Patent Publication Number: US-2018035666-A1

Title: Agrochemical Compositions Comprising Alkyl Polypropylene Glycol Polyethylene Glycol

Description:
This application is a divisional application of U.S. application Ser. No. 12/879,758, filed Sep. 10, 2010, which claims the benefit of U.S. Provisional Application No. 61/242,119, filed Sep. 14, 2009 and claims priority to EP 09170160.7, filed Sep. 14, 2009, the contents of each are incorporated herein by reference in their entireties. 
     The present invention relates to specific agrochemical compositions comprising alkyl polypropylene glycol polyethylene glycol, processes for their preparation and the use of corresponding compositions in the agrochemical field. 
     The present invention furthermore relates to the use of alkyl polyropylene glycol polyethylene glycol as penetrant or as spontaneity enhancer for agrochemically active compounds. 
     It is generally known that many agrochemically active compounds, in particular those having systemic action, have to penetrate into the plant so that their activity can unfold uniformly in the entire plant. Thus, when the active compounds are taken up via the leaves, the active compounds have to overcome the penetration barrier of the cuticles. It is furthermore of importance that the agrochemically active compounds penetrate into the plant quickly and distributed via a surface which is as large as possible, since there would otherwise be a risk of the active components being washed off by rain. 
     It is furthermore generally known that additives used in some crop protection compositions, such as, for example, surfactants, mineral oils and vegetable oils, promote the penetration of agrochemically active compounds into the plant and are thus able to increase the activity of the active compounds. Specifically, the additives may enhance wettability, improve adhesion of the spray droplets on the surfaces of the plants (=retention), lead to better distribution of the spray coating on the surface(=spreading) of the plant, increase the availability of the active compound in the dried spray residue by incipient dissolution or directly promote penetration of the active compound through the cuticles. Here, the additives are either incorporated directly into the formulation (which is possible only up to a limited percentage), or else added by the tank mix method to the application liquor in question. 
     Independently of the abovementioned properties of the additives, it is furthermore desirable for the additives to have advantageous properties when preparing the application liquor from a concentrate, i.e. even before the actual application to the plant. When preparing the application liquor, for example, high spontaneity is desirable, i.e, on introduction into water, for example, the concentrate should quickly and without major external aid distribute itself uniformly, without any crystals or oily substances separating off. 
     The use of alkyl polypropylene glycol polyethylene glycol compounds in agrochemical compositions for achieving various effects is known from the prior art. 
     Thus, for example, WO 2008/077921 A1 discloses the use of a surfactant for preparing nanoparticles of water-insoluble active compounds in agrochemical formulations. In the formulations according to WO 2008/077921 A1, it is exclusively water-insoluble active compounds that are formulated in the form of nanoparticles. The surfactants to be used according to WO 2008/077921 A1 are preferably block copolymers of ethylene oxide units (C 2  building block) and alkylene oxide units have 3 to 10 carbon atoms. 
     This prior art neither uses water-soluble agrochemical compounds, nor is it indicated in the prior art how to improve penetration or spontaneity of agrochemical compositions. 
     WO 03/090531 A1 describes the use of certain alkoxylates as adjuvants for the agrochemical field. The alkoxylates are those which have a branched C 5 - to C 30 -alcohol moiety. Alkoxylates having a straight-chain alcohol moiety or having a branched alcohol moiety having up to four carbon atoms are not used in WO 03/090531 A1. 
     WO 00/42847 A1 relates to compositions consisting of a biocide component and an adjuvant component, the adjuvant component comprising at least surfactant from the group of specific alkoxylates. The alkoxylates described in WO 00/42847 A1 are all based on alcohol units having at least 6 carbon atoms. 
     WO 01/30147 A1 describes pesticide compositions and growth regulators for plants, insects or pests, comprising, as adjuvant, inter alia alkoxylates. The alkoxylates contain a terminal alkyl moiety based on higher alcohol homologs, for example a straight-chain C 12 -C 14 -alcohol. WO 01/30147 A1 does not disclose any alkoxylates based on lower alcohol homologs. 
     EP 0 356 812 A2 and WO 01/030147 A1, too, disclose agrochemical compositions comprising alkoxylates based on higher alcohol homologs. 
     Both with respective to enhancing penetration into the plant and with respect to enhancing spontaneity, these alkoxylates known from the prior art and based on higher alcohol homologs offer scope for improvement. 
     Accordingly, it is an object of the present invention to provide, based on the prior art illustrated above, further agrochemical preparations. 
     In a first embodiment, these agrochemical preparations and the application liquor prepared therefrom should preferably provide improved penetration of the agrochemically active compound comprised therein into the plants. 
     In a second embodiment, these agrochemical preparations should preferably have improved spontaneity on introduction into water for generating an application liquor. 
     In a third embodiment, these agrochemical preparations and the application liquors prepared therefrom should preferably simultaneously provide improved penetration of the agrochemically active compound comprised therein into the plants and have improved spontaneity of the preparation on introduction into water for generating an application liquor. 
     In a fourth embodiment, the improved spontaneity and/or penetration should not result in a simultaneous worsening of the other properties, in particular retention. 
     According to the invention, it has now been found that a composition comprising at least one active compound selected from the group consisting of compound B and compound A and at least one alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) 
       R—O—(C m H 2m O) x —(C n H 2n O) y —R′  (I)
 
     in which the individual radicals and indices have the following meanings: 
     R and R′ independently of one another represent hydrogen, a straight-chain C 1 - to C 5 -alkyl radical or a branched C 3 - or C 4 -alkyl radical; 
     m is 2 or 3; 
     n is 2 or 3; 
     x is from 5 to 150 and 
     y is from 5 to 150, 
     where one radical n or m has the meaning 2 and the other radical n or m has the meaning 3 can achieve the technical object. 
     Accordingly, the present invention firstly provides a composition comprising at least one active compound selected from the group consisting of compound B and compound A and at least one alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) 
       R—O—(C m H 2m O) x —(C n H 2n O) y —R′  (I)
 
     in which the individual radicals and indices have the following meanings: 
     R and R′ independently of one another represent hydrogen, a straight-chain C 1 - to C 5 -alkyl radical or a branched C 3 - or C 4 -alkyl radical; 
     m is 2 or 3; 
     n is 2 or 3; 
     x is from 5 to 150 and 
     y is from 5 to 150, 
     where one radical n or m has the meaning 2 and the other radical n or in has the meaning 3. 
     In the context of the present invention, a straight-chain C 1 - to C 5 -alkyl radical is understood as meaning a methyl, ethyl, n-propyl, n-butyl or n-pentyl radical. 
     In the context of the present invention, a branched C 3 - or C 4 -alkyl radical is understood as meaning an isopropyl, isobutyl or tert.-butyl radical. 
     In a preferred embodiment, the radicals R and R′ are independently of one another selected from the group consisting of a methyl radical, an n-butyl radical and hydrogen. 
     In an even more preferred embodiment, the radicals R and R′ are independently of one another selected from the group consisting of an n-butyl radical and hydrogen. 
     With a view to the arrangement of the polyethylene and polypropylene moieties,
         (a) either m has the value 2 and n has the value 3;   (b) or m has the value 3 and n has the value 2.       

