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(21)Application Number: KE/P/2DD9/ DDD994

(22) Filing Date: 28/D512DD8

(3D) Priority data: 2DD71DD22965.D  28/D5/2DD7  CN

(86)  PCT data PCT/CNDS/D71116 28/D5/2DD8 wo 2DD8/145D63 D4/1212DD8

(73) Owners: ROTAM AGROCHEM INTERNATIONAL CO., LTD. of 7/FCheung Tat Centre, 18 Cheung Lee Street, Chai
Wan, Hong Kong 999077, China

(72)    Inventors: YIN, Amanda, No. 88, Rotam Road, ETDZ, Kunshan, Jiangsu 215301, China; CHEN, Sonia, No. 88, Rotam Road, ETDZ, Kunshan, Jiangsu 215301, China; WU, Yifan, No. 88, Rotam Road, ETDZ, Kunshan, Jiangsu 215301, China; P. Moorthy, No.88 Rotam Road, ETDZ, Kunshan Jiangsu, 215301, China and LO, Chang Yuan, No.88 Rotam Road, ETDZ, Kunshan Jiangsu, 215301, China

(74)    Agent/address for correspondence: MURIU, MUNGAI & COMPANY ADVOCATES, P. 0. BOX 75362-DD2DD, NAIROBI

(54)    Title: AGROCHEMICAL COMPOSITION AND METHOD FOR PREPARING AND USING THE SAME

(57)    Abstract: An agrochemical composition comprises an azote active ingredient and an N,N-dialkyl long chain alkylamide. The N,N-dialkyllong chain alkylamide is persent in sufficient amount to prevent or inhibit

the crystallization of the azote 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 nonnal alkyl radicals having 2 carbon atoms, and R represents an alkyl group having from 10 to 30 carbon atoms; or

(b) R 1 and R2 are independently nonnal alkyl radicals having 3 carbon atoms, and R represents an alkyl group having from 9 to 30 carbon atoms; or 20 (c) R 1 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 fonnulated with a fungicide, in particular one or more of tebuconazole, cyproconazole, difenoconazole, diniconazole, triticonazole, hexaconazole, triflumiazole, metconazole, tricylazole, flusilazole, flutrafol, and myclobutanil.
 
AGROCHEMICAL COMPOSITION AND METHOD FOR PREPARING AND USING THE SAME 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
10    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

15    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.

20    Certain pesticidally active azote 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

25    pesticidal composition. Thus, US Patent No. 5,206,225 descnbes the use of certain alkyl carboxylic acid dimethylamides as crystallization inhibitors of azole fungicides. Further, US Patent No. 5,369,118 describes the use of alkyllactam 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 TKE INVENTION

In the present invention it is surprisingly found that certain N, N~dialkyllong chain alkylamides are useful for preventing the crystallization during the application of aqueous
10    spray liquors having azole derivatives as the active agrochemical ingredient.

US Patent No. 5,206,225 discloses the use of varieties of alkylcarboxy/ic acid dimethylamide of the formula R-CO~N(CH3)2 as crystaiJization inhibitors of azole fungicides. Although US 5,206,225 describes the R group may represent alkyl having 5 to 19 carbon

15    atoms, the amide group is exclusively dimethyl amide. Thus, US 5,206,225 teaches away from developing other dialkylamide derivatives for using as a crystallization inhibitor in agrochemical composition comprising azole derivatfves as active ingredients.

DE 4,341,986 is concerned with the use of carboxylic acid amides having the general

20    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 lium 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

25    atoms, cycloalkly having from 5 to 7 carbon atoms, aralkyl having from 6to 10 carbon atoms In lhe 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 aikenyl chain, phenoxyalkyl h~uinn frnm 1 tn d. r.:=~rhnn ;:Jtnms in thP. a(kvl nra wide mnae of~mirlA arouos. and in which R1 is
 
hydrogen, alkyl having from 1 to 12 carbon atoms, hydroxyalkyl having from 1 fo 8 carbon atoms, alk:enyl having from 2 to 12 carbon atoms, optionally substituted cycloalkyl having from 5 to 7 carbon atoms, phenyl, benzyl or phenethyl, and R2is 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 azofe derivatives.

DE 4,341,986 indicates a very large number of carboxylic acid amides and prefers to haveR, R1 and R2 different classes of groups, in particular mixing saturated groups, such as

10    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 amldes. 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
15    amides specifically exemplified in table 2 of DE 4,341 ,986, representing a minority of the carboxylic amides exemplified in table 2 of 98~', R is an alkyl group having 11 carbon atoms orfewe:r, with an emphasis be1ng placed on R being a /ower 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 ex~eed 16.

20

In the present invention, the surprising finding is that alkyl am ides ofthe general formula ofDE 4,341,986 in which R is a higher alkyl group, in particular, depending upon the nature of R1 and R2 in the fonnula having at least 6 carbon atoms, and/orthe total number of carbon atoms in the alkyl groups of R, R1 and R2 exceeds 16, exhibit a markedly superior

25    activity to inhibiting crystallization of a specific class of azote 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~Dialkyllong 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 a/ky/amide.

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)
10    0
II
R --    C -- N

(I)

in which:

15 (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 20 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 (H) 25
(II)

in which R, 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 tonnula (Ill):
-cH-<J
I
10    CH,   
       

(Ill)

and

R3 represents hydroxyl, oxygen or cyano,

and optionally at least one member selected from the group consisting of a 15 surface-active agent, organic diluent and low temperature stabilizer.

The azole active ingredients are water insoluble compounds and such compounds are prone to CJYStallizing 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.
20    The N, N-dialkyllong 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 theN, N-dialkyl long chain alky/amides are effective in reducing and/or inhibiting crystal growth of azole active compounds. Thus, the inclusion of one or more N, N-dialky\

Jorig chain alky\amides in the aqueous composition prevents the spray equipment and the

25    like from being blocked and makes the spray liquor free of any crystals. This in tum maintains the composition in a more homogeneous condition. In addition, it has been found that the use of the N, N-dialkyllong chain alkylamides to prevent crystal formation and growth improves the efficiency and efficacy of the active ingredient.
 
TheN, N~dialky/ long chain alkylamides are present in an amount sufficient to reduce and/or inhibit crystal growth of the azole compounds. The amount of theN, N-dialkyllong chain alkylamide present may depend upon the concentration of the azole active ingredient and may be determined by routine experimentation. TheN, N-dialkyllong chain alkylamldes are preferably present in an amount such as to give a weight ratio of the azofe active ingredient to theN, N-dialkyllong chain alkylamide of from 1:0.1 to 1:5, more preferably from 1:1 to 1:4.

10 The composition may comprise a single N, N-dialkyl\ong chain a\kylamide or a combination of two or more N, N-dialkyllong chain alkylamides.

