FR2645709A1 - EMULSIFIABLE SOLID PESTICIDE COMPOSITIONS - Google Patents

Abstract

The present invention describes solid emulsifiable pesticidal compositions obtained by heating and melting pesticides and at least one water-soluble polymer chosen from polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, in solid form at room temperature, with or without addition. surfactants, solvents and / or water-soluble supports for mixing them, and by solidification of the resulting mixture. The present invention also describes the process for the preparation of these compositions. The emulsifiable solid concentrates obtained are easy to handle and can be easily emulsified.

Description

The present invention relates to solid pesticide compositions

  emulsifiers which can be easily emulsified when diluted with water

at the time of use.

  Emulsifiable pesticide concentrates are uniform solutions obtained by dissolving pesticides and surfactants in organic solvents. Emulsifiable concentrates are general formulations that are easy to handle

  and can exhibit their effects stably.

  However, since the emulsifiable concentrates contain organic solvents in large quantities, they involve problems of environmental pollution, unpleasant odors, flammability, etc., due to the vaporization of the organic solvent. In addition, these formulations sometimes present, due to the solvents, problems such as

  phytotoxicity towards cultivated plants.

  To solve these problems, various researches have been done until now to transform emulsifiable concentrates into a pulverulent form. For example, a method is described which consists in absorbing an emulsifiable concentrate on supports such as starch, cellulose powders, urea, cork powder, mineral silicates, anhydrous gypsum type II, etc. In conventional techniques, however, problems are encountered that the absorption capacity of the emulsifiable concentrate on the supports is too low to prepare solid emulsifiable pesticidal compositions which have good fluidity, or that the attitude to emulsification is insufficient. when diluted with

1 water.

  In order to obtain excellent solid emulsifiable pesticidal compositions, the present inventors have carried out various researches and consequently they have obtained a process for the preparation of solid emulsifiable pesticidal compositions with good fluidity which can be easily emulsified, and therefore have been successful

O10 has the present invention.

  The present invention provides solid emulsifiable pesticidal compositions obtained by heating and melting pesticides with at least one water-soluble polymer, which is in solid form at room temperature (about 25 ° C.) and is chosen from

  polyethylene glycol, polyoxyethylene polyoxypropylene-

  glycol, polyoxyethylenepolyoxybutylene glycol and zolyoxvethylenepolyoxypropylenepolyoxybutylene glycol, in the presence or absence of surfactants, solvents and / or water-soluble supports, so as to

  mix, and by solidification of the resulting mixture.

  In general, it is difficult to solidify pesticides from a liquid form at room temperature. It is also difficult to solidify even pesticides that have melting points near room temperature. In addition, these pesticides present a problem of storage stability even when they are prepared in a solid form. According to the present invention, it is however possible to obtain excellent solid emulsifiable pesticidal compositions even if the pesticides have a

melting of 70'C or less.

  The term pesticide as used herein means not only a single compound but also includes mixtures of two or more compounds. In the case of a mixture, the present invention relates to a mixture having a melting point which is not greater than 'C. As the polyethylene glycol used in the present invention, mention may be made of polyethylene glycol having an average molecular weight of 1,000 or more; he is

  particularly suitable to use a polyethylene-

  glycol having an average molecular weight of 4000 to 000, from the standpoint of water solubility, etc. As polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight of 80% or folds in the molecule and having an average molecular weight of 1,000 or more is used.

  more in the propylene oxide part.

  As polyoxyethylene polyoxybutyleneglycol and as polyoxyethylene polyoxypropylene polyoxybutyleneglycol, those generally having an ethylene oxide weight of 80% or more in the molecule and having an average molecular weight of 1000 or more in the part are generally used.

  butylene oxide or in the propylene oxide part.

  What the term "solid form at room temperature" as used herein specifically refers to is the state in which the melting point is approximately

'C or more.