     Preferred is embodiment (b) where m is 3 and n is 2. 
     Very particular preference is given to alkyl polypropylene glycol polyethylene glycol compounds of the formula (I) in which 
     m is 3, 
     n is 2, 
     x is from 5 to 80, 
     y is from 5 to 80, 
     R is n-butyl or hydrogen and 
     R′ is hydrogen. 
     According to the invention, it has been found that corresponding compositions generally have penetration-enhancing properties for water-soluble agrochemically active compounds. 
     According to the invention, it has furthermore been found that corresponding compositions generally increase spontaneity when preparing the application liquor from the concentrate. 
     According to the invention, it has furthermore been found that corresponding compositions generally have penetration-enhancing properties for water-soluble agrochemically active compounds and increase spontaneity when preparing the application liquor from the concentrate. 
     In the context of the present invention, the term “water-soluble agrochemically active compound” is generally understood as meaning an insecticidally and/or acaricidally active compound (i.e. an active compound that controls insects and/or Acarina) which has (at 20° C.) a solubility of ≧10 mg/l in water. Compounds A and B meet this requirement. 
     Suitable agrochemically active compounds which can be used in the composition according to the present invention are the active compounds below: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     The compounds mentioned above and their use in the agrochemical field, for example as insecticides, are known. 
     Further insecticides or acaricides which, besides the agrochemically active compounds mentioned above, may additionally be present in the composition according to the invention are, for example, active compounds from the group of the pyrethroids, the phthalamides (flubendiamide), anthranildiamides (CYAZYPY, RYNAXYPYR) or the ketoenol derivatives. The following compounds may be mentioned in an exemplary manner: 
     cypermethrin, 
     deltamethrin, 
     permethrin, 
     transfluthrin, 
     natural pyrethrum, 
     fenpropathrin, 
     cyfluthrin, 
     β-cyfluthrin and also 
     from the group of the ketoenol derivatives spirodiclofen, spiromesifen and spirotetramat. 
     These further insecticides or acaricides which may be present in the composition according to the invention as mixing partners with the at least agrochemically active compound can be either water-soluble or else water-insoluble 
     Suitable fungicides which, besides the agrochemically active compounds mentioned above, may additionally be present in the composition according to the invention are active compounds, for example, from the group of the azoles, the strobilurin derivatives and the amino acid derivatives. The following compounds may be mentioned in an exemplary manner: 
     prothioconazole, 
     tebuconazole, 
     cyproconazole, 
     propiconazole, 
     triadimenol, 
     myclobutanil, 
     trifloxystrobin, 
     azoxystrobin, 
     kresoxim-methyl, 
     pyraclostrobin, 
     fluoxystrobin, 
     iprovalicarb, 
     fluopicolide, 
     bixafen and 
     fluopyram. 
     The agrochemically active compounds mentioned above are known per se to the person skilled in the art (cf. Pesticide Manual; British Crop Protection Council; Edition: 14 (30 November 2006)). 
     These further fungicides, which may be present as mixing partners in the composition according to the invention, can be water-soluble or else water-insoluble. 
     In a further embodiment of the present invention, the composition generally comprises from 1 to 50% by weight, more preferably from 5 to 40% by weight, particularly preferably from 10 to 25% by weight, in each case based on the entire composition, of the water-soluble agrochemically active compound. 
     In the composition according to the invention, the alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) is preferably used in a concentration of from 0.1 to 80% by weight, more preferably from 0.5 to 60% by weight, particularly preferably from 5 to 45% by weight, in each case based on the entire composition. 
     In a further embodiment of the present invention, the weight ratio of water-soluble agrochemically active compound to the alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) is generally from 1:0.1 to 1:6, more preferably from 1:0.2 to 1:4, particularly preferably from 1:0.5 to 1:2.5. If in the present invention the weight ratio of water-soluble agrochemically active compound to the alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) is in the range indicated above, a preferred balance between the effect of the alkyl polypropylene glycol polyethylene glycol compound of the general formula (I) and the costs associated with using this compound is achieved. 
     The use according to the invention of alkyl polypropylene glycol polyethylene glycol compounds of the general formula (I) has a number of advantages. Thus, these alkyl polypropylene glycol polyethylene glycol compounds are products which can be handled without any problems and which are also available in relatively large amounts. Moreover, they are biodegradable and allow a marked increase in effectiveness when applying water-soluble agrochemically active compounds against insects or Acarina and/or in the vector control associated therewith, and/or significant improvement of spontaneity. 
     Corresponding alkyl polypropylene glycol polyethylene glycols are commercially available and sold inter alia under the names ANTAROX® B/848, ANTAROX® B/500, EMULSOGEN® 3510, EMULSOGEN® EP 4901, EMULSOGEN® V 1816 or GENAPOL® PF 40. 
     The general formula (I) provides a general definition of the alkyl polypropylene glycol polyethylene glycol compounds which can be used according to the invention. These alkyl polypropylene glycol polyethylene glycol compounds are generally mixtures of compounds of this type having various chain lengths. Accordingly, the indices x and y are average values in the ranges defined above which may also deviate from whole numbers. 
     In the context of the present invention, it is also possible to use mixtures of the alkyl polypropylene glycol polyethylene glycol compounds defined under the general formula (I), for example of two, three, four or five different alkyl polypropylene glycol polyethylene glycol compounds. If, in the context of the present invention, mixtures of a plurality of alkyl polypropylene glycol polyethylene glycol compounds are used, it is possible, for example, to select one alkyl polypropylene glycol polyethylene glycol compound such that the penetration of the agrochemically active compound is optimized and the other alkyl polypropylene glycol polyethylene glycol compound such that the spontaneity of the agrochemically active compound is optimized. 
     Furthermore, the composition according to the invention may generally comprise from 1 to 90% by weight, more preferably from 15 to 75% by weight, particularly preferably from 30 to 60% by weight, in each case based on the composition, of one or more solvents. 
     Suitable solvents which may be used in the context of the present invention are preferably water-soluble and/or water-miscible solvents. Corresponding examples of suitable solvents are γ-butyrolactone, dimethyl isosorbide, dimethyl sulfoxide (DMSO), propylene glycol, propylene carbonate, benzyl alcohol, dimethylamides, short-chain alcohols, in particular ethanol, n-propanol, isopranol, n-butanol, isobutanol and tert-butanol, N-methyl-2-pyrrolidone (NMP), polyethylene glycol, methoxy-2-propanol, triethylene glycol diacetate and water. 
     Further optional components of the composition according to the invention are, for example, additives in amounts of in general from 0 to 30% by weight, more preferably from 0 to 20% by weight, particularly preferably from 0 to 10% by weight. Additives which may be present in the crop treatment compositions according to the invention are to be understood as being further agrochemically active compounds, and also crystallization inhibitors. wetting agents, emulsifiers and water. 
     Crystallization inhibitors which may be present in the compositions according to the invention are all compounds which can customarily be used for such purposes it agrochemical compositions. N-alkylpyrrolidones, such as N-octylpyrrolidone and N-dodecylpyrrolidone, may be mentioned as being preferred, furthermore copolymers of polyvinylpyrrolidone and polyvinyl alcohol, such as, for example, the polyvinylpyrrolidone/polyvinyl alcohol copolymer known under the name LUVISKOL VA 64 (from BASF), furthermore alkylcarboxylic acid dimethylamides, such as decanoic acid dimethylamide or the C 6-12 -alkanecarboxylic acid dimethylamide mixture known under the name HALLCOMID® (from. Hall Comp.), and furthermore copolymers of ethylenediamine with ethylene oxide and propylene oxide, such as, for example, the product known under the name SYNPERONIC T 304 (from Uniqema). 
     Suitable wetting agents are all compounds which can customarily be used for such purposes in crop treatment compositions. Alkylphenol ethoxylates, alkylnaphthalenesulfonates, dialkyl sulfosuccinates, such as dioctyl sulfosuccinate sodium, lauryl ether sulfates and polyoxyethylene sorbitan fatty acid esters may be mentioned as being preferred. 
     For their part, the alkyl polypropylene glycol polyethylene glycol compounds to be used according to the invention and employed for improving penetration and/or for improving spontaneity have emulsifier properties. Nevertheless, in the context of the present invention, a further emulsifier may optionally be used in the composition according to the invention. 
     In this case, suitable emulsifiers are all customary nonionogenic, anionic, cationic and zwitterionic compounds having surface-active properties which are customarily used in agrochemical compositions. These compounds include reaction products of fatty acids, fatty esters, fatty alcohols, fatty amines, alkylphenols or alkylarylphenols with ethylene oxide and/or propylene oxide and/or butylene oxide, and also their sulfuric esters, phosphoric monoesters and phosphoric diesters, furthermore reaction products of ethylene oxide with propylene oxide, furthermore alkylsulfonates, alkyl sulfates, aryl sulfates, tetraalkylammonium halides, trialkylarylammonium halides and alkylaminesulfonates. The emulsifiers may be used individually or else as a mixture. Reaction products of castor oil with ethylene oxide in a molar ratio of from 1:20 to 1:60, reaction products of C 6 -C 20 -alcohols with ethylene oxide in a molar ratio of from 1:5 to 1:50, reaction products of fatty amines with ethylene oxide in a molar ratio of from 1:2 to 1:25, reaction products of 1 mol of phenol with 2 to 3 mol of styrene and 10 to 50 mol of ethylene oxide, reaction products of C 8 -C 12 -alkylphenols with ethylene oxide in a molar ratio of from 1:5 to 1:30, alkyl glycosides, C 8 -C 16 -alkylbenzenesulfonic acid salts, such as, for example, calcium, monoethanolammonium, diethanolammonium and triethanolammonium salts, may be mentioned by way of preference. 
     Examples of nonionic emulsifiers which may be mentioned are the products known under the names PLURONIC PE 10 100 (from BASF) and ATLOX 4913 (from Uniqema). Also suitable are tristyrylphenyl ethoxylates. Examples of anionic emulsifiers which may be mentioned are the product commercially available under the name BAYKANOL SL (=condensate of sulfonated ditolyl ether and formaldehyde), and also phosphated or sulfated tristyrylphenol ethoxylates, where specific mention is given to SOPROPHOR FLK and SOPROPHOR 4D 384 (from Rhodia). 
     The content of the individual components in the plant treatment compositions according to the invention may be varied within a certain range. Preference is given to plant treatment compositions in which the concentrations
         of alkyl polypropylene glycol polyethylene glycol compounds of the general formula (I) are from 0.1 to 80% by weight;   of agrochemically active compound are from 1 to 50% by weight;   of solvents are from 1 to 90% by weight and   of additives are from 0 to 30% by weight.       