TheN, 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 1:
15
    0       
    II    R 1   
R --    C -- N  __.../    R'   
    .........__       

(I)

20

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 nonnal alkyl radicals having 3 carbon atoms, then R represents an 25 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 offonnula (l) 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,

10    N-dialkyllong chain alkylamides are selected from the group consisting of diethyldodecanamide, diethyltridecanamide, N,N-diethyltetradecanamide, N,N-diethylhexadecanamide, N,N-diethylheptadecanamide, N,N-diethy/octadecanamide, N,N-diethylnonadecanamide, N,N-dipropyldecanamide, N,N-dipropyldodecanamide, N,N-dipropyltridecanamide, N,N-dipropyltetradecanamide, N,N-diethylhexadecanamide,

15    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-<libutyltridecanamide,

N,N-dibutyltetradecanamide,N,N-dibutylhexadecanamide,N,N-dibutylheptadecanamide,

20    N,N-dibutyloctadecanamide,N,N-dibutylnonadecanamide, N,N-dipentyloctanamide,N,N-dipentyldecanamide, N,N-dipentyldodecanamide,N,N-dipentyftetradecanamide, N,N-dipentylhexadecanamide, N,N-dipenty/octadecanamide,or any mixture thereof.

25 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-dialkyllong chain alkylamJdes 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~dlalkyllong 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 parHcuJarly effective in preventing the   
    crystallization of azole derivatives that are active as fungicides.  In particular, the N,   
    N~dialkyllong chain alkylamides have been found to be effective as inhibiting crystal growth   
10    in aqueous formulations of azole derivatives of the general formula (11):   
15       
    (II)   
    formula(lll):   
    -cH--<1   
25    I   
20    CH;   
    and   
    RJ represents hydroxyl, oxygen or cyano.   
    in which R1 represents phenyl, 4~chlorophenyl, 4~chloropheny\ethyl, 4-fluorophenyl,   
2,4-dicholorophenyl, or 4-chlorophenyloxy;
R2 represents n-buty/, tert-butyl, phenyl, 2-fluorophenyl or a group of the general




(Ill)
 
Preferred compounds of the general formula (II) are those in which R, represents 4-chloropheny\. Compounds of the general formula (II) in which R, 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 te~-butyl and R3 is hydroxyl. The concentrate of the present invention has been

10    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 wen known compound in the art and is available commercially.

A further preferred compound for use in the composition of the present invention is

15    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 particularty stable when used to fonnulate 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.

20

A further preferred compound for use in the composition of the present invention is cyproconazote, that is the compound of general formula (I!) in which R1 1s 4-ch/oropheny/, R2 is a group of general formula (Ill) and R, is hydroxyl. The concentrate of the present invention has been found to be particularly stable when used to formulate cyproconazole,

25    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 fonnula (II) in which R, is 4-chlorophenyl, R2 is n-bufy/ 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 (11) in which R1 is 4-fluorophenyl, R2 is 2-fluorophenyl and R3 is hydroxyl. The concentrate of the present invention has been

10    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 weir known compound in the art and is available commercially.

The compositions of the present invention have also been found to be effective in

15    preventing the crystallization oftriadimefon, 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

20    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, difenoconazo\e,

25    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 derivatrve in any suitable concentration. As noted above, the spray liquors are typically prepared by the dilulion 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-dialkyllong 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.

10

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.

IS

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
sui phonates and aryl sulphonates. Other suitable surface active components will also be 20 known to the person skilled in the art.

Further components comprised in 1he 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.
25

In a further aspect, the present invention provides an aqueous spray composition comprising an azole active ingredient and anN, N~dialkyl fang chain alkylamide, as hereinbefore defined, and wafer.
 
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-dialky/ long chain alkylamides, in particular theN, N-dia!kyl long chain alkylamides as hereinbefore defined, to inhibit the crystal growth of pesticidally active azole derivatives.

10    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 tong chain alkylamide
15    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 fa 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

20    mixture further agitated to ensure homogeneity. A further agitation time of about 1 hour is typical.

When the composition is to be sprayed, the fonnulation is diluted with water to the desired concentration of active ingredient, for example by adding the concentrated

25    formulation to water in a vessel with stirring.

In a further aspect, the present invention comprises a method of preventing crystaUization of pesticidal liquid formulations comJ)!ising azoJe derivatives during
 
application, the method comprising adding a N, N-diafky/long chain alky/amide 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 fonnulatlon. The method is particularly suitable for the application of fungicides to treat fungal infestations of plants in the locus.

10

Embodiments of the present invention will now be described, by way of example only.

EXAMPLES

15    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
20    hot water circulation; agitate the solution; add one or more azote active ingredients into the blending tank; continue agitating for 30 minutes until all azote active ingredients are dissolved completely; add the emulsifiers to the tank; continue agitating for one hour until the mixture is uniform; stop agitating.

25    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 azote 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 azo!e derivative active ingredient.
10

The preparation and the crystallization behavior of various spray liquors according to the presen~ invention, prepared and tested as described above, are described in the foJJowing examples, taken in conjunction with comparative test results given in the respective table.

15

Example 1

The liquid formulation described in Table 1 was prepared containing N, N--dialkyl long chain alkylamides, wherein the weight ratio of tebucona~ole and N, N-dialkyllong chain alkylamides was approx 1:1.8. Crystal formation of this formulation was compared with a
20    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-dialky!Jong chain alkylamides in an amount of 45% wt. Table 1 describes the liquid formulation of Example 1 and the

25    comparison formulation, Comparison A. Table 1.
 

    EXAMPLE 1: Tebuconazole EC (with    ~COMPARISON A: Tebuconazole EC            Remark   
    Crystallization Inhibitors)        !;        (without CtysfaJJization inhibitors)                   
    Component            Composition; Component            Composition           
    Tebuconazole tech        250kg( as        ~ Tebuconazole tech    250kg Cas            Active   
                    pure)        i                        pure)            ingredient   
    Calcium                100kg        ~'.Calcium            100kg            Emulsifier   
                                $                                           
    dodecylphenylsulfonate                ~ dodecylpheny/sulfonate                       
                                I                                           
                                '                                           
                                                                    Emulsifier   
    iWEEN 80        100kg        '        lWEEN 80    100kg               
                                J                                       
    Sorbitan monooleate                ~ Sorbitan monooleate                       
    ethoxylate                        ~ ethoxylate                               
                                                           
    Cyclohexanone        100kg        ~ Cycfohexanone    550kg            Solvent   
    N,N-diethyl            450kg        .                            Crystallization   
                                                       
    dodecanamide                        ~                                    inhibitor   
                            l                                       
    Total                1000kg        'jTotal            1000kg                   
    Use Example    I                                                               
    The experimental results are set forth in the following table.                       
                                                                       