  Specific examples of water-soluble polymers such as polyethylene glycol include polyethylene glycols having an average molecular weight of 1,000, 4,000, 6,000, 10,000 and 20,000 (hereinafter called PEG-1000, PEG-4000, PEG-6000, PEG-10000 and PEG-20000 respectively); NEWPOLe PE-68 (manufactured by Sanyo

  Chemical Industries Co., Ltd .; polyoxyethylene polyoxy-

  propylene glycol which has an ethylene oxide weight of 80% in the molecule and which has an average molecular weight of 1,750 in the propylene oxide part), NEWPOL PE-78 (manufactured by Sanyo Chemical Industries Co., Ltd. ; polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight of 80% in the molecule and which has an average molecular weight of 2,050 in the propylene oxide part), NEWPOL PE-88 (manufactured by Sanyo Chemical

  Industries Co., Ltd .; polyoxyethylenepolyoxypropylene-

  glycol having an ethylene oxide weight of 80% in the molecule and having an average molecular weight of 2,250 in the propylene oxide part), NEWPOL PE-108 (manufactured by Sanyo Chemical Industries Co., Ltd .; polyoxyvethylenepolyoxypropylene glycol which has an ethylene oxide weight of 80% in the molecule and which has an average molecular weight of 3,250 in the propylene oxide part), etc. These water-soluble polymers can be used alone or in suitable mixtures. The water-soluble polymers can be used in sufficient quantity to take a solid form in the form of final preparation. That is to say, this amount is generally between 20 and 9% by weight, preferably between 50 and 90% by weight, relative to the

total weight of the composition.

  In the present invention, surfactants can also be used when fusing pesticides with water-soluble polymers. Examples of the surfactants that can be used include fatty acid and glycerin esters, fatty acid and sucrose esters, fatty acid and sorbitan esters, fatty acid salts, alkyl sulfates , salts of alkylbenzenesulfonic acids, alkyla.-nnium salts, quaternary ammonium salts, alkylarylethers and their polyoxyethylene products, adducts of ethylene oxide on higher alcohols; a polyoxyethylene polyoxypropylene glycol in liquid or pasty form at room temperature such as NEWPOL PE-64 (manufactured by Sanyo Chemical

  Industries Co., Ltd .; polyoxyethylenepolyoxypropylene-

  glycol having an ethylene oxide weight of 40% in the molecule and having an average molecular weight of 1,750 in the propylene oxide part), etc. These surfactants can be used alone or in an appropriate combination. The amount of surfactants added is generally between 0.1 and 20% by weight, preferably between 1 and 10% by weight, relative to the total weight of the composition. Surfactants which become liquid by heating and melting are preferred, but it is not always necessary to use such surfactants. It is sufficient that the surfactants dissolve in water when the preparation is diluted with water. When the melting point of a pesticide is between 0 and 70 ° C. or when the surfactants are in a chewy or solid state at room temperature, a small amount of solvent can also be added to the composition, if necessary and indicated, in order to reduce the viscosity during the preparation and to prevent the crystallization of pesticides in the composition when it is stored at low temperature. As the solvent, non-volatile solvents or low volatile solvents can be used. Examples of such solvents used to regulate the viscosity of the composition and prevent the crystallization of pesticides in the composition include vegetable oils, mineral oils, liquid paraffins, aromatic hydrocarbons, ketones, polyethylene glycols having an average molecular weight of 200 to 600 and being liquid at room temperature, polypropylene glycols and glycol ethers, etc. The amount of solvent added is generally between 10 and 1000% by weight, preferably between 30 and 200% by weight, relative to the pesticide. During the melting of the pesticides and the water-soluble polymer in the present invention, one can also add to the composition of the water-soluble supports. Examples of water-soluble carriers which can be used include water-soluble polymers such as hydroxypropylcellulose, sodium CMC, etc .; urea, lactose, ammonium sulfate, sucrose, sodium chloride, sodium sulfate decahydrate, etc. These water-soluble supports can be added in an appropriate amount such that the concentration of the supports in a spray mixture prepared by spraying is lower than the solubility limit of these supports.

in water.

  In addition to pesticides, surfactants, solvents and water-soluble supports, the solid emulsifiable pesticidal compositions according to the present invention can also suitably contain stabilizers, synergists, dyes, etc. However, mineral supports should not be added since the preparations are

  solid emulsifiable pesticide compositions.

  The solid emulsifiable pesticidal compositions of the present invention are used by dilution with water to the appropriate dilution order of magnitude. Special examples of pesticides

  can use in the present invention are given below

  below but the present invention should not be

  considered to be limited only to these examples.

