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1400
0
38
1398
0


solution


After 1 h
40
1380
−1.43
39
685
−51.0


After 2 h
40
1300
−7.14
Nozzles 100%






blocked


After 3 h
40
1280
−8.57
Nozzles 100%






blocked


After 4 h
42
1200
−14.3









Example 8
The formulation of Example 8 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of Myclobutanil to N,N-dialkyl long chain alkylamides was approx 1:0.5. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 8 contained N,N-dialkyl long chain alkylamides in an amount of 20% wt. Table 8 describes the liquid formulation of Example 8 and the comparison formulation, Comparison H.









TABLE 8







EXAMPLE 8:
COMPARISON H:



Myclobutanil EC (with
Myclobutanil EC (without



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark





Myclobutanil
400 kg
Myclobutanil
400 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Alkamuls
100 kg
Alkamuls
100 kg
Emulsifier


OR/36

OR/36




Castor oil

Castor oil




ethoxylate

ethoxylate




Methanol
200 kg
Methanol
400 kg
Solvent


N,N-dipentyl-
100 kg


Crystal-


octanamide



lization






inhibitor


N,N-diethyl-
100 kg


Crystal-


dodecanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example VIII
The experimental results are set forth in the following table.














Example 8
Comparison H














Pressure


Pressure





(PSI) 200
Myclobutanil
Myclobutanil
(PSI) 200
Myclobutanil
Myclobutanil



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1700
0
38
1660
0


solution


After 1 h
40
1657
−2.53
Nozzles 100%






blocked


After 2 h
40
1605
−5.59
Nozzles 100%






blocked


After 3 h
40
1574
−7.41


After 4 h
42
1526
−10.23









Example 9
The formulation of Example 9 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of diniconazole to N,N-dialkyl long chain alkylamides was approx 1:3. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 9 contained N,N-dialkyl long chain alkylamides in an amount of 30% wt. Table 9 describes the liquid formulation of Example 9 and the comparison formulation, Comparison I.









TABLE 9







EXAMPLE 9:
COMPARISON I:



Diniconazole EC (with
Diniconazole EC (without



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
composition
Remark





Diniconazole
100 kg
Diniconazole
100 kg
Active


tech
(as pure)
tech
(as part)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 360

EL 360




Castor oil 

Castor oil




ethoxylate

ethoxylate




Dimethyl
400 kg
Dimethyl
700 kg
Solvent


formamide

formamide




N,N-dipentyl-
300 kg


Crystal-


decanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example IX
The experimental results are set forth in the following table.














Example 9
Comparison I














Press. (PSI)


Press. (PSI)





200
Diniconazole
Diniconazole
200
Diniconazole
Diniconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
435
0
38
443
0


solution


After
40
430
−1.15
38
346
−21.89


1 h


After
40
421
−2.07
39
270
−39.06


2 h


After
40
417
−4.14
40
184
−58.47


3 h


After
42
410
−5.75
40
107
−75.85


4 h









Example 10
The formulation of Example 10 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole to N,N-dialkyl long chain alkylamides was approx 1:4. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 10 contained N,N-dialkyl long chain alkylamides in an amount of 40% wt. Table 10 describes the liquid formulation of Example 10 and the comparison formulation, Comparison J.









TABLE 10







EXAMPLE 10:
COMPARISON J:



Tebuconazole EC (with
Tebuconazole EC (without



Crystallization inhibitor)
Crystallization inhibitor)












Component
Composition
Component
Composition
Remark





Tebuconazole
100 kg
Tebuconazole
100 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium 

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 360

EL 360




Castor oil

Castor oil




ethoxylate

ethoxylate




Xylene
300 kg
Xylene
700 kg
Solvent


N,N-dipentyl-
400 kg


Crystal-


octa-



lization


decanamide



inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example X
The experimental results are set forth in the following table.














Example 10
Comparison J














Pressure


Pressure





(PSI) 200
Tebuconazole
Tebuconazole
(PSI) 200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
438
0
38
447
0


solution


After 1 h
40
430
−1.83
38
300
−32.89


After 2 h
40
414
−5.48
41
143
−68.00


After 3 h
39
408
−6.85
Nozzles






100%






blocked


After 4 h
42
400
−8.68
Nozzles






100%






blocked









Example 11
The formulation of Example 11 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tricyclazole to N,N-dialkyl long chain alkylamides was approx 1:2.2. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 11 contained N,N-dialkyl long chain alkylamides in an amount of 55% wt. Table 11 describes the liquid formulation of Example 11 and the comparison formulation, Comparison K.