                    Example I                        Comparison A                   
                                               
        Press.    Tebuconazole        Tebuconazole    Press.    Tebuconazofe                   
        (PSI)        (ppm)        decrease%        (PSI)        (ppm)    Tebuconazole       
        200                                        200            decrease%       
        mesh                                    mesh                           
                                                               
    Initial        40    1059                    0        38        1141    0       
                                                               
    solution                                                                       
                                                                           
                                                               
    After    40    1043                -1.51        Nozzles                           
                                                                           
 
                   
1h                100%   
                blocked   
                   
After    40    1028    -2.93    Nozzles   
2h                100%   
                   
                blocked   
                   
                   
After    41    1002    -5.38       
3h                   
                   
After    41    988    -6.70       
4h                   
                   

Example2

The liquid formulation was prepared containing N, N'"1:1ialk:yllong chain alkylamides,

wherein the weight ratio of diniconazole and N, NMdialkyl 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 fonnulalion of Example 2 contained N,N-dialkyllong chain alkylamides in an

10    amount of 80% wt. Table 2 describes the liquid formulation of Example 2 and the comparison formulation, Comparison B.

Table 2.                       
                   
EXAMPLE2:  Diniconazole EC (with l COMPARISON B:    Diniconazole EC    Remark   
        j               
Crystallization inhibitors)    j (without Crystallization inhibitors)       
Component    Composition    ~ Component    I Composition       
Diniconazole tech    160kg (as    i Diniconazole tech    1160kg (as    Active   
    pure)    1    pure)    ingredient   
        !           
                   
                   
Rhodocal70    10kg    I Rhodocal70    10kg    Emulsifier   
Calcium        '               
dodecylphenylsulpho        ~ ~:~::;phenylsulphonate               
nate        I               
                       
Tween 80    10kg    ! Tween 80    10kg    Emulsifier   
Sorbitan monooleate        ~ Sorbitan monooleate               
ethoxylate        ethoxylate               
                   
N-methyl pyrrolidone    20kg    ~ N-methyl pyrrolidone    820kg    Solvent   
N,N-diethylnonadeca    800kg    I~            Crystalliza   
namide                    tion   
                    inhibitors   
Total    1000kg    fTotal    1000kg       


Use Example  II

The experimental results are set forth in the fallowing table.

            Example2        Comparison 8   
                               
        Pressure    Diniconazole    Diniconazole    Pressure    Diniconazole    Diniconazole
        (PSI)    (ppm)    decrease%    (PSI)    (ppm)    decrease%
    200            200           
        mesh            mesh           
                               
Initial    39    755    0    38    780        0
solution                               
                           
After1h    39    746    ~1.19    40    532        -31.75
                           
After2h    39    732    -3.05    42    440        -43.70
                               
 

Example 3

The liquid formulation was prepared containing N, N~dialkyllong chain alkylamides, wherein the weight ratio of difenconazole and N, N-dialkyllong chain alkylamides was approx 1:3.33. Crystal fonnation 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.

10    The formulation of Example 3 contained N,N-dialkyllong 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.        !COMPARISON C: Difenoconazole           
    EXAMPLE 3: Difenoconazole EC               
                Remark   
    (with Crystallization inhibitors)    j EC (without Crystallization inhibitors)       
    Component    Composition    ~ Component    j Composition       
                           
    Difenoconazole    150kg (as    j Difenoconazole tech        1150kg <as    Active   
    tech    pure)    ~        pure)    ingredient   
    Rhodocal70    100kg    l Rhodocal 70        100kg    Emulsifier   
            '                   
    Sodium        I Sodium                   
            I                   
    dodecylphenylsulp        I dodecylphenylsulph                   
                               
    honate        '                   
                               
            I onate                   
            ~                   
            ~                   
    IGEPALBC/9    100kg    IIGEPAL BC/9        100kg    Emulsifier   
 

Nonylphenol            iNonylphenol                                   
                                                   
ethoxylate            1ethoxylate                                       
                                                       
Dimethyl            150kg    j Dimethyl fonmamide    650kg        Solvent   
formamide            '                                       
                                                   
                1                                       
N,N-dipropyldecan    200kg    '                            Crystallization   
                                       
amide                l                            inhibitor   
                                                       
N,  N-diethyl-        300kg    i                            Crystallization   
            f                               
                                                       
dodecanamide            I'                            inhibitor   
Total            1000kg        ~Total        1000kg                   
Use Example III                                                       
The experimental results are set forth in the following table.                                   
                                           
            Example3    Comparison C               
                                           
    Press.    Difenoco    Difenoconazole    Press.        Difenocona    Difenocon       
    (PSI)    nazole    decrease%    (PSI) 200        zole    azole           
                                       
    200    (ppm)            mesh        (ppm)    decrease           
                                       
    mesh                                            %           
                                                   
Initial    40    660    0    38        664                0           
solution                                                           
                                                           
                                                   
After    40    655    -0.70    40        459                -30.97           
1h                                                           
                                                           
                                                   
After    40    647    -1.84    42        373                -43.81           
2h                                                           
                                                   
After    40    643    -2.54    44        313                -52.82           
3h                                                           
                                                   
After    41    611    -7.44    44        282                -57.55           
                                                           
 
Example4

The formulation of Example 4 was prepared with a combination of tebuconazale and

triadimefon.  The liquid fonnulation was prepared containing N, NMdialkyllong chain

alkylamides, wherein the weight ratio of tebuconazole and triadimefon to N, N-dialkyllong 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.

10    The formulation of Example 4 contained N,N-dialkyllong 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

EXAMPLE4:            ~    COMPARISON D:        Remark   
Tebuconazole•Triadimefon EC    ~ Tebuconazole•Triadimefon EC               
(Containing Crystallization    j (Not containing Crystallfzation               
inhibHor)            i inhibitor)                       
Component        Composition    I Component        Composition               
                                   
Tebuconazole        100kg(as pure)! Tebuconazole        100kg (as        Active   
tech            ~'        pure)        ingredient   
            1tech                   
                           
Triadimefon        400kg(as pure)~ Trtadimefon        400kg (as        Active   
tech            '            pure)        ingredient   
            I tech                   
Rhodocal 70        100kg    ~    Rhodocal 70        100kg        Emulsifier   
Calcium            I Calcium                       
dodecylphenyl            '                       
            l dodecylphenyl                       
            ,                           
sulphonate            i sulphonate                       
                                   
       
                               
Emulsogen            '        Emulsffier   
            i Emulsogen           
El540        100kg        ~ El540    100kg       
Castor oil            f Castor oil           
ethoxylate                    , ethoxylate           
                               
Dimethyl        250kg            tDimethyl'    300kg    Solvent   
formamide            ~formamide           
                           
N,  N-dipropy\-        25kg    l        Cl)'stallization   
            ~           
nona dec an-                    inhibitor   
            j           
amide            .           
                '        Crystallization   
N,  N-dipropy\-        25kg                   
decanamide            i        inhibitor   
            ?           
Total        1000kg    hotal    1000kg       
            '           
                       

Use Example IV

The experimental results are set forth in the following table.