  Compose No. Compound (1) 2- (4-Chlorophenyl) -3-methylbutyrate a-cyano-3phenoxybenzyl (2) (S) -2- (4-chlorophenyl) -3-methylbutyrate (S) -a-cyano3 -phenoxybenzyl (3) 2,2,3,3-Tetramethylcyclopropanecarboxylate acyano-3-phenoxybenzyl

  (4) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  3-phenoxybenzyl propanecarboxylate (5) 3phenoxybenzyl chrysanthemate

  (6) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  a-cyano-3-phenoxy-benzyl propanecarboxylate

  (7) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  a-cyano-3- (4-bromo-) propanecarboxylate

phenoxy) benzyl

  (8) 3- (2,2-Dichlorovinyl) -2,2-di = ethylcyvclo-

  a-cyano-3- (4-fluoro- propanecarboxylate)

phenoxy) benzyl

  (9) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  a-cyano-3- propanecarboxylate (3-bro "o-

phenoxy) benzyl

  (10) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  a-cyano-3- (4-chloro- propanecarboxylate)

  phenoxy) benzyl (11) α-cyano-3-phenoxybenzyl chrysanthemate (12) 2- (4Chlorophenyl) -3-methyl-butano-3- <4-bromophenoxy) benzyl benzyl (13) 2- (4-Chlorophenyl) A- (cyano-3- (3-bromophenoxy) benzyl (14) 2- (4-Chlorophenyl) -3-methyvlbutyrate a-cyano-3- (4chlorophenoxy) benzyl 2- (4) -A-cyano3- (4-fluorophenoxy) benzyl (16) 2- (4-Bromophenyl) -3-acyano-3-phenoxybenzyl (17) 2- (4-tert-Butylphenyl) chlorophenyl) -3-methylbutyrate> Acyano-3-phenoxybenzyl-3-methylbutyrate (18) 2- (3,4-! Ethylenedioxyphenyl) -3-α-cyano-3-phenoxybenzyl methylbutyrate

  (19) 3- (2,2-Dichlorovinyl) -2,2-dimethylcyclo-

  a-cyano- <4-fluoro-3- propanecarboxylate

phenoxy) benzyl

  (20) 2-Chloro-4-Ctrifluoromethyl) anilino-3-methyl-

  a-cyano-3-phenoxybenzyl (21) butyrate 2- (4-Difluoromethoxyphenyl) -3m-cyano-3-phenoxybenzyl (22) methylbutyrate (22) 3- (2,2-Dichlorovinyl) -2,2dimethylcyclo-

  cyano- (5-phenoxy-2- propanecarboxylate)

pyridyl) methyl

  (23) 2,2-Dimethyl-3- (1,2,2,2-tetrabromoethyl) -

  a-cyano-3-phenoxy- cyclopropanecarboxylate

benzyl

  (24) 2,2-Dimethyl-3- (1,2-dichloro-2,2-dibromo-

  a-cyano-3- ethyl) cyclopropanecarboxylate

phenoxybenzyl

  (25) 1- (4-Ethoxyphenyl) -2,2-dichlorocyclopropane-

  a-cyano-3-phenoxybenzyl carboxylate

  (20) 2,2-Dimethyl-3- (2-chloro-3-trifiuoromethyl-

  vinyl) a-cyano-3- cyclopropanecarboxylate

  phenoxybenzyl (27> 2- (4-ethoxyphenyl) -2-methylpropyl and 3phenoxybenzyl oxide

  (28) 3-phenoxybenzyl and 2- (4-ethoxy-

  phenyl) -3,3,3-trifluoropropyl (29) O, O-dimethyl and O- (3-methyl-4-nitrophenyl) phosphorothioate (30) O, O-dimethyl and S- phosphorothicate [1, 2-di4ethoxycarbonyl) -ethyl] (31) Phosphorothicate of O, Odimethyl and O- (4-cyanophenyl) (32) Phosphorodithioate of O, Odimethyl and S- (4-ethoxycarbonylbenzyl) (33) Phosphorothicate of O, Odiethyl and O- (2-isopropyl-4-methyv-6-pyrimidinyl (34) O, O-dimethyl and O-E3-methyl-4- (methylthio) phenyl phosphorothioate] (35) O-ethyl phosphorodithicate, O - (2,4-dichlorophenyl and S-npropyl