     The present invention furthermore relates to the preparation of the composition according to the invention. The crop treatment compositions according to the invention are generally prepared by mixing the individual components in the respective desired ratios. In general, one agrochemically active compound is initially charged, and the other components are then added with stirring, in any order. 
     When preparing the composition according to the invention, the temperatures may be varied within a certain range. In general, the operations are carried out at temperatures between 10 and 70° C., preferably at room temperature. 
     Suitable for preparing the composition according to the invention are customary apparatus used for preparing agrochemical formulations. 
     The compositions according to the invention can be applied either as such or after prior dilution with water or other diluents, i.e., for example, as emulsions, suspensions, solutions or aerosols. In the case of direct application, the composition according to the invention improves at least the penetration of the agrochemically active compound. 
     In a particularly preferred embodiment, the composition according to the invention is present in the form of a concentrate which is diluted with a solvent, in particular water, prior to the actual application. In this case, the composition according to the invention improves the penetration of the agrochemically active compound and/or the spontaneity of the preparation when preparing the application liquor. 
     In addition, the present invention also relates to the use of corresponding compositions in the agrochemical field. The present invention relates in particular to the use of the compositions according to the invention for controlling insects and/or Acarina. In the context of the use according to the invention, the composition according to the invention is generally initially introduced into an aqueous phase, which is then applied. 
     Here, application is carried out using customary methods, i.e., for example, by spraying, watering, atomizing, injecting or spreading. 
     The application rate of the plant treatment compositions according to the invention can be varied within a relatively wide range. It depends on the respective active compounds present and their concentration in the formulations. 
     With the aid of the plant treatment compositions according to the invention, it is possible to apply water-soluble insecticidally and/or acaricidally active compounds in a particularly advantageous manner to the plants and/or their habitat. Here, the penetration power of the active compounds is enhanced, the biological activity of the active compounds is increased compared to conventional formulations and/or the spontaneity of the products on introduction into water is improved. 
     The present invention furthermore relates to the use of alkyl polypropylene glycol polyethylene glycol compounds of the general formula (I) 
       R—O—(C m H 2m O) x —(C n H 2n O) y —R′  (I)
 