                                                                   
                            Example4                Comparison D           
                                                                   
                Press.        Tebuc-    Triadi    TB    TRI    Press.        Tebu-    Tria-    TB    TRI   
                            m-e fan                        dime-           
                (PSI)        onazo-        deere    Deere    (PSI)        con a-        deer    deer   
                            (TRI)                        fon           
                                                               
                                        ase%                           
            200            Je (TB)    (ppm)    ase        200        zole    (TRI)    eas    ease   
                                                               
                mesh                %        mesh        (TB)    (ppm)    e%    %   
                        (ppm)                                       
                                                               
                                                    (ppm)               
                                                                   
                                                               
    Initial    40        448    1765    0    0    38        445    1760    0    0   
    So\u-                                                           
    tion                                                           
                                                                   
    After    40        432    1756    -3.57    -0.51    Nozz-                       
                                                       
    1h                                    Jes                       
                                                               
       
                                       
                            100%           
                            blocke           
                            d           
                                       
                                       
After    40    426    1743    -4.91    -1.25    Nozz-           
2h                            Jes           
                            100%           
                                       
                            blocke       
                            d       
                                       
After    41    410    173    -8.48    -1.70               
3h                5                       
                                   
After    42    402    1720    -10.2    -2.55               
4h                    6                   
                                       



Example 5

The liquid formulation was prepared containing N, N~dialkyl long chain alkylamides,

wherein the weight ratio of propiconazole and N, N~dialkyllong 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.

10

The formulation of Example 5 contained N,N•dialkyllong chain alkylamides in an amount of 40% wt. Table 5 describes the liquid formulation of Example 5 and the comparison formulation, Comparison E.

15   Table 5.    iCOMPARISON E:   
EXAMPLE 5: Propiconazole EC       
 

    (Containing Crystallization inhibitor)   Propiconazole EC  <Not   
                    Containing Crystallization   
                    inhibitor)       
                           
    Component    Composition    Component    composition   
                       
    Propiconazole tech    200kg (as    Propiconazole    200kg (as    Active
                pure)    tech    pure)    ingredient
                   
    Agnique ASS 70 C    100kg    AgniqueABS    100kg    Emulsifier
    Calcium        7DC       
    dodecylphenyl        Calcium       
    sulphonate        dodecylphenyl       
                    sulphonate       
                   
    EmUisogen    100kg    Emulsogen    100kg    Emulsifier
    El540        EL540       
    Castor oil ethoxylate        Castor oil       
                    ethoxylate       
                   
    Dimethyl form amide    200kg    Dimethyl    600kg    Solvent
                    formamide       
                   
    N,  N-dielhyl    300kg            Cryslalli:zation
    dodecanamide                inhibitor
                           
    N,N-dibutylheptamide    10Dkg            Crystallization
                            inhibitor
                   
    Total    1000kg    Total    1000kg   
                           

Use Example  V

The experimental results are set forth in the following table.

Example 5    Comparison E
 


    Pressur    Propicona    Propiconazole    Pressure    Propico       
    e (PSI)    zole (ppm)    decrease%    (PSI)200    nazo!e    Propicon   
                           
    200                mesh    (ppm)    azote   
    mesh                                decrease   
                                       
                                    %   
Initial    39    878    0        38        884        0   
solution                                       
                                       
After1h    39    862    -1.82        40        624        -29.41   
                                   
After2h    39    850    -3.19        Nozzles 100               
                    %blocked               
                                   
After3h    40    838    -4.56        Nozzles 100               
                    %blocked               
                                       
After4h    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 fonnulation was prepared containing N, N-dialkyl long chain alkylamides, wherein the weight ratio of hexaconazole and myc!obutanil
toN, N-<lialkyllong chain alkylamides was approx 1:1.8. Crystal formation of this

formulation was compared with a second liquid fonnulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
10

The formulation of Example 6 contained N,N-dialky! long chain alkylamides in an

amount of 45% \\1.   Table 6 describes the liquid formulation of Example 6 and the

comparison formulation, Comparison F.
 

Table6.

EXAMPLE6:                ; COMPARISON F:        Remalk   
                    <                           
Hexaconazloe•Myclobutanil EC    ~ Hexaconazloe•Myclobulanil EC               
(Containing Crystallization    ~ (without Crystallization               
inhibitor)                ~inhibitor)                       
                    '                           
Component    Composition    '~Component    Composition        I   
Hexaconazole    1OOkg (as pure) i Hexaconazole    100kg (as        Active   
tech                f. tech    pure)        ingredient   
                                           
Myclobutanil    150kg (as pure) ~ Myclobutanil    150kg (as        Active   
tech                    j tech    pure)        ingredient   
                                                   
AgniqueABS    100kg    ; Agnique ABS        100kg        Emulsifier       
                               
70 c                : 70C                           
Calcium                ; Calcium                           
dodecylphenyl                ; dodecylphenyl                           
sulphonate                : sulphonate                           
                                               
Alkamuls    100kg    (Aikamuls        100kg        Emulsifier       
OR/36                ~~ OR/36                           
Castor ail                ~Castor oil                           
ethoxylate                ~                               
                ~ ethoxylate                           
                               
Dimethyl    100kg    ;'Dimethyl        550kg        Solvent       
formam ide                ~formamide                    ICrystallization       
N,  N-diethyl    450kg    i                           
dodecanamide                i'                    inhibitor       
                '                           
                    '                           
Total    1000kg    ~Total        1000kg    I       

Use Example VI

The experimental results are set forth in the following table.

            Example 6                Comparison F               
                                                               
    Press    Hex a-        Myclo-    HEX    MYC    Press.(P    Hex-    Myclo    HEX        MYC   
        con-        butanil    deer    deere a    81)200    aeon-    butan    deer        Deere   
                (MYC)                    il               
                                                   
    (PSI)    azole        (ppm)    ease    se%    mesh    azole    (MYC    ease        ase   
                                                   
    200    (HEX)            %                (HEX)    )        %           
                                        (ppm)            %   
                                                           
    mesh    (ppm)                            (ppm)                       
Initial    40    450        657    0    0    38        445        664        0        0   
sol uti                                                               
on                                                               
                                                               
After    40    438        848    2.67    -1.37    Nozzles                               
1h                            100   %                               
                            blocked                               
                                                               
After    40    430        633    4.44    -3.65    Nozzles                               
2h                            100%                               
                            blocked                               
                                                           
                                                               
After    41    422        625    6.22    -4.88                                       
3h                                                               
                                                               
After    42    408        614    9.33    -6.55                                       
4h                                                               
                                                               
                                                               


Example 7

The fonnulation of Example 7 was prepared containing N, N-dialkyllong chain

alkylamides, wherein the weight ratio of tebuconazole to N, N-dialkyllong 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 identictf~l manner, but without any crystallization inhibitors.