  (36) 0- (4-bromo-2,5-) phosphorodithioate

  dichlorophenyl and 0,0-diethyl

  (37) 2-Methoxy-4H-1,3,2-benzodioxaphospholine-

  2-sulfide (38) 0.0-diethyl and 0- (2,3-dihydro-3oxo-2-phenyl-6-pyridazyl) phosphorothioate (39) 0,0-dimethyl and 0 (2, 4,5-trichlorophenyl) (40) 0,0-diethyl and 0- (3,5,6-trichloro-2-pyridyle) phosphorothicate (41) 0,0-dimethyl and 0 (3,5 phosphorothioate , 6-trichloro-2-pyridyle)

  (42) 0- (4-bromo-2,5-dichloro- phosphorothicate)

  phenyle) and 0,0-dimethyl (43) Phosphorothicate of 0- (4-cyanophenyle), 0-ethyl and 0-phenyle (44) Phosphorodithioate of 0.0-dimethyl and S- (N-methylcarbamoylmethyl) (45 ) 2-secbutylphenyl N-methylcarbamate (46) 3-methylphenyl (47) N-methylcarbamate 3,4-dlmeethylphenyl (48) NMethylcarbamate (2) 2isopropoxyphenyl (49) N-methylcarbamate 5-Ethoxy-3-trichloromethyl-1,2 , 4-thiadiazole (50) 0, O-diisopropyl and S-benzyl phosphorothiolate (51) 0-ethyl and S, S-diphenyl dithiophosphate (52) Polyoxin (53) Blasticidine S (54) 3,4- Isopropyl dichloropropionanilide (55) N- (3-Chlorophenyl) carbamate (56) Ethyl di-n-propyl thiocarbamate (57) N- (3-Methylphenyl) carbamate 3-methoxycarbonylaminophenyl

  (58) 2-Chloro- (2,6-diethyl-N-methoxymethyl) -

acetanilide

  (5), a, a-Trifluoro-2,6-dinitro-N, N-dipropyl-

  p- toluidine (60) N ,, S- (4-chlorophenyl) methyl (61) N-Diethylthiolcarbamate (61) S-ethyl hexahydro-1H-azepine-1-carbothioate

  (62) N-Butoxymethyl-2-chlorc-2,6-diethyl-

  O-ethyl and Q- (5methyl-2-nitrophenyl) acetanilide (63) sec-Butylphosphoramidcthioate

  (64) N- (chloroacetyl) -N- ethyl ester (2,6-

  diethylphenyl) glycine These pesticides are generally contained at a rate of 1 to 80% by weight, preferably 10 to 40% by weight,

  relative to the total weight of the composition.

  The solid emulsifiable pesticidal compositions according to the present invention can be prepared, by

example, as follows.

  The solid emulsifiable compositions can be prepared by heating the water-soluble polymer in solid form at room temperature, for example

  polyethylene glycol or polyethylene polyoxypropylene-

  glycol, in a container at a temperature of 50'C or more, generally at 80-95'C; by adding pesticides and, if necessary and desired, surfactants, solvents and / or water-soluble carriers to the water-soluble polymer while stirring to mix them uniformly; spreading of the molten mixture thus obtained in a tank, on a glass plate, etc., and by cooling to solidify the product ;, by spraying then sieving. On a large preparation scale, the solid emulsifiable compositions can be obtained by spraying and solidifying the molten mixture described above in

  a room equipped with a cooling device.

  The invention will be described below in more detail with reference to the preparation examples and the test examples but should not be considered as their

being limited.

  In the following preparation examples, the

  parts are by weight unless otherwise indicated.

  Preparation example 1 90 parts of PEG-6000 are added to 10 parts of each of the compounds Nos. (1), (2), (3), (4), (5), (6), (31), (33), (46), (47), (48), (49) and (66 ) respectively. Each mixture is heated to 80 ° C to carefully melt and mix the components. The melted mixture is spread on a glass plate and cooled and solidified. Then the solid is ground and sieved at 1000-297 µm to obtain a composition

  solid emulsifiable pesticide in granular form.