     in which the individual radicals and indices have the following meanings: 
     R and R′ independently of one another represent hydrogen, a straight-chain C 1 - to C 5 -alkyl radical or a branched C 3 - or C 4 -alkyl radical; 
     m is 2 or 3; 
     n is 2 or 3; 
     x is from 5 to 150 and 
     y is from 5 to 150, 
     where one radical n or m has the meaning 2 and the other radical n or m has the meaning 3 
     as penetrant for water-soluble insecticidally and acaricidally active compounds and/or for increasing the spontaneity when preparing application liquors. 
     The water-soluble insecticidally and/or acaricidally active compounds for the use according to the invention are preferably selected from the group consisting of compound B, compound A, the group of the neonicotinoids (i.e. imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran), sulfoxaflor and flonicamid. Particular preference is given to compound B and compound A and the neonicotinoids. Very particular preference is given to compound B and compound A. 
     In the context of the present invention, a straight-chain C 1 - to C 5 -alkyl radical is understood as meaning a methyl, ethyl, n-propyl, n-butyl or n-pentyl radical. 
     In the context of the present invention, a branched C 3 - or C 4 -alkyl radical is understood as meaning an isopropyl, isobutyl or tert.-butyl radical. 
     In a preferred embodiment, the radicals R and R′ are independently of one another selected from the group consisting of a methyl radical, an n-butyl radical and hydrogen. 
     In an even more preferred embodiment, the radicals R and R′ are independently of one another selected from the group consisting of an n-butyl radical and hydrogen. 
     With a view to the arrangement of the polyethylene and polypropylene moieties,
         (a) either m has the value 2 and n has the value 3;   (b) or m has the value 3 and n has the value 2.       

     Preferred is embodiment (b) where m is 3 and n is 2. 
     Very particular preference is given to alkyl polypropylene glycol polyethylene glycol compounds of the formula (I) in which 
     m is 3, 
     n is 2, 
     x is from 5 to 80, 
     y is from 5 to 80, 
     R is n-butyl or hydrogen and 
     R′ is hydrogen. 
     According to the invention, it has been found that corresponding compositions generally have penetration-enhancing properties for water-soluble agrochemically active compounds. 
     According to the invention, it has furthermore been found that corresponding compositions generally increase spontaneity when preparing the application liquor from the concentrate. 
     According to the invention, it has furthermore been found that corresponding compositions generally have penetration-enhancing properties for water-soluble agrochemically active compounds and increase spontaneity when preparing the application liquor from the concentrate. 
     For further embodiments of the use according to the invention, reference is made to what was discussed above. 
     The invention is illustrated by the examples below. 
    
    
     PREPARATION EXAMPLES 
     General Example 
     To produce a formulation, 
     
       
         
           
               
               
               
             
               
                   
               
             
            
               
                 20-40 
                 g 
                 of alkyl polypropylene glycol polyethylene glycol 
               
               
                   
                   
                 compound of the formula (I) (the exact amount of 
               
               
                   
                   
                 additive is stated in Table 1), 
               
               
                 43-63 
                 g 
                 of solvent (the exact amount is adapted to the 
               
               
                   
                   
                 amount of alkyl polypropylene glycol polyethylene 
               
               
                   
                   
                 glycol compound of the formula (I)) and 
               
               
                 25 
                 mg 
                 of antifoam are successively added with stirring 
               
               
                   
                   
                 at room temperature to 
               
               
                 17 
                 g 
                 of active compound. 
               
               
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature until a transparent solution has formed. This gives a homogeneous liquid. 
     Comparative Example A 
     To prepare a formulation, 
     
       
         
           
               
               
             
               
                   
               
             
            
               
                 40 g 
                 of emulsifier KS (structure: [RCOO(EO) x/y/z ][CH(CH 2 ) 2 ]), 
               
               
                 43 g 
                 of solvent (for example propylene carbonate, 1-methoxy-2- 
               
               
                   
                 propanol, benzyl alcohol, etc.) and 
               
               
                 25 mg 
                 of antifoam 
               
            
           
           
               
            
               
                 are successively added with stirring at room temperature to 
               
            
           
           
               
               
            
               
                 17 g 
                 of compound B. 
               
               
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature for another 5 minutes. This gives a homogeneous liquid. 
     Comparative Example B 
     To prepare a formulation, 
     
       
         
           
               
               
               
             
               
                   
               
             
            
               
                 40 
                 g 
                 of emulsifier AGNIQUE 3551 (structure: 
               
               
                   
                   
                 1-Et—Hex—O-(PO) x -(EO) y -H), 
               
               
                 43 
                 g 
                 of solvent (for example propylene carbonate, 
               
               
                   
                   
                 1-methoxy-2-propanol, benzyl alcohol, etc.) and 
               
               
                 25 
                 mg 
                 of antifoam are successively added with stirring 
               
               
                   
                   
                 at room temperature to 
               
               
                 17 
                 g 
                 of compound B. 
               
               
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature for another 5 minutes. This gives a homogeneous liquid. 
     Comparative Example C 
     To prepare a formulation, 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 40 g 
                 of emulsifier AGNIQUE KE 3552 (structure: 
               
               
                   
                   
                 n-Octyl-O—(PO) x —(EO) y —H), 
               
               
                   
                 43 g 
                 of solvent (for example propylene carbonate, 
               
               
                   
                   
                 1-methoxy-2-propanol, benzyl alcohol, etc.) and 
               
               
                   
                 25 mg 
                 of antifoam 
               
            
           
           
               
               
            
               
                   
                 are successively added with stirring at room temperature to 
               
            
           
           
               
               
               
            
               
                   
                 17 g 
                 of compound B. 
               