TABLE 11







EXAMPLE 11:
COMPARISON K:



Tricyclazole EC
Tricyclazole EC



(Containing
(Not containing



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark





Tricyclazole
250 kg
Tricyclazole
250 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
 80 kg
Agnique ABS
 80 kg
Emul-


70 C

70 C

sifier


Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
120 kg
Emulsogen
120 kg
Emulsifier


EL 360

EL 360




Castor oil

Castor oil




ethoxylate

ethoxylate




Dimethyl

Dimethyl
550 kg
Solvent


formamide

formamide




N,N-dipropyl-
350 kg


Crystal-


dodecanamide



lization






inhibitor


N,N-dibutyl-
200 kg


Crystal-


decanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example XI
The experimental results are set forth in the following table.














Example 11
Comparison K














Pressure


Pressure





(PSI) 200
Tricyclazole
Tricyclazole
(PSI) 200
Tricyclazole
Tricyclazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1250
0
40
1262
0


solution


After 1 h
40
1197
−4.24
40
863
−31.62


After 2 h
40
1138
−8.96
41
654
−48.18


After 3 h
39
1106
−11.52
Nozzles 100%






blocked


After 4 h
42
1097
−12.24
Nozzles 100%






blocked









Example 12
The formulation of Example 12 was prepared containing flutriafol as the active ingredient and N,N-dialkyl long chain alkylamides, wherein the weight ratio of flutriafol to N,N-dialkyl long chain alkylamides was approx 1:1.6. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
The formulation of Example 12 contained N,N-dialkyl long chain alkylamides in an amount of 40% wt. Table 12 describes the liquid formulation of Example 12 and the comparison formulation, Comparison L.









TABLE 12







EXAMPLE 12: 
COMPARISON L:



Flutriafol EC (Containing
Flutriafol EC (Not containing



Crystallization inhibitors)
Crystallization inhibitors)












Component
Composition
Component
Composition
Remark





Flutriafol tech
250 kg
Flutriafol tech
250 kg
Active



(as pure)

(as pure)
ingredient


Agnique ABS
 80 kg
Agnique ABS
 80 kg
Emul-


70 C

70 C

isifier


Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emul-


EL 360

EL 360

isifier


Castor oil

Castor oil




ethoxylate

ethoxylate




Dimethyl
170 kg
Dimethyl
570 kg
Solvent


formamide

formamide




N,N-dipropyl-
300 kg


Crystal-


dodecanamide



lization






inhibitor


N,N-dipentyl-
100 kg


Crystal-


octanamide



lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example XII
The experimental results are set forth in the following table.














Example 12
Comparison L














Pressure


Pressure





(PSI) 200
Flutriafol
Flutriafol
(PSI) 200
Flutriafol
Flutriafol



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1133
0
40
1253
0


solution


After 1 h
40
1106
−2.38
42
690
−44.96


After 2 h
40
1059
−8.96
Nozzles






100%






blocked


After 3 h
39
1022
−9.79
Nozzles






100%






blocked


After 4 h
42
998
−11.92









Example 13
The formulation of Example 13 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole to N,N-dialkyl long chain alkylamides was approx 1:1.2. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but containing an alkylamide with a lower alkyl constituent group.
The formulation of Example 13 contained N,N-dialkyl long chain alkylamides in an amount of 30% wt. Table 13 describes the liquid formulation of Example 13 and the comparison formulation, Comparison M, in which the lower alkyl alkylamide was used.









TABLE 13







EXAMPLE 13:
COMPARISON M:



Tebuconazole EC (with
Tebuconazole EC (with



long chain alkylamide)
lower chain alkylamide)












Component
Composition
Component
Composition
Remark





Tebuconazole
250 kg
Tebuconazole
250 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 360

EL 360




Castor oil

Castor oil




ethoxylate

ethoxylate




Xylene
250 kg
Xylene
250 kg
Solvent


N,N-diethyl-
300 kg
N,N-diethyl-
300 kg
Crystal-


dodecanamide

octanamide

lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example XIII
The experimental results are set forth in the following table.














Example 13
Comparison M














Press.


Press.