The formulation of Example 7 contained N,N-dialkyllong 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: Tebuconazole EC (with    '~COMPARISON G:    Remark   
            '           
    Crystallizalion inhibitor)        '~Tebuconazole EC (without       
            ~' Crystallization inhibitor)       
    Component    Composition  ~Component    / Composition       
                       
    Tebuconazole tech    300kg  (as    aTebuconazole    300kg (as    Active   
        pure)    ~tech    pure)    ingredient   
                       
    Agnique ABS 70 C    100kg    ~Agnique ASS    100kg    Emulsifier   
    Calcium dodecylphenyl        i70C           
    sulphonate        ~Calcium           
            : dodecylphenyl           
            ~           
            ~ sulphonate           
                       
    Alkamuls OR/36    100kg    '~Aikamuls    100kg    Emulsifier   
    Castor oil ethoxylale        ~ OR/36           
            '           
            aCastor oil           
            ; ethoxylate           
                       
    sutanole    200kg    ~' Butanole    isookg    Solvent   
    N,N-dibutylnonadecanamide    150kg    ~        Crystallization   
                    inhibitor   
                       

N,  N-dibutyldecanamide    150kg    ~        Crystaflization   
        '           
        1        inhibitor   
        '               
                       
Total    1000kg    ~Total    1000kg       

Use Example Vll

The experimental results are set forth in the following table.

                                               
        Example7        Comparison G   
                                               
    Pressure    Tebucon    Tebuconazole        Pressure            Tebucon        Tebuconazole   
    (PSI)200    azole    decrease%        (PSI)200            azo/e        decrease%   
    mesh    (ppm)                mesh    .    (ppm)           
                                               
Initial    40    1400    0            38        13        0   
solution                                98           
                                           
                                               
After1h    40    1380    -1.43            39        685        -51.0   
                                               
After2h    40    1300    -7.14            Nozzles 100                       
                        %blocked                       
                                               
After3h    40    1280    -8.57            Nozzles 100                       
                        %blocked                       
                                               
                                               
After4h    42    1200    -14.3                                   
                                               


Example 8

The formulation of Example 8 was prepared containing N, N-dialkyllong chain

alkylamides, wherein the weight ratio of Myclobutanil to N, N-dialkyllong chain alkylamides

10    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 crystafli~ation inhibitors.
 

The formulation of Example 8 contained N,N-dialkyllong 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: M~clobutanil EC (with    i COMPARISON H:    Remark   
        (                           
                                   
Crystallization inhibitors)        f Myclobutanil EC (without               
        l Crystallization inhibitors)               
Component    Composition ~ Component        Com•pasition               
                           
Myclobutanil tech    400kg (as    ~ Myclobutanil        400kg (as    Active   
    pure)    ~tech        pure)    ingredient   
                           
AgniqueABS 60C    100kg    ~ Agnique ABS        100kg    Emulsifier   
Calcium dodecylphenyl        '                           
        :aoc                           
        j                           
sulphonate        ~ Calcium                           
        f dodecylphenyl                           
        '                           
        tsulphonate                           
Alkamuls ORI36    100kg    JAikamuls'        100kg    Emulsifier   
Castor oil ethoxylate        '                           
        ~ ORJ36                           
        i~Castor oil                           
        '                           
        ~ ethoxylate                           
Methanol    200kg    ! Methanol                       
                /400kg    Solvent   
N,N-dipentyloclanamide        ~                Crystallization   
    1100kg    '                   
        ?'                inhibitor   
                           
        '                   
N,N-diethyldodecanamide    100kg    ;'                           
                                   
                        Crystallization   
        i'    I       
                Inhibitor   
        1           
                           
Total    1000kg    tTotal    /1000kg               
        '                           

Use Example VIII

The experimental results are set forth in the following table.

                                                       
        ExampleS    Comparison H               
                                                       
    Pressure    Myclobu    Myclobutanil    Pressure    Myclobutanil    Myclobutanil   
    (PSI) 200    tanil    decrease%    (PSI) 200    (ppm)    decrease%   
    mesh    (ppm)            mesh                               
                                                       
Initial    40    1700    0        38        1660                0       
solution                                                       
                                                       
After1h    40    1657    -2.53        Nozzles 100                               
                    %blocked                               
                                                   
After2h    40    1605    -5.59        Nozzles 100                               
                    %blocked                               
                                                   
                                                       
After3h    40    1574    -7.41                                           
                                                       
After4h    42    1526    -10.23                                           
                                                       



Example 9

10    The formulation of Example 9 was prepared containing N, N-dialkyllong chain

alky\amides, wherein the weight ratio of dinicanazole to N, N-dialkyllong 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.

15
 

The formulation of Example 9 contained N,N~dialkyf fang chain alkylamides in an amount of 30% 'Nt. Table 9 describes the liquid formulation of Example 9 and the comparison fonnulation, Comparison I.

    Table 9.                       
                           
    EXAMPLE 9: Diniconazole EC (with    f COMPARISON 1:    Remark   
    Crystallization inhibitor)        aDiniconazole EC (without       
            ~Crystallization inhibitor)       
    Component    Composition~ Component    composition       
                       
    Diniconazote tech    100kg <as    '~ Diniconazole    100kg (as    Active   
        pure)    itech    part)    ingredient   
                       
    Agnique ABS SOC    100kg    ~ Agnique ABS    100kg    Emulsifie:r   
    Calcium dodacylphenyl        ~soc               
    sulphonate        ~               
            ~Calcium               
            i dodecylphenyl               
            ~'sulphonate               
    Emutsogen    100kg    ( Emufsogen    100kg    Emulsifier   
    EL360        I EL 360               
    Castor oil ethoxylate        ~Castor oil               
            ~ ethoxylate               
                           
    Dimethyl form amide    400kg    '~Dimethyl    1700kg    Solvent   
                       
            ~fonnamide               
            '               
                           
    N1N-dipentyldecanamide    300kg    •            Crystallization   
            ~               
            ~            inhibitor   
    Total    1000kg    ~Total    ltOOOkg       
                           

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

        ExampleS            Comparison I       
                                   
    Press.    Diniconazol    Diniconazo[e    Press.    Diniconazar        Diniconazole   
    (PSI)    e(ppm)    decrease%    (PSI)    e (ppm)        decrease%   
    200            200                   
                                   
    mesh            mesh                   
                                   
                                   
Initial    40    435    0    38        443        0   
solutio                                   
n                                   
                                   
AHer    40    430    -1.15    38        346        -21.89   
1h                                   
                                   
After    40    421    -2.07    39        270        -39.06   
2h                                   
                                   
After    40    417    -4.14    40        184        -58.47   
3h                                   
                                   
After    42    410    -5.75    40        107        -75.85   
4h                                   
                                   


Example 10

The formulation of Example 10 was prepared containing N, N-dialkyllong chain

alkylamides, wherein the weight ratio oftebuconazole toN, N-dialkyllong 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

10    without any crystanization inhibitors.
 