               
                   
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature for another 5 minutes. This gives a homogeneous liquid. 
     Comparative Example D 
     To prepare a formulation, 
     
       
         
           
               
               
               
             
               
                   
               
             
            
               
                 40 
                 g 
                 EMULSOGEN ITA 200 (structure: Iso-C 13 H 27 —O- 
               
               
                   
                   
                 (PO) x -(EO) y -H), 
               
               
                 43 
                 g 
                 of solvent (for example propylene carbonate, 
               
               
                   
                   
                 1-methoxy-2-propanol, benzyl alcohol, etc.) and 
               
               
                 25 
                 mg 
                 of antifoam are successively added with stirring 
               
               
                   
                   
                 at room temperature to 
               
               
                 17 
                 g 
                 of compound B. 
               
               
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature for another 5 minutes. This gives a homogeneous liquid. 
     Comparative Example E 
     To produce a formulation, 
     
       
         
           
               
               
               
             
               
                   
               
             
            
               
                 30 
                 g 
                 of ANTAROX B/848 (structure: n-Bu—O-(PO) x -(EO) y -H), 
               
               
                 43 
                 g 
                 of solvent (for example NMP, butyrolactone, 
               
               
                   
                   
                 dimethylimidazolinone, etc.) 
               
               
                   
                   
                 and 
               
               
                 25 
                 mg 
                 of antifoam are successively added with stirring 
               
               
                   
                   
                 at room temperature to 
               
               
                 8.5 
                 g 
                 of flonicamid or sulfoxaflor. 
               
               
                   
               
            
           
         
       
     
     After the addition has ended, the mixture is stirred at room temperature for another 5 minutes. This gives a homogeneous liquid. 
     Use Example I 
     Determination of the spontaneity of a formulation according to the above recipe. 
     A 100 ml glass cylinder with ml scale (diameter about 3 cm, height about 25 cm) and ground-glass neck is filled to the 100 ml mark with water (CIPAC C) and adjusted to the respective temperature. For the actual test, 1.0 ml of the formulation are added dropwise to the water from a height of 1 cm above the surface of the water, and the behaviour on emersion and sinking is observed. If the drops fall to the bottom, the spontaneity is unsatisfactory; however, if the drops dissolve within the first section of the fall, i.e. within a few cm, the spontaneity is very good. In cases where there is incomplete dissolution on introduction into water, the cylinder is closed with a stopper and inverted up to three times to achieve mixing. The resulting mixture is examined for phase separation (crystalline or oily phases). 
     The results of such spontaneity tests are summarized in Table I. Remarkable is in particular the observation that the spontaneities of Test Series 2 (with emulsifiers covered inter alia by patent WO 03/090531 A1 mentioned above) are unsatisfactory, whereas the analogous formulations with ANTAROX B/848 (from Rhodia, Tests 1a to 1c) or ANTAROX B/500 (from Rhodia, Tests 1d and 1e) or EMULSOGEN 3510 (from Clariant, Tests 1f and 1g) or EMULSOGEN EP 4901 (from Clariant, Tests 1h 1i) show good spontaneities. These additives are covered by the definition of the additives to be used according to the invention. 
     Mixtures of ANTAROX B/848 and EMULSOGEN 3510 or EMULSOGEN EP 4901, too, have good spontaneities (examples 1l to 1q). In addition, Tests 3a to 3c, where the emulsifier AGNIQUE KE 3552 (from Cognis) is used, show, compared to Tests 2a to 2c (emulsifier AGNIQUE KE 3551, from Cognis), that a straight-chain terminal octyl group, compared to a branched group, results in virtually no improvement of spontaneity. Accordingly, it is not the branching but the chain length of the terminal alkyl group that matters, short alkyl groups (or hydrogen) offering advantages with respect to spontaneity properties. 
     This observation is highly surprising since the alkyl chains are located at the lipophilic (PO) end of the emulsifier and, in spite of their short length, have a very substantial impact on the properties of the emulsifier, compared to the much longer lipophilic (PO) moiety. 
     Table I: Results of the spontaneity tests 
     Formulations of compound B with propylene carbonate, benzyl alcohol or butyrolactone as solvent 
     
       
         
           
               
             
               
                 TABLE I 
               
             
            
               
                   
               
               
                 Formulations (SL-200) of compound B with propylene carbonate as solvent 
               
            
           
           
               
               
               
            
               
                   
                 Emulsifier 
                 SPONTANEITY* 
               
            
           
           
               
               
               
               
               
               
            
               
                 No. 
                 Concentration, name 
                 Structure 
                 10° C. 
                 RT (20° C.) 
                 30° C. 
               
               
                   
               
               
                 1a 
                 40% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 3.5 
                 3 
                 3 
               
               
                   
                 B/848 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1b 
                 30% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 3.5 
                 2 
                 1.5 
               
               
                   
                 B/848 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1c 
                 20% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 4 
                 2.5 
                 2 
               
               
                   
                 B/848 
                   
                 (PS) 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1d 
                 40% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 3 
                 2.5 
                 2.5 
               
               
                   
                 B/500 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1e 
                 30% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 3 
                 2 
                 2 
               
               
                   
                 B/500 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 5a 
                 30% WITCONOL NS 
                 nBu—O—(PO) x —(EO) y —H 
                   
                 1 
               
               
                   
                 500 K (ETHYLAN NS 
               
               
                   
                 500 LQ) according to 
               
               
                   
                 the invention 
               
               
                 5b 
                 10% WITCONOL NS 
                 nBu—O—(PO) x —(EO) y —H 
                   
                 4 (PS) 
               
               
                   
                 500 K (ETHYLAN NS 
               
               
                   
                 500 LQ) according to 
               
               
                   
                 the invention 
               
               
                 5c 
                 30% ATLAS G 5000 
                 nBu—O—(PO) x —(EO) y —H 
                   
                 2 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 5d 
                 10% ATLAS G 5000 
                 nBu—O—(PO) x —(EO) y —H 
                   
                 2 (PS) 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 5e 
                 30% PLURONIC PE 
                 H—(EO) w —(PO) x —(EO) y —H 
                   
                 5 (PS) 
               
               
                   
                 10500 (ETHYLAN 
               
               
                   
                 324) 
               
               
                 1f 
                 40% 
                 nBu—O—(PO) x —(EO) y —H 
                 2.5 
                 3 
                 3.5 
               
               
                   
                 EMULSOGEN 3510 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1g 
                 20% 
                 nBu—O—(PO) x —(EO) y —H 
                 4 
                 2.5 
                 2.5 
               
               
                   