(PSI)


(PSI)



200
Tebuconazole
Tebuconazole
200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1133
0
40
1253
0


solution


After 1 h
40
1106
−2.38
40
1054
−15.88


After 2 h
40
1059
−8.96
41
906
−27.66


After 3 h
39
1022
−9.79
41
579.4
−53.76


After 4 h
42
998
−11.92
40
504.3
−59.75









Example 14
The formulation of Example 14 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole to N,N-dialkyl long chain alkylamides was approx 1:1.2. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but containing an alkylamide with lower alkyl constituent groups.
The formulation of Example 14 contained N,N-dialkyl long chain alkylamides in an amount of 30% wt. Table 14 describes the liquid formulation of Example 14 and the comparison formulation, Comparison N.









TABLE 14







EXAMPLE 14:
COMPARISON N:



Tebuconazole EC
Tebuconazole EC



(with long chain alkylamide)
(with lower chain alkylamide)












Component
Composition
Component
Composition
Remark





Tebuconazole
250 kg
Tebuconazole
250 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 360

EL 360




Castor oil

Castor oil




ethoxylate

ethoxylate




Xylene
250 kg
Xylene
250 kg
Solvent


N,N-dipropyl-
300 kg
N,N-dipropyl-
300 kg
Crystal-


dodecanamide

nonamide

lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example XIV
The experimental results are set forth in the following table.














Example 14
Comparison N














Press.


Press.





(PSI)


(PSI)



200
Tebuconazole
Tebuconazole
200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1098
0
40
1148
0


solution


After 1 h
40
1057
−3.73
40
712
−37.98


After 2 h
40
1044
−4.92
42
564
−50.87


After 3 h
39
1026
−6.56
46
484
−57.88


After 4 h
42
994
−9.47
46
402
−65.03









Example 15
The formulation of Example 15 was prepared containing N,N-dialkyl long chain alkylamides, wherein the weight ratio of tebuconazole to N,N-dialkyl long chain alkylamides was approx 1:1.2. Crystal formation of this formulation was compared with a second liquid formulation, which was prepared from identical components in an identical manner, but containing an alkylamide with lower alkyl groups.
The formulation of Example 15 contained N,N-dialkyl long chain alkylamides in an amount of 30% wt. Table 15 describes the liquid formulation of Example 15 and the comparison formulation, Comparison O












EXAMPLE 15:
COMPARISON O:



Tebuconazole EC (with
Tebuconazole EC (with



long chain alkylamide)
lower chain alkylamide)












Component
Composition
Component
Composition
Remark





Tebuconazole
250 kg
Tebuconazole
250 kg
Active


tech
(as pure)
tech
(as pure)
ingredient


Agnique ABS
100 kg
Agnique ABS
100 kg
Emulsifier


60C

60C




Calcium

Calcium




dodecylphenyl

dodecylphenyl




sulphonate

sulphonate




Emulsogen
100 kg
Emulsogen
100 kg
Emulsifier


EL 360

EL 360




Castor oil

Castor oil




ethoxylate

ethoxylate




Xylene
250 kg
Xylene
250 kg
Solvent


N,N-dibutyl-
300 kg
N,N-dibutyl-
300 kg
Crystal-


octanamide

hexamide

lization






inhibitor


Total
1000 kg 
Total
1000 kg 









Use Example No. XV
The experimental results of the test for crystal formation are set out in the table which follows.














Example 15
Comparison O














Press.


Press.





(PSI)


(PSI)



200
Tebuconazole
Tebuconazole
200
Tebuconazole
Tebuconazole



mesh
(ppm)
decrease %
mesh
(ppm)
decrease %

















Initial
40
1243
0
40
1234
0


solution


After
40
1195
−3.86
40
743
−39.79


1 h


After
40
1154
−7.16
Nozzles


2 h



100%






blocked


After
39
1138
−8.45
Nozzles


3 h



100%






blocked


After
41
1102
−11.3


4 h









From the experimental data set out above, it can be seen that the long chain alkyl amides of Formula I above exhibit significant performance in inhibiting the crystallization of the pesticidally active azole derivatives. In particular, the long chain alkyl amides perform significantly better than the corresponding lower alkyl compounds and exhibit a markedly higher activity in preventing crystallization of the azole derivatives.
The foregoing written specification is considered to be sufficient to enable one skilled in the art to practice the invention. The present invention is not to be limited in scope by examples provided, since the examples are intended as a single illustration of one aspect of the invention and other functionally equivalent embodiments are within the scope of the invention. Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art form the foregoing description and fall within the scope of the appended claims. The advantages and objects of the invention are not necessarily encompassed by each embodiment of the invention.