The formulation of Example 10 contained N,N-dialkyllong chain alkylamides in an amou11t of 40% wt. Table 10 describes the liquid formulation of Example 10 and the comparison fonnulation, Comparison J.

Table 10.

    EXAMPLE 10: Tebuconazole EC (with    ~COMPARISON J:    Remark   
    Crystallization inhibitor)        ~ Tebuconazo/e EC (without       
            ~Crystallization inhibitor)       
    Component    Composition ~ Component    Composition       
                       
    Tebuconazo!e tech    100kg (as    ~ Tebuconazole    100kg (as    Active   
        pure)    ~tech    pure)    ingredient   
                       
    Agnique ABS 60C    100kg    ~AgniqueABS    100kg    Emulsifier   
    Calcium dodecy/phenyl        ~ 60C           
    sulphonate        ~Calcium           
            ~ dodecylphenyl           
            ~ sulphonate           
    Emulsogen    100kg    f Emulsogen    100kg    Emutsifier   
    EL360        hL360           
    Castor oil ethoxylate        ~Castor oil           
            I ethoxylate           
                       
    Xylene    300kg    •~Xylene    700kg    Solvent   
    N,N-dipentyloctadecanamide    400kg    ~        Crystallizat   
            ~        ion   
                       
                       
            ~           
                       
            I        inhibitor   
                       
    Total    1000kg    lTotal    11000kg       
                       

Use Example X
 

The experimental results are set forth in the following tab(e.

                Example 10            Comparison J   
                                                   
    Pressure    Tebucona    Tebuconazo[e        Pressure    Tebucona    Tebuconazo   
    (PSI)200    zole (ppm)    decrease%            (PSI)    zole        le   
                                       
    mesh                    200    (ppm)        decrease%   
                                       
                                mesh                       
                                                   
Initial    40            438    0        38    447            0   
solution                                                       
                                                   
After1h    40            430    -1.83        38    300            -32.89   
Mer2h    40            414    -5.48            41    143            -68.00   
                                                       
After3h    39            408    -6.85            Nozzles                       
                            100%                       
                                                   
                                blocked                       
                                                       
After4h    42            400    -8.68            Nozzles                       
                            100%                       
                                blocked                       
                                                       



Example 11

The formulation of Example 11 was prepared containing N1 N-dialkyl long chain

alkylamides, wherein the weight ratio of tricyclazole to N, N-dialkyllong chain alkylamldes

was approx 1:2.2.   Crystal formation of this formulation was compared with a second liquid

10    formulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.
 
The formulation of Example 11 contained N,N-dialkyllong chain a/ky/amides in an amount of 55% wt. Table 11 describes the liquid fonnulation of Example 11 and the comparison formulation, Comparison K.

Table11.    i COMPARISON K:       
EXAMPLE 11: Tricyclazole EC        Remark   
(Containing Crystallization inhibitors)    ~ Tricyclazole EC (Not       

~    containing Crystallization

~    inhibitors)

Component    I Composition JComponent    I Composition
    Tricyclazole tech        1250kg (as    f:• Tricyclazole        250kg (as    Active   
                pure)    ~tech        pure)    ingredient   
                                       
    Agnique ABS 70 C        BOkg    ! Agnique ABS        BOkg    Emulisifier   
    Calcium dodecylphenyl            '                   
                    !70 c               
    sulphonate            ~Calcium               
                    ~                   
                    ~ dodecylphenyl               
                    f-sulphonate               
                                   
    Emulsogen        120kg    JEmulsogen        120kg    Emulsifier   
    EL360            IEL360               
                               
    Castor oil ethoxylate            ~Castor oil               
                    ,                   
                    ~ ethoxylate               
        Dimethyl formam ide        I    ;f Dimethyl    1550kg    Sotvent   
                    ~ fonnamide               
        N,N-<Iipropyldodecanamide 135Dkg    ~        I    Crystalliztion   
                    ~            inhibitor   
                                   
        N,N-dibutyldecanamide    120Dkg    '                Crystalliztion   
                !        I       
                    ~t.            inhibitor   
 




            36   
           
    j Total    j1000kg    11000kg   

Use Example  XI

The experimental results are set forth in the following table.

        Example 11    Comparison K   
                       
    Pressure    Trtcyc\    Tricyclazole    Pressure    ricyclazole    Tricyclazole
    (PSI) 200    azole    decrease%    (PSI) 200    (ppm)    decrease%
    mesh    (ppm)        mesh       
                       
Initial    40    1250    0    40    1262    0
solution                       
                       
After1h    40    1197    -4.24    40    863    -31.62
                       
After2h    40    1138    -8.96    41    654    -48.18
                       
After3h    39    1106    -11.52    Nozzles 100       
                %blocked       
                       
After4h    42    1097    -12.24    Nozzles 100       
                %blocked       
                       


Example 12

The formulation of Example 12 was prepared containing fiutriafol as the active

ingredient and N, N-dia\ky\Jong chain alkylamides, wherein the weight ratio offlulriafol toN,

10    N-dialky\long chain alkylamides was approx 1:1.6. Crystal formation of this formulation was compared with a second liquid fonnulation, which was prepared from identical components in an identical manner, but without any crystallization inhibitors.

The formulation of Example 12 contained N,N-dialky/ long chain a/ky/amides in an
 

amount of 40% wt.  Table 12 describes the liquid fonnulation of Example 12 and the

comparison formulation, Comparison L.

Table 12.