                 EMULSOGEN 3510 
                   
                 (PS) 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1h 
                 40% 
                 nBu—O—(PO) x —(EO) y —H 
                 4 
                 3 
                 3 
               
               
                   
                 EMULSOGEN EP 
                   
                 (PS) 
               
               
                   
                 4901 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1i 
                 40% 
                 HO—(PO) x —(EO) y —H 
                 3.5 
                 3 
                 4 
               
               
                   
                 EMULSOGEN V 1816 
                   
                 (PS) 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1j 
                 20% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 3.5 
                 3 
                 2.5 
               
               
                   
                 B/848, 10% 
                 HO—(PO) x —(EO) y —H 
               
               
                   
                 EMULSOGEN V 1816 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1k 
                 15% ANTAROX 
                 nBu—O—(PO) n —(EO) m —H, 
                 4 
                 3 
                 2.5 
               
               
                   
                 B/848, 15% 
                 HO—(PO) x —(EO) y —H 
               
               
                   
                 EMULSOGEN V 1816 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1l 
                 20% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 2.5 
                 2.5 
                 2 
               
               
                   
                 B/848, 10% 
                 nBu—O—(PO) x —(EO) y —H 
                 (PS) 
               
               
                   
                 EMULSOGEN 3510 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1m 
                 15% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 2.5 
                 2 
                 1.5 
               
               
                   
                 B/848, 15% 
                 nBu—O—(PO) x —(EO) y —H 
               
               
                   
                 EMULSOGEN 3510 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1n 
                 10% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 2.5 
                 2 
                 1.5 
               
               
                   
                 B/848, 20% 
                 nBu—O—(PO) x —(EO) y —H 
               
               
                   
                 EMULSOGEN 3510 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1o 
                 20% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 3 
                 2 
                 2 
               
               
                   
                 B/848, 10% 
                 nBu—O—(PO) x —(EO) m —H 
                 (PS) 
               
               
                   
                 EMULSOGEN EP 
               
               
                   
                 4901 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1p 
                 15% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 2.5 
                 2.5 (PS) 
                 2 
               
               
                   
                 B/848, 15% 
                 nBu—O—(PO) x —(EO) y —H 
                 (PS) 
               
               
                   
                 EMULSOGEN EP 
               
               
                   
                 4901 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 1q 
                 10% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H, 
                 3 
                 2.5 
                 2 
               
               
                   
                 B/848, 20% 
                 nBu—O—(PO) x —(EO) y —H 
                 (PS) 
               
               
                   
                 EMULSOGEN EP 
               
               
                   
                 4901 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                 2a 
                 40% AGNIQUE 3551 
                 Et—Hex—O—(PO) x —(EO) y —H 
                 6 
                 6 (PS) 
                 6 (PS) 
               
               
                   
                 comparative 
                   
                 (PS) 
               
               
                 2b 
                 30% AGNIQUE 3551 
                 Et—Hex—O—(PO) x —(EO) y —H 
                 6 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                 comparative 
                   
                 (PS) 
               
               
                 2c 
                 20% AGNIQUE 3551 
                 Et—Hex—O—(PO) x —(EO) y —H 
                 6 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                 comparative 
                   
                 (PS) 
               
               
                 2d 
                 40% 
                 Iso-C 13 H 27 —O—(PO) x —(EO) y —H 
                 6 
                 6 (PS) 
                 5 (PS) 
               
               
                   
                 EMULSOGEN ITA 
                   
                 (PS) 
               
               
                   
                 200 
               
               
                   
                 comparative 
               
               
                 2e 
                 40% 
                 RO—(PO) x —(EO) y —H 
                 6 
                 5 (PS) 
                 4 (PS) 
               
               
                   
                 GENAPOL EP 2584 
                 R = long-chain 
                 (PS) 
               
               
                   
                 comparative 
                 alcohol (not 
               
               
                   
                   
                 according to the 
               
               
                   
                   
                 invention) 
               
               
                 3a 
                 40% 
                 n-Oct—O—(PO) x (EO) y —H 
                 6 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                 AGNIQUE KE 3552 
                   
                 (PS) 
               
               
                   
                 comparative 
               
               
                 3b 
                 30% 
                 n-Oct—O—(PO) x —(EO) y —H 
                 6 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                 AGNIQUE KE 3552 
                   
                 (PS) 
               
               
                   
                 comparative 
               
               
                 3c 
                 20% 
                 n-Oct—O—(PO) x —(EO) y —H 
                 6 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                 AGNIQUE KE 3552 
                   
                 (PS) 
               
               
                   
                 comparative 
               
               
                 4 
                 40% 
                 [RCOO(EO) x/y/z ][CH(CH 2 ) 2 ] 
                 6 
                 6 (PS) 
                 6 (PS) 
               
               
                   
                 EMULGATOR KS 
                   
                 (PS) 
               
               
                   
                 comparative 
               
               
                   
               
               
                 *Evaluation scale 1-6, i.e. 1 = very good, 6 = insufficient; PS = phase separation; RT = room temperature (20° C.), x, y, z, n, m are integers ≧2. 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE II 
               
             
            
               
                   
               
               
                 Formulations (SL-200) of compound B with different solvents 
               
            
           
           
               
               
               
            
               
                   
                 Emulsifier 
                 SPONTANEITY* 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                 Concentration, 
                   
                   
                 RT 
                   
               
               
                 No. 
                 Solvent 
                 Name 
                 Structure 
                 10° C. 
                 (20° C.) 
                 30° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Propylene 
                 No emulsifier 
                 6 (PS) 
                 6 (PS) 
                 6 (PS) 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1a 
                 carbonate 
                 40% ANTAROX 
                 nBu—O-(PO) x - 
                   3.5 
                 3 
                 3 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                 1b 
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                   3.5 
                 2 
                   1.5 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                 1c 
                   
                 20% ANTAROX 
                 nBu—O-(PO) x - 
                 4 (PS) 
                   2.5 
                 2 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                 3b 
                   
                 30% AGNIQUE KE 
                 n-Oct-O-(PO) x - 
                 6 (PS) 
                 3 (PS) 
                 3 (PS) 
               
               
                   
                   
                 3552 comparative 
                 (EO) y -H 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Benzyl 
                 No emulsifier 
                 6 (PS) 
                 6 (PS) 
                 6 (PS) 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 alcohol 
                 40% ANTAROX 
                 nBu—O-(PO) x - 
                 4 
                 4 
                 4 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 4 
                 5 (PS) 
                 6 (PS) 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 20% ANTAROX 
                 nBu—O-(PO) x - 
                 6 (PS) 
                 6 (PS) 
                 6 (PS) 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 30% AGNIQUE KE 
                 n-Oct-O-(PO) x - 
                 6 (PS) 
                 6 (PS) 
                 6 (PS) 
               