## Claims

1. An agrochemical composition comprising an N,N-dialkyl long chain alkylamide of the formula (I)




in which:
R1 and R2 are each independently normal alkyl radicals having from 2 to 20 carbon atoms and R represents an alkyl group having from 6 to 30 carbon atoms;
wherein the total number of carbon atoms in R, R1 and R2 is greater than 18;
and at least one azole active ingredient;
and optionally at least one member selected from the group consisting of a surface-active agent, organic diluent and low temperature stabilizer.

2. The composition according to claim 1, wherein R represents an alkyl group having from 6 to 25 carbon atoms.

3. The composition according to claim 1, wherein R1 and R2 each represent an alkyl group having from 4 to 12 carbon atoms.

4. The composition according to claim 1, wherein R is a normal alkyl group.

5. The composition according to claim 1, wherein the ratio of azole active ingredient and N,N-dialkyl long chain alkylamide is from 1:0.1 to 1:5.

6. The composition according to claim 1, wherein two or more N,N-dialkyl long chain alkylamides are present.

7. The composition according to claim 1, wherein two or more azole active ingredients are present.

8. The composition according to claim 1, wherein the N,N-dialkyl long chain alkylamide is selected from the group consisting of N,N-diethylhexadecanamide, N,N-diethylheptadecanamide, N,N-diethyloctadecanamide, N,N-diethylnonadecanamide, N,N-dipropyltetradecanamide, N,N-diethylhexadecanamide, N,N-dipropylheptadecanamide, N,N-dipropyl octadecanamide, N,N-dipropylnonadecanamide, N,N-dibutyldodecanamide, N,N-dibutyltridecanamide, N,N-dibutyltetradecanamide, N,N-dibutylhexadecanamide, N,N-dibutylheptadecanamide, N,N-dibutyloctadecanamide, N,N-dibutylnonadecanamide, N,N-dipentyloctanamide, N,N-dipentyldecanamide, N,N-dipentyldodecanamide, N,N-dipentyltetradecanamide, N,N-dipentylhexadecanamide, N,N-dipentyloctadecanamide, or any mixture thereof.

9. The composition according to claim 1, wherein the N,N-dialkyl long chain alkylamide is present in an amount of from 5% to 80% by weight.

10. The composition according to claim 1, wherein the azole active ingredient is selected from tebuconazole, cyproconazole, triticonazole, hexaconazole, flutriafol, myclobutanil and mixtures thereof.

11. The composition according to claim 1, wherein the azole active ingredient is selected from difenoconazole, diniconazole, propiconazole, tricyclazole, triticonazole, triflumizole, flusilazole, metconazole.

12. The composition according to claim 1, further comprising a solvent or diluent.

13. The composition according to claim 12, wherein the solvent or diluent is dimethyl formamide or xylene.

14. The composition according to claim 1, further comprising an emulsifier.

15. An aqueous spray composition comprising a composition according to claim 1 and water.

16. The composition according to claim 15, wherein the azole active ingredient is present in an amount of from 0.0001% to 3% by weight.

17. A method of preventing crystallization of pesticidal liquid formulations comprising azole active ingredient as defined in claim 1 during application, the method comprising adding a N,N-dialkyl long chain alkylamide as defined in claim 1 to the formulation in an amount sufficient to reduce crystallization of the azole active ingredient.

18. A method of treating pests at a locus comprising applying to the locus a composition according to claim 1.

19. The method according to claim 18, wherein the composition is applied in the form of a diluted aqueous formulation.

20. The method according to claim 17, wherein the composition comprises a fungicidally active compound and treats fungal infestations of plants in the locus.

21. The method according to claim 18, wherein the composition comprises a fungicidally active compound and treats fungal infestations of plants in the locus.

22. The composition according to claim 1, wherein R represents an alkyl group having from 6 to 18 carbon atoms.

23. The composition according to claim 1, wherein R1 and R2 each represent an alkyl group having from 4 to 8 carbon atoms.

24. The composition according to claim 1, wherein the total number of carbon atoms in R, R1 and R2 is greater than 20.

25. The composition according to claim 1, wherein the ratio of azole active ingredient and N,N-dialkyl long chain alkylamide is from 1:1 to 1:4.

26. The composition according to claim 1, wherein the N,N-dialkyl long chain alkylamide is present in an amount of from 20% to 60% by weight.

27. The composition according to claim 15, wherein the azole active ingredient is present in an amount of from 0.002% to 2% by weight.