EXAMPLE 12: Flutriafol EC (Containing ~COMPARISON L: Flutriafol        Remark   
            .                   
Crystallization inhibitors)            ~ EC (Not containing           
            .                   
            ~ Crysta111zaf1on inhibitors)           
                               
Component        Composition 'j Component        Composition           
Flutriafol tech        250kg (as    SFlutriafol tech        250kg (as        Active   
        pure)    ~        pure)        ingredient   
Agnique ABS 70 C        80kg    ~ Agnique ASS        BOkg        Emulisifier   
            .                   
Calcium dodecylphenyl            ~70 c                   
            ~                   
sulphonate            ~Calcium                   
            1                   
            ~ dadecylphenyl                   
            ~~ sulphonate                   
Emulsogen        100kg    ~ Emulsogen        100kg        Emulisifier   
                               
            >                   
EL360            eEl 360                   
Castor oil ethoxylate            ~                   
            ~Castor oil                   
            ~                   
            ~ ethoxylate                   
Dimethyl formamide        1170kg    ~Dimethyl        570kg        Solvent   
            ~                   
                               
            ~formamide                   
N,  N-<iipropyl-        300kg    ;        I        Crystallization   
            ~                   
                               
dodecanamide            ~                inhibitor   
            ~                   
                               
N,N-dipentyloctanamide        100kg    ~                Crystallization   
                    I        I   
            ~                inhibitor   
            ''                   
Total        1000kg    ~Total        1000kg           
                               
 




38

Use Example XII

The experimental results are set forth in the following table.

                Example 12            Comparison L   
                                       
        Pressure    Flutriafol    Flutriafol    Pressure        Flutriafol        Flutriafol
        (PSI) 200    (ppm)    decrease%    (PSI)        (ppm)        decrease
        mesh            200                %
                        mesh               
                                       
    Initial    40    1133    0    . 40        1253        0
    solution                                   
                                   
    After 1h    40    1106    -2.38    42        690        -44.96
                                   
                                       
    After 2h    40    1059    -8.96    Nozzles               
                        100%               
                        blocked               
                                   
    After3h    39    1022    -9.79    Nozzles               
                        100%               
                        blocked               
                                   
    After4h    42    998    -11.92                   
                                       


Example 13

The formulation of Example 13 was prepared containing N, N-dia!kyl long chain

alkylamides, wherein the weight ratio oftebuconazole toN, N-dialkyllong chain alkylamides

was approx 1: 1.2.  Crystal formation of this formulation was compared with a second liquid

10    formulation, which was prepared from identical components in an identical manner, but containing an alkylamide with a lower alkyl constituent group.
 




39

The formulation of Example 13 contained N,N-dialkyl long chain alkylamide:s 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: Tebuconazole EC (with    '~COMPARISON M: Tebuconazole        Remark   
               
        I                       
long chain alkylamide)        .~EC (with lower chain alkylamide)               
Component        '    Composition               
    Composition !Component                   
Tebucanazole tech    1250kg <as    ~ Tebuconazole tech    250kg (as        Active       
    pure)    '    pure)        ingredient   
        ;               
Agnique ABS 60C    100kg    SAgnique ABS SOC    100kg        Emulsifier   
        ~                       
Calcium dodecylphenyl        ~Calcium                       
        ~                       
sulphonate        ~ dodecyJphenyl                       
        ~ sulphonate                       
                       
Emulsogen    100kg    ~ Emulsogen    100kg        Emulsifier   
EL360        ~ EL 360                       
Castor oil ethoxylate        j                       
        ~ Castor oil ethoxylate                       
                               
Xylene    250kg    iXylene    250kg        Solvent   
                       
N,N-diethyldodecanamid    300kg    £N,N-diethyloctanami    300kg        Crystallizati   
e        ~de                on inhibitor   
Total    j1000kg    ~Total    1000kg               


Use Example XIII

The experimental results are set forth in the following table.

10

Example 13    Comparison M
 




40

    Press.    Tebucona    Tebucona    Press.    Tebuconazole            Tebuconazo/e   
                                   
                                   
    (PSI)    zole    zole    (PSI)    (ppm)            decrease%   
    200    (ppm)    decrease                               
                    200                       
    mesh        %            mesh                       
Initial    40    1133    0            40    1253        0   
solution                                               
                                               
                                       
After 1h    40    1106    •2.38            40    1054        •15.88   
                                       
After2h    40    1059    •8.96            41    906        •27.66   
                                               
After3h    39    1022    •9.79            41    579.4        -53.76   
                                       
                                               
After4h    42    998    -11.92            40    504.3        -59.75   
                                               


Example 14

The formulation of Example 14 was prepared containing N, N-dialky/long chain alkylamides, wherein the weight ratio oftebuconazole toN, N-dialkyllon9 chain alkylamides was approx 1:1.2. Crystal fonnation 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.

to The formulation of Example 14 contained N,N-dialkyl Jon9 chain alkylarrUdes 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: Tebuconazole EC    ~COMPARISON N: Tebuconazole EC   IRemark
(with long chain alkylamide)    l (with lower chain alkylamide)   
        iComponent    I Composition I   
Component    ) Composition           
 




        41                           
                                   
Tebuconazole tech    250kg (as    ~ Tebuconazole tech    1250kg (as    Active   
    pure)    ~    pure)    ingredient   
        i           
        ~ Agnique ABS 60C                           
Agnique ABS SOC    100kg        100kg        Emulsifier   
                       
Calcium        '                           
                                   
        ~ Calcium dodecylphenyl                           
dodecylphenyl        '                           
        ~sulphonate                           
        '                           
        :                           
sulphonate        :                           
Emulsogen    100kg    ~' Emu/sogen    100kg        Emulsifier   
EL360        EL 360                           
Castor oil ethoxylate        ~'                           
        : Castor oil ethoxytate                           
                       
Xylene    250kg    ! Xylene    250kg        Solvent   
N,N-dipropyldodeca    300kg    ~ N,N-dipropylnonamide    1300kg        Crystallizati   
namide                        on inhibitor   
                               
Total    1000kg    :Total    1000kg                   
                                   


Use Example XIV

The experimental results are set forth in the foffowing table.