  Preparation example 2 90 parts of NEWPOL PE-68 (above) are added to parts respectively of the compounds Nos. <2), (3), (4), (5), (6) and (31). Each mixture is heated to 80 ° C. to melt them and mix the components carefully. The molten mixture is spread on a glass plate, cooled and solidified. The solid is then ground and sieved at 1000-297 µm to give a solid emulsifiable pesticidal composition in granular form. Preparation example 3 40 parts of NEWPOL PE-68 (above) and parts of PEG-6000 are added to 10 parts respectively of the compounds Nos. (2), <3) and (31). Each mixture is heated to 80 ° C to melt and mix the components thoroughly. The molten mixture is spread on a glass plate, cooled and solidified. Then the solid is ground and sieved to 1000-297 gm to give a solid emulsifiable pesticidal composition in granular form. Preparation example 4 5 parts of SORPOL 355LSA (surfactants, manufactured by Toho Cemical Co., Ltd.) and PEG-6000 are added to, 20, 30 and 40 parts of compound No. (31) to make each time 100 parts. Each mixture is heated to 'C to melt and mix the components carefully. The molten mixture is spread on a glass plate, cooled and solidified. The solid is then ground and sieved at 1000-297 µm to give a solid emulsifiable pesticidal composition in granular form. Preparation example 5 20 parts of HISOL SAS-296 (solvent manufactured by Nippon Petrochemicals Co., Ltd.), 10 parts of SORPOL 3598 (surfactant manufactured by Toho Chemical Co., Ltd.) and 60 parts of PEG-6000 are added. to 10 parts respectively of the compounds Nos (2), (3), (4), (5), (6) and (29). Each mixture is heated to 80 ° C to melt and mix the components thoroughly. The molten mixture is spread on a glass plate, cooled and solidified. Then the solid is ground and sieved at 1000-297 pm, which gives a composition

  solid emulsifiable pesticide in granular form.

Preparation example 6

  60 parts of PEG-l000, PEG-4000, PEG- are added

  20000, NEWPOL PE-68 (see above Y, NEWPOL PE-78 (see above)> NEWPOL PE-88 (see above) or NEWPOL PE-108 (see above) with 10 parts of compound No . (3), 20 parts of HISOL SAS-296 (see above) and 10 parts of SORPOL 3598 (see above). Each mixture is heated to 80 ° C to melt and carefully mix the components. melted mixture

  on a glass plate, it is cooled and solidified.

  Then the solid is ground and sieved to 1000-297 gm to give a solid pesticide composition

  emulsifiable in granular form.

  Preparation example 7 90 parts of PEG-20000 are added to 10 parts of compound No. (3). The mixture is heated to 80 ° C to melt and mix the components carefully with each other. After the molten mixture has cooled to around 50 ° C, it is sprayed into a chamber cooled to -5 ° C and solidified, which gives a composition

  solid emulsifiable pesticide in granular form.

  Preparation example 8 80 parts of PEG-6000 are added to 20 parts of compound No. (1) and the mixture is heated to 80 ° C to melt and mix the components thoroughly with each other. The molten mixture is spread on a glass plate, cooled and solidified. Then the solid is ground and sieved at 1000-297 µm, which gives a solid emulsifiable pesticidal composition in granular form. Preparation example 9 60 parts of PEG-6000 are added to 10 parts of

  compound No. (3), 10 parts of HISOL SAS-296, (see below

  above) and 5 parts of SORPOL 3598 (see above) and the mixture is heated to 80 ° C to melt and mix the components carefully with each other. After addition to the reaction mixture and dispersion of 15 parts of lactose, urea or sodium sulphate decahydrate, the dispersion is spread on a glass plate, cooled and solidified. Then the solid is ground and sieved at 1000-297 ym, which gives a solid emulsifiable pesticidal composition in the form

granular.

  Comparative Example 1 90 parts of PEG-6000 powder are added to 10 parts of Nos (31), (33) and (34) respectively. We try to mix each mixture carefully in a mortar with a pestle. However, the resulting mixture is so sticky that no material can be obtained.

fluid product.