               
                   
                   
                 3552 comparative 
                 (EO) y -H 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Benzyl alcohol/ 
                 No emulsifier 
                 6 (PS) 
                 6 (PS) 
                 6 (PS) 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 □-butyrolactone 
                 40% ANTAROX 
                 nBu—O-(PO) x - 
                 3 
                 2 
                 2 
               
               
                   
                 (1:1) 
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 1 
                 1 
                 1 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 20% ANTAROX 
                 nBu—O-(PO) x - 
                 1 
                 1 
                 1 
               
               
                   
                   
                 B/848 according to 
                 (EO) y -H 
               
               
                   
                   
                 the invention 
               
               
                   
                   
                 30% AGNIQUE KE 
                 n-Oct-O-(PO) x - 
                 4 
                 5 
                 5 
               
               
                   
                   
                 3552 comparative 
                 (EO) y -H 
               
               
                   
                   
               
               
                   
                 *Evaluation scale 1-6, i.e. 1 = very good, 6 = insufficient; 
               
               
                   
                 PS = phase separation 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE III 
               
             
            
               
                   
               
               
                 Acetamiprid formulation with benzyl alcohol as solvent 
               
            
           
           
               
               
               
            
               
                   
                 Emulsifier 
                 SPONTANEITY* 
               
            
           
           
               
               
               
               
               
               
            
               
                 No. 
                 Name 
                 Structure 
                 10° C. 
                 RT (20° C.) 
                 30° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 30% ANTAROX 
                 nBu—O—(PO) x —(EO) y —H 
                 2 
                 2 (clear) 
                 2 
               
               
                   
                 B/848 
                   
                 (clear) 
                   
                 (clear) 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE IV 
               
             
            
               
                   
               
               
                 Flonicamid formulations with NMP as solvent 
               
            
           
           
               
               
            
               
                   
                 SPONTANEITY* 
               
            
           
           
               
               
               
            
               
                   
                 RT 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Emulsifier 
                 10° 
                 (20° 
                 30° 
               
            
           
           
               
               
               
               
               
               
            
               
                 No. 
                 Name 
                 Structure 
                 C. 
                 C.) 
                 C. 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 30% AGNIQUE 
                 Et—Hex—O-(PO) x - 
                 2.5 
                   
               
               
                   
                 3551 comparative 
                 (EO) y -H 
                 (turbid) 
               
               
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 2 (clear) 
               
               
                   
                 B/848 
                 (EO) y -H 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 2 (clear) 
               
               
                   
                 B/500 
                 (EO) y -H 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE V 
               
             
            
               
                   
               
               
                 Sulfoxaflor formulations with dimethylimidazolinone 
               
               
                 (DMI) as solvent 
               
            
           
           
               
               
            
               
                   
                 SPONTANEITY* 
               
            
           
           
               
               
               
            
               
                   
                 RT 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Emulsifier 
                 10° 
                 (20° 
                 30° 
               
            
           
           
               
               
               
               
               
               
            
               
                 No. 
                 Name 
                 Structure 
                 C. 
                 C.) 
                 C. 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 30% AGNIQUE 
                 Et—Hex—O-(PO) x - 
                 2.5 
                   
               
               
                   
                 3551 comparative 
                 (EO) y -H 
                 (turbid) 
               
               
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 2 (clear) 
               
               
                   
                 B/848 
                 (EO) y -H 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE VI 
               
             
            
               
                   
               
               
                 Formulations of compound A with propylene carbonate as solvent 
               
            
           
           
               
               
            
               
                   
                 SPONTANEITY* 
               
            
           
           
               
               
               
            
               
                   
                 RT 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Emulsifier 
                 10° 
                 (20° 
                 30° 
               
            
           
           
               
               
               
               
               
               
            
               
                 No. 
                 Name 
                 Structure 
                 C. 
                 C.) 
                 C. 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 30% AGNIQUE 
                 Et—Hex—O-(PO) x - 
                 3.5 (PS) 
                   
               
               
                   
                 3551 comparative 
                 (EO) y -H 
               
               
                   
                 30% ANTAROX 
                 nBu—O-(PO) x - 
                 2.5 
               
               
                   
                 B/848 
                 (EO) y -H 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                   
                 20% ANTAROX 
                 nBu—O-(PO) x - 
                 3 
               
               
                   
                 B/848 
                 (EO) y -H 
               
               
                   
                 according to the 
               
               
                   
                 invention 
               
               
                   
                   
               
            
           
         
       
     
     Use Example II 
     Determination of the penetration properties of a formulation according to the above recipe. 
     This test measures the penetration of active compounds (a.i.) by enzymetically isolated cuticles from apple tree leaves. 
     Fully developed leaves cut from apple trees of the Golden Delicious variety are used. The cuticles are isolated by
         initially filling, by vacuum infiltration, leaf discs which had been marked on the underside with dye and punched out, with a pectinase solution (0.2 to 2% strength) buffered to a pH between 3 and 4,   then adding sodium azide and   allowing the leaf discs treated in this manner to stand until the original leaf structure has been dissolved and the non-cellular cuticles have been detached.       

     Subsequently, only the cuticles free from stomata and hairs of the upper sides of the leaves are used. They are washed repeatedly, alternating with water and a buffer solution of pH 7. The resulting clean cuticles are then mounted on Teflon plates and straightened and dried using a gentle stream of air. 
     In the next step, the cuticle membranes obtained in this manner are, for membrane transport studies, placed into diffusion cells (=transport chambers) made from stainless steel. To this end, the cuticles are, using a pair of tweezers, placed into the middle of the edges of the diffusion cells, which have been coated with silicone fat, and the cuticles are closed using a ring which had also been treated with fat. The arrangement is chosen such that the morphological outside of the cuticles is facing out, i.e. to the atmosphere, whereas the original inside is facing the inside of the diffusion cell. The diffusion cells are filled with water or a water/solvent mixture. 
     To determine penetration, in each case 5 μl of an active compound-comprising application liquor of the formulations mentioned below are applied to the outside of a cuticle. The active compound concentration corresponds to the outer application rate customary in practice. 
     In each case, tap water is used for the application liquors. 
     After the application of the application liquors, the water is in each case allowed to evaporate, and the chambers are then inverted and placed into thermostatic taps, where in each case air of a defined atmospheric humidity and temperature is blown onto the outside of the cuticles. Accordingly, the penetration that sets in takes place at a relative atmospheric humidity of 60% and a temperature adjusted to 25° C. Using an autosampler, samples are taken at regular intervals, and the content of penetrated active compound is measured. 
     The test results for various active compounds can be seen in the examples below. The stated numbers are average values of in each case 10 individual measurements. 
     Example I 
     Penetration of Acetamiprid (0.5 g of a.i./l) through Apple Leaf Cuticles 
       