        Example 14        Comparison N
                       
    Press.    Tebucona    Tebuconazole    Press.    Tebucona    Tebucona
    (PSI)    zole (ppm)    decrease%    (PSI)    zole    zole
    200            200    (ppm)    decrease
    mesh            mesh        %
                       
Initial    40    1098    0    40    1148    0

solution
 




43

    EL360                            ~EL360        I    I   
                                               
    Castor oil ethoxylate                ~ Castor oil ethoxy/ate       
                                                       
    Xylene                    250kg    ~Xylene        J250kg    J Solvent   
                                                       
    N,N-dibutyloctanamide    300kg    iN,N-dibutylhexamide 1300kg    ICrystallizati   
                                       
                                                    on inhibitor   
                                                           
    Total                    1000kg    !Total'        J1000kg    I   
    Use Example No. XV                                   
    The experimental results of the test for crystal formation are set out in the table which   
    follows.                                                       
                                                       
                        Example 15            Comparison 0           
                                                   
        Press.        Tebuco    Tebuconazole        Press.    Tebuconaz        Tebuconazole       
        (PSI)        nazole    decrease%        (PSI)    ole (ppm)        decrease%       
        200            (ppm)                200                   
        mesh                            mesh                   
                                                       
    Initial    40            1243        0        40    1234        0       
    solution                                                       
                                                           
                                                       
    After    40            1195        -3.86        40    743        -39.79       
    1h                                                       
                                                           
                                                           
    After    40            1154        -7.16        Nozzles                   
    2h                                    100%                   
                                        blocked                   
                                                       
    After    39            1138        -8.45        Nozzles                   
    3h                                    100%                   
                                                           
                                                           
 




44


-11.3



From the experimental data set out above, it can be seen that the long chain alkyl am ides of Formula I above exhibit significant perfonnance in inhibiting the crystalfization of the pesticida11y aCtive azole derivatives. In particular, the long chain alkyl amides perform significantly beHer 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

10    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

15    within the scope of the appended calims. The advantages and objects of the invention are not necessarily encompassed by each embodiment of the invention.
 

45


AMENDED CLAIMS

received by the International Bureau on 27 October 2008(27.10.2008)

1.    An agrochemlcal composition comprising an N,N~dialkyllong chain alkylamide of the formula (I)

0
II
R --    C -- N

(I)

In which:

(a)    R1 and R2 are each normal alkyl radicals having 2 carbon atoms, and R represents an alkyl group having from 10 to 30 carbo•n atoms; or
(b)    R1 and R2 are each normal alkyl radicals having 3 carbon atoms, and R represents an alkyr group haVIng from 9 to 30 carbon atoms; or
(c)    R1 and R2 are each normal alkyii'C'Idlcalshaving from 4 to .20 carbon atoms and R represents an alkyl group having from 6 to 30 carbon atoms;
and at least one azol.e active Ingredient having the general formula (II)







01)

in which R1 represents phenyl, "4-chlorophenyl, 4-<:hlorophsnylethyJ,

4-flucrophsnyl, 2,4-dlcholorophenyl, or 4-chlorophenyloxy;

R, represents n-butyl, tert•butyl, phenyl, 2-fluorophenyl or a group of the general
 

46




-cH-<J
I
CH3

(Ill)

and

R3 represents hydroxyl, oxygen or cyano,

and optionally ~t least one member selected From the group consisting of a surface~actrve

10    agent, organic diluent and low temperatura stabilizer.

2. The composition according to claim 1, wherein in case (a},•R represents an alkyl group having from 10 to 25 carbon atoms, more preferably from 11 to 18 carbon atoms.

15    3. The composition according to claim 1, wherein in oase (b), R represents an alkyl group having from 9 to 25 carbon atoms, more preferably from 9 to 18 carbon atoms.

4. The composltfon according to claim 1, wherein In case (c), R represents an alkyJ group having from 6 to 25 carbon atoms, morfel preferably from 6 to 1B carbon atoms.
20

5.    The composition according to either of claims 1 or 4, wherein In case (c), R1 and Rz

each represent an alkyl group having from 41o 12 carbon atoms, more preferably from 4 to

B carbon atoms.

25    6.  The composition according to any preceding claim, wherein R Is a nonnal alkyl group.

1.    The composition according to any preaeding claim, wherein the total number of carbon

atoms In R, R1 and R2 Jsgrea.terthan 18, preferably greater than 18, more preferably
 

47



greater than 20.

8,    The composition according to any preceding claim, wherein the ratio of azole active

Ingredient and N, N-dialkyiiong chain ali<yiamlde Is from 1:0.1 to 1:5, more preferabiyfrom

1:1 to 1:4.

9,    The composltlon according to any preceding claim, wherein two or more N, Nwd!alkyl

long chain alkylamldes are present.

10    10. The compasitfan according to any preceding claim, wherein two or more azoJe active Ingredients are present.

11.    The composition according to any preceding claim, wherein theN, N-dlalkyllong chain

alkylamide Is selected from the group consisting of diethyldodecanamlde,

IS    diethyltrldecanamlde, N,N-dlethyltetradecanamide, N,N-dlethyihexadecanamide,

N,N-dlethylhsptadecanamicle, N,N-dlethyloctadecanamlde,   N,N-dlethylnonadecanamide,

N,N-dlpropy\decanamlde, N,N-dipropyldodecanamlde, N,N-dlpropy\trldecanamlds,

N,N-dipropyite~adecanemlde, N,N-dlethylhexadecanamide, N,N-dlpropylheptadecanamlde,

N,N-dipropyi ocladeeanamlde, N,N-dlpropylnonadecanamide, N,N-dibutylheptamlde,

20    N,N-dlbutyloctanamlde.N,N-dibutylnonamide, N,N-dibutyldecanamlde, N,N-dibutyidodecanamlde, N,N-dibutyitrldecanamlde, N,N-dibutyltetradecanamide,N,N-dibutyihexadeoanamlde,N,N-d!butylheptadecanamlde, N,N-dibutylocladecanamlde,N,N-dlbulylnonadecanamlde,

N,N~dlpentyloctanamlde,N,N-dlpentyldecanamlde,

25    N,N-dipentyidodecanamide,N,N-dlpentylte\radecanamide, N,N-dipentylhexadecanamide,

N,N-dipentyloctadecanamlde1  or any mixture thereof,

12.  The composition according to any preceding claim, wherein theN, N-diaikyliong chain
 

48



afkyfamfde is present in an amount of from 5% to BOo/o by weight, more preferably from 20%

to 60% by weight,

13.  The composition according to any preceding claim, wherein the azale derivative Is

selected from tebuconazote, cyproconazole, tr1t1conazo/e, hexaconazole, flutr1afol,

myclobutanll and mixtures thereof.

14.  The composition according to any of claims 1 to 12, wherein the azote derivative Is

selected from difenoconazole, dinicona~ole, prop/conazole, tricyclazo/e, tritlconazo/e, lO trifJumizole, flusllazole, metconazole.

15. The composition according to any preceding claim, further comprising a solvent or

diluent.

15    16. The composition according to claim 15, wherein the solvent or diluent is dimethyl formamlde or xylene.

17. The composition accordlng to any precedlng claim, further comprising an emulsifier.

20    18. An aqueous spray composltioh comprising a composition according to any preceding claim and water.

19. The composition according to claim 18, wherein the azote derivative is present In an amount of from 0.0001% to 3% by weight, more preferably from 0.002% to 2% by weight.
25

20. A use of N, N-dlalkyllong chain alkylamldes as daRned in any preceding claim to Inhibit and/or prevent the cryslol growth of pestlcldally active azole derivatives.

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