  Comparative Example 2 60 parts of PEG-20000 powder are added to 10 parts of compound No. (3), 20 parts of HISOL SAS-296

  (see above) and 10 parts of SORPOL 3598 (see above)

  above). We try to mix the mixture carefully in a mortar with a pestle. However, the resulting mixture is so sticky that you cannot get any

fluid product.

  Comparative Example 3 After adding 15 parts of lactose, urea or sodium sulphate decahydrate to 10 parts of compound No. (3), 10 parts of HISOL SAS-296 (see above), 5 parts of SORPOL 3598 (see above) and 60 parts of PEG-6000 powder, we try to mix

  carefully mix in a mortar with a pestle.

  However, the resulting mixture is so sticky that

  cannot get any fluid.

  Test example 1 100 mg of each of the emulsifiable solid pesticidal compositions in granular form obtained in Preparation Examples 1, 2 and 3 are introduced into 250 ml glass stopper test tubes which each contain 100 ml of hardness water. 3 (hard water at 53.4 ppm CaO>. The inversion of the test piece is repeated 30 times at the rate of 1 time per 2 seconds to emulsify. The granules dissolve completely in all the compositions. Then each test piece is kept for 15 minutes in a thermostats bath at 'C. to determine the stability of the emulsion In all cases, only a little oily "cream" is observed separately Test example 2 1 g of each of the pesticidal compositions is introduced emulsifiable solids in granular form obtained in Preparation Examples 4, 5 and 6 in 250 ml test tubes with glass stopper which each contain 100 ml of water of hardness 3 '. The inversion of the test tube is repeated. 30 times at the rate of 1 time per 2 seconds to emulsify. The granules are completely dissolved in all the compositions. Then each specimen is kept for 2 hours in a bath thermostatically controlled at 20 ° C. to determine the stability of the emulsion. In all cases, we observe only a few

separate oily "cream".

  Test example 3 1 g of each of the emulsifiable solid pesticidal compositions in granular form obtained in example of preparation 9 are introduced into 250 ml test tubes with glass stopper which each contain 100 ml of water of hardness 3 '. The inversion of the test piece is repeated 30 times at the rate of 1 time per 2 seconds to emulsify. The granules completely dissolve in all compositions. Then each specimen is kept for 2 hours in a bath thermostatically controlled at 20 ° C. to determine the stability of the emulsion. In all cases, we observe only a few

separate oily "cream".

  Reference Example An acute toxicity test is carried out to determine the LD 50 by oral administration of the solid emulsifiable pesticidal compositions of the present invention, obtained in Preparation Example 8 to male and female mice of the ICR strain aged 6.

weeks.

  Compared to an emulsifiable concentrate of conventional composition [this emulsifiable concentrate was prepared by mixing 20 parts of compound No. (1), 10 parts of SORPOL 30005X (surfactants manufactured by Toho Chemical CO., Ltd) and 70 parts of xylene ], we

  also determines the DL & o in a similar way.

  The results are given in the table below.

  LD = o (mg / kg) AT Mouse ni; L Female mouse Preparation example 8 1330 944 Classic emulsifiable concentrate 514 510 The solid emulsifiable pesticidal compositions according to the present invention are excellent preparations having good fluidity and having properties leading to a easy handling. Furthermore, the solid emulsifiable compositions can easily be emulsified when diluted with water.

Claims (3)

  1.- Process for the preparation of a solid emulsifiable pesticidal composition, which consists. heating and melting (a) a pesticide having a melting point which is not higher than 70 ° C, and (b) at least one water-soluble polymer yes is in solid form at room temperature and is chosen from the group comprising polyethylene glycol,   polyoxyethylene polyoxypropylene glycol, polyoxy-   ethylene polyoxybutylene glycol and polyoxyethylene   polyoxypropylenepolyoxybutyleneglycol, in the presence or absence of (c) a surfactant, a solvent and / or a water-soluble support,   and solidifying the resulting mixture.   2. A process for preparing an emulsifiable solid pesticidal composition according to claim 1, in which the amount of said water-soluble polymer is between 50 and 90% by weight relative to the weight total of the composition.   3.- Solid emulsifiable pesticide composition obtained   by a method according to claim 1.