     
       
         
           
               
               
             
               
                   
               
               
                   
                 Penetration 
               
               
                 Application liquor 
                 after 24 h (in %) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 a.i. in water 
                 61 
               
               
                 a.i. in water &amp; ANTAROX B/848 
                 100 
               
               
                 a.i. in water &amp; ANTAROX B/500 
                 100 
               
               
                 Comparative example 1: a.i. in water &amp; emulsifier 
                 82 
               
               
                 W (styrenated α-phenyl-ω-hydroxylpolyoxyethane- 
               
               
                 1,2-diyl, CAS 104376-72-9) 
               
               
                   
               
            
           
         
       
     
     Example II 
     Penetration of Compound A (0.5 g of a.i./l) through Apple Leaf Cuticles 
       
     
       
         
           
               
               
             
               
                   
               
               
                 Application liquor 
                 Penetration after 24 h (in %) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 a.i. in water 
                 2 
               
               
                 a.i. in water &amp; ANTAROX B/848 
                 49 
               
               
                 Comparative example 1: a.i. in water &amp; 
                 7 
               
               
                 emulsifier W (styrenated α-phenyl-ω- 
               
               
                 hydroxylpolyoxyethane-1,2-diyl, CAS 
               
               
                 104376-72-9) 
               
               
                   
               
            
           
         
       
     
     Example III 
     Penetration of Compound B (0.3 g of a.i./l) through Apple Leaf Cuticles 
       
     
       
         
           
               
               
             
               
                   
               
               
                 Application liquor 
                 Penetration after 24 h (in %) 
               
               
                   
               
             
            
               
                 Labor-EC &amp; ANTAROX B/848, 0.3 g/l 
                 23 
               
               
                 Labor-EC &amp; ANTAROX B/848, 0.6 g/l 
                 64 
               
               
                 Comparative example 1: Aqueous 
                 18 
               
               
                 application liquor consisting of 0.5 g/l 
               
               
                 of active compound BYI 02960, 0.5 g/l 
               
               
                 emulsifier W (styrenated α-phenyl-ω- 
               
               
                 hydroxylpolyoxy 
               
               
                 ethane-1,2-diyl, CAS 104376-72-9) and 
               
               
                 20 g/l dimethylacetamide 
               
               
                   
               
            
           
         
       
     
     Example IV 
     Penetration of Adjuvant-Comprising SL Formulations of Compound B (0.3 g of a.i./l) Through Apple Leaf Cuticles 
       
     
       
         
           
               
               
             
               
                   
               
               
                 Spray liquor 
                 Penetration after 24 h (in %) 
               
               
                   
               
             
            
               
                 SL 200 (2008-000189) with ANTAROX 
                 72 
               
               
                 B/848 (40%) 
               
               
                 Comparative example: SL 300 (without 
                 10 
               
               
                 adjuvant) 
               
               
                   
               
            
           
         
       
     
     More active compound was used in the comparative example than in the spray liquor according to the invention, so that an increased penetration would have been assumed for the comparative example. 
     Example V 
     Penetration of Compound B (0.5 g of a.i/l) through Apple Leaf Cuticles 
       
     
       
         
           
               
               
             
               
                   
               
               
                 Spray liquor 
                 Penetration after 24 h (in %) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 a.i. in water 
                 4 
               
               
                 a.i. in water &amp; ANTAROX B/848, 1 g/l 
                 48 
               
               
                 a.i. in water &amp; ANTAROX B/500, 1 g/l 
                 52 
               
               
                 Comparative example 1: 
                 13 
               
               
                 a.i. in water &amp; emulsifier W, 1 g/l 
               
               
                   
               
            
           
         
       
     
     Use Examples III 
     Determination of the retention of spray liquors. 
     Retention is to be understood as meaning the adherence of spray mists to surfaces, for example plants or plant parts (leaves), after spray application. The retention depends both on the composition of the spray liquor and on the nature of the treated surface. 
     Routinely, the retention of a spray liquor is determined using a poorly wettable leaf in comparison to a reference surface with 100% retention. The reported results were obtained using primary leaves of barley seedlings which had been cultivated in a greenhouse (18° C., 80% atmospheric humidity, 16 h of light). 
     Individual cut leaves are subjected to standard treatment in a spray cabin using a track sprayer—nozzle: XR 11002 VS; pressure: 3 bar; 300 l/ha. Weight and leaf area are determined prior to the treatment, and the adhering spray coating is correspondingly determined gravimetrically and normalized to the leaf area. A nonwoven-fabric paper cloth serves as reference surface for 100% retention with a precisely known area. 
     Per spray liquor variant, at least 5, better 8-10, individual leaves are treated, and the calculated retentions are then averaged. In general, a test series with pure tap water is carried out as negative control (lowest retention). 
     In such a comparative test, spray liquors with the additive ANTAROX B/848 (from Rhodia, chemical structure n-Bu-O-(PO) x -(EO) y -H) or AGNIQUE 3551 (from. Cognis, chemical structure 2-ethyl-hexyl-O-(PO) x -(EO) y -H) or AGNIQUE KE 3552 (from Cognis, chemical structure n-Oct-O-(PO) x -(EO) y -H) all gave excellent and, within the accuracy of the method, equal retention values. 
     This Test Series III confirms that, in spite of improved penetration and improved spontaneity, other properties, in particular retention, are not adversely affected. 
     Use Examples IV 
     Comparison of the Biological Activity 
     Translaminar Action of Compound B Against Myzus Persicae on Cabbage Leaves 
     Cabbage leaves are infected with a mixed population of the green peach aphid (Myzus persicae). Once the aphids have colonized the underside of the leaf, the plants are sprayed with the substances listed in the table using a bar sprayer such that only the upper side of the leaf is treated with insecticide (volume of water: 300 l/ha). The translaminar efficacy of the treatment against a mixed population of the green peach aphid in % mortality was determined at the stated points in time: