GB2230954A - Preparation of emulsifiable pesticidal solid compositions - Google Patents

Abstract

An emulsifiable pesticidal solid composition is prepared by heating and melting a pesticide having a melting point of not higher than 70 DEG C and at least one water soluble polymer selected from polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxythylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, which is in a solid form at room temperature, optionally in the presence of a surfactant, solvent and/or water soluble carrier, and solidifying the resulting mixture. The resultant emulsifiable solid concentrate is easy to handle and can be readily emulsified.

Description

EMULSIFIABLE PESTICIDAL SOLID COMPOSITIONS The present invention relates to emulsifiable pesticidal solid compositions which can be readily emulsified, when diluted with water upon use.

Emulsifiable concentrates of pesticides are uniform solutions obtained by dissolving pesticides and surfactants in organic solvents. The emulsifiable concentrates are general formulations which are easy in handling and can stably exhibit their effects.

However, since the emulsifiable concentrates contain organic solvents in large quantities, problems of environmental pollution, malodor, inflammability, etc., due w2 vaporization of the organic solvent, are involved.

In acd tion, these formulations have sometimes such problems as phytotoxity to crops due the solvents.

To solve these problems, various investigations have seen hitherto made to make emulsifiable concentrates into powdery form. For example, there is reported a method which comprises absorbing emulsifiable concen onto onto carriers such as starch, cellulose powders, urea, zork powders, inorganic silicates, type II anhydrous gypsu, etc. In conventional techniques, however, these encounter problems that an absorbability of emulsifiable concentrate onto the carriers is too small to prepare emulsifiable pesticidal solid composition which has good flowability, or emulsifiability is insufficient when diluted with water.

In order to obtain excellent emulsifiable pesticidal solid compositions, the present inventors have made various investigations and as a result, they have found a process for preparing emulsifiable pesticidal solid compositions having good flowability which can be readily emulsified, and have accomplished the present invention.

That is, the present invention provides emulsifiable pesticidal solid compositions obtained by heating and melting pesticides together with at least one water soluble polymer, which is in a solid form at ambient or room temperature (ca. 250C) and is selected from polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, in the presence of or absence of surfactants, solvents and/or water soluble carriers to mix them and solidifying the resulting mixture.

In general, it is difficult to solidify pesticides in a liquid form at room temperature. It is also difficult to solidify even pesticides which have melting points around room temperature. In addition, these pesticides involve a problem in storage stability even if they are prepared into a solid form. According to the present invention, however, excellent emulsifiable pesticidal solid compositions can be obtained even if the pesticides have a melting point of 70"C or below.

The pesticide as used herein not only refers to a single compound but also include a mixture of two or more compounds. In the case of mixture, the present invention is directed to a mixture showing a melting point of not higher than 700C.

As polyethylene glycol used in the present invention, there is generally used polyethylene glycol having an average molecular weight of 1,000 or more; it is particularly preferred to use polyethylene glycol having an.average molecular weight of 4,000 to 20,000 from the viewpoint of water solubility, etc.

As polyoxyethylene polyoxypropylene glycol, there is generally used polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight of 80% or more in the molecule thereof and having an average molecular weight of 1,000 or more in the propylene oxide moiety.

As polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, there are generally used those having an ethylene oxide, weight of 80% or more in the molecule thereof and having an average molecular weight of 1,000 or more in the butylene oxide moiety or in the propyleneoxide moiety.

What is specifically meant by the solid form at room temperature as used herein refers to the state in which the melting point is approximately 300C or higher.

Specific examples of the water soluble polymer such as polyethylene glycol include polyethylene glycol having an average molecular weight of 1,000, 4,000, 6,000, 10,000 and 20,000 (hereinafter referred to PEG-1000, PEG-4000, PEG-6000, PEG-10000 and PEG-20000, respectively); NEWPOL PE-68 (manufactured by Sanyo Chemical Industries Co., Ltd.; polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight of 80% in the molecule thereof and having an average molecular weight of 1,750 in the propylene oxide moiety), NEWPOL PE-78 (manufactured by Sanyo Chemical Industries Co., Ltd.; polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight o SC in the molecule thereof and having an average molecular weight of 2,050 in the propylene oxide moiety), NEW PE-88 (manufactured by Sanyo Chemical Industries Cm., -d.; polyoxyethylene polyoxypropylene glycol having an ec > .-lene oxide weight of 80% in the molecule thereof and haing an average molecular weight of 2,250 in the propyiene oxide moiety), NEWPOL PE-108 (manufactured by Sanyo Chemical Industries Co., Ltd.; polyoxyethylene polyoxypropylene glycol having an ethylene oxide weight of 80% in the molecule thereof and having an average molecular weight of 3,250 in the propylene oxide moiety), and the like. These water soluble polymers may be used singly or as appropriate admixture thereof. The water soluble polymer may be used in an amount sufficient to take a solid form in the final preparation form. That is, the amount is generally in a range of 20 to 99 wt%, preferably in a range of 50 to 90 wt%, based on the total weight of the composition.

In the present invention, surfactants may also be used upon fusion of pesticides together with the water soluble polymers. Examples of such surfactants which can be used include glycerine fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, fatty acid salts, alkyl sulfates, alkylbenzene sulfonic acid salts, alkylammonium salts, quaternary ammonium salts, alkyl aryl ethers and polyoxyethylenated products thereof, ethvl oxide addition products of higher alcohol; pol-c: ethylene polyoxypropylene glycol in a liquid or paste -orm at room temperature such as NEWPOL PE-64 (man -~ctured by Sanyo Chemical Industries Co., Ltd.; poi--::-ethylene polyoxypropylene glycol having an ethj---:e oxide weight of 408 in the molecule thereof and having an average molecular weight of 1,750 in the proylene oxide moiety) , etc. These surfactants may be used singly or in a suitable combination. An amount of the surfactants added is generally in a range of 0.1 to 20 tl preferably in a range of 1 to 10 wt%, based on the total weight of the composition.Surfactants which become liquid by heating and fusion are preferred but it is not always necessary to use such surfactants.

It is sufficient that surfactants be dissolved in water when the preparation is diluted with water.

Where a melting point of pesticide is in a range of 0 to 700C or where surfactants are in a paste or solid form at room temeprature, a small quantity of solvent may also be added to the composition, if necessary and desired, for purposes of reducing a viscosity upon preparation and preventing crystallization of the pesticides in the composition when stored at a low temperature. As the solvent, non-volatile solvents or low volatile solvents are used. Examples of such solvents used to regulate the viscosity of the composition and prevent crystallization of pesticides in the composition include vegetable oil, mineral oil, liquid paraffin, aromatic hydrocarbons, ketones, plyethylene glycol which have an average molecular weight of 200 to 600 and are liquid at room tmperature, polypropylene glycol and glycol ethers, etc.An amount of the solvents added is generally in a range of 10 to 1000 wt%, preferably in a range of 30 to 200 wt%, based on the pesticide.

Upon fusion of pesticides and the water soluble polymer in the present invention, water soluble carriers may also be added to the composition. Examples of the water soluble carrier which can be used include water soluble polymer such as hydroxypropyl cellulose, sodium CMC, etc.; urea, lactose, ammonium sulfate, sucrose, sodium chloride, Glauber's salt, etc. These water soluble carriers may be appropriately added in such an amount that a concentration of the carriers in a spray mix prepared upon sprinkling is less than the solubility of these carriers in water.

In addition to pesticides, surfactants, solvents and water soluble carriers, the emulsifiable pesticidal solid compositions in accordance with the present invention may also appropriately contain stabilizers, synergists, coloring agents, etc.

However, mineral carriers should not be added, in view of the nature that the preparations are emulsifiable pesticidal solid compositions.

The emulsifiable pesticidal solid compositions in accordance with the present invention are used by diluting with water to a suitable dilution magnification.

Specific examples of the pesticides which can be used in the present invention are given below but the present invention is not deemed to be limited only to these examples.

Compound No. Compound (1) a-Cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutyrate (2) (S)-a-Cyano-3-phenoxybenzyl (S)-2-(4-chlrophenyl)-3-methylbutyrate (3) a-Cyano-3-phenoxybenzyl 2,2,3,3-tetra methylcyclopropanecarboxylate (4) 3-Phenoxybenzyl 3-(2,2-dichlorovinyl) 2,2-dimethylcyclopropanecarboxylate (5) 3-Phenoxybenzyl chrysanthemate (6) a-Cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate (7) a-Cyano-3-(4-bromophenoxy)benzyl 3- (2, 2-dichlorovinyl) -2, 2-dimethyl- cyclopropanecarboxylate (8) a-Cyano-3-(4-fluorophenoxy)benzyl 3- (2, 2-dichlorovinyl) -2, 2-dimethyl cyclopropanecarboxylate (9) a-Cyano-3-(3-bromophenoxy)benzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate 10) a-Cyano-3-(4-chlorophenoxy)benzyl 3- (2 ,2-dichlorovinyl) -2, 2-dimethyl- cyclopropanecarboxylate 11) a-Cyano-3-phenoxybenzyl chrysanthemate 12) a-Cyano-3-(4-bromophenoxy)benzyl 2- (4-chlorophenyl) -3-methylbutyrate 813) a-Cyano-3-(3-bromophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutyrate (14) a-Cyano-3-(4-chlorophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutyrate (15) a-Cyano-3-(4-fluorophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutyrate (16) a-Cyano-3-phenoxybenzyl 2-(4-bromophenyl)-3-methylbutyrate (17) a-Cyano-3-phenoxybenzyl 2-(4-tert butylphenyl) -3-methylbutyrate (18) a-Cyano-3-phenoxybenzyl 2-(3,4 methylenedioxyphenyl)-3-methylbutyrate (19) a-Cyano-(4-fluoro-3-phenoxy)benzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate (20) a-Cyano-3-phenoxybenzyl 2-chloro 4-(trifluoromethyl)anilino-3-methyl butyrate (21) a-Cyano-3-phenoxybenzyl 2-(4-difluoro methoxyphenyl)-3-methylbutyrate (22) Cyano-(5-phenoxy-2-pyridyl)methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate (23) a-Cyano-3-phenoxybenzyl 2,2-dimethyl 3-(1,2,2,2-tetrabromoethyl)cyclopropane carboxylate (24) a-Cyano-3-phenoxybenzyl 2,2-dimethyl 3-(1,2-dichloro-2,2-dibromoethyl)cyclo propanecarboxylate (25) a-Cyano-3-phenoxybenzyl 1- (4-ethoxy- phenyl) -2, 2-dichlorocyclopropane- carboxylate (26) a-Cyano-3-phenoxybenzyl 2,2-dimethyl 3-(2-chloro-3-trifluoromethylvinyl) cyclopropanecarboxylate (27) 2-(4-Ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (28) 3-Phenoxybenzyl 2-(4-ethoxyphenyl) 3,3, 3-trifluoropropyl ether (29) O,O-Dimethyl-O-(3-methyl-4-nitro phenyl)phosphorothioate (30) O,O-Dimethyl-S- [1,2-di(ethoxycarbonyl) - ethylj phosphorothioate (31) O,O-Dimethyl-O-(4-cyanophenyl) phosphorothioate (32) O,O-Dimethyl-S- (a-ethoxycarbonyl- benzyl) phosphorodithioate !33) O,O-Diethyl-O-(2-isopropyl-4-methyl 6-pyrimidinyl)phosphorothioate r21) O,O-Dimethyl-O-[3-methyl-4-(methyl- thio)phenyl3phosphorothioate ::25) O-Ethyl-O-(2,4-dichlorophenyl)-S- n-propylphosphorodithioate 36) 0- (4-Bromo-2,5-dichlorophenyl-O,O- diethylphosphorothioate (37) 2-Methoxy-4H-1,3,2-benzodioxa phospholine-2-sulfide (3S) O,O-Diethyl-O-(2,3-dihydro-3-oxo 2-phenyl-6-pyridazyl)phosphorothioate (39) O,O-Dimethyl-O- (2,4 ,5-trichloro- phenyl)phosphorothioate (40) O,O-Diethyl-O-(3,5,6-trichloro-2 pyridyl)phosphorothioate (41) O,O-Dimethyl-O-(3,5,6-trichloro-2 pyridyl)phosphorothioate (42) 0- (4-Bromo-2 , 5-dichlorophenyl) -0,0- dimethylphosphorothioate (43) 0- (4-Cyanophenyl) -O-ethyl-O-phenyl- phosphorothioate (44) O,O-Dimethyl-S-(N-methylcarbamoyl methyl)phosphorodithioate (45) 2-sec-Butylphenyl N-methylcarbamate (46) 3-Methylphenyl N-methylcarbamate (47) 3,4-Dimethylphenyl N-methylcarbamate (48) 2-Isopropoxyphenyl N-methylcarbamate (49) 5-Ethoxy-3-trichloromethyl-1,2,4- thiadiazole (50) O,O-Diisopropyl-S-benzyl phosphorothiolate (51) O-Ethyl-S,S-diphenyl dithiophosphate (52) Polyoxin (53) Blasticidin S (54) 3, 4-Dichloropropionanilide (55) Isopropyl N-(3-chlorophenyl)carbamate (56) Ethyl-di-n-propyl thiocarbamate (57) 3-methoxycarbonylaminophenyl N-(3-methylphenyl)carbamate (58) 2-Chloro-(2,6-diethyl-N-methoxy methyl)acetanilide (59) α;,α,α-Trifluoro-2,6-dinitro-N,N- dipropyl-p-toluidine (60) S-(4-Chlorophenyl)methyl-N,N diethylthiol carbamate (61) S-Ethylhexahydryl-lH-azepine-l carbothioate (62) N-Butoxymethyl-2-chloro-(2,6-diethyl acetanilide (63) O-Ethyl-O-(5-methyl-2-nitrophenyl) sec-butylphosphoramidothioate (64) N- (Chloroacetyl) -N- (2 ,6-diethyl- phenyi)glycine ethyl ester These pesticides are contained generally in a range f 1 to 80 wt%, preferably in a range of 10 to 40 wt-, ased on the total weight of the composition.

The emulsifiable pesticidal solid compositions in accordance with the present invention can be prepared, or =example, as follows.

The emulsifiable solid compositions can be prepared by heating the water soluble polymer in a solid form at room temeprature, e.g., polyethylene glycol or polyethylene polyoxypropylene glcyol, in a container at a temperature of 50CC or higher, generally at 80 to 95"C; adding pesticides and if necessary and desired, surfactants, solvents and/or water soluble carriers to the water soluble polymer while stirring to uniformly mix them; spreading the thus obtained melt mixture onto a vat, a glass plate, or the like and cooling to solidify; pulverizing and then sieving. In a larger scale of preparation, the emulsifiable solid compositions can be obtained by spraying and solidifying the melt mixture described above in a chamber equipped with a cooling apparatus.

[Examples] Hereafter the present invention is described in more detail by referring to the preparation examples and test examples but is not deemed to be limited only thereto.

In the following preparation examples, parts are all by weight, unless otherwise indicated.

Preparation Example 1 Ninety parts of PEG-6000 were added to 10 parts of Compound Nos. (1), (2), (3), (4), (5), (6), (31), (33), (46), (47), (48), (49) and (66), respectively.

Each mixture was heated to 800C to fuse and thoroughly mix them with each other. The melt mixture was spread onto a glass plate and cooled and solidified. Then, the solid was ground and sieved to 1000 to 297 pm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 2 Ninety parts of NEWPOL PE-68 (supra) were added to 10 parts of Compound Nos. (2), (3), (4), (5), (6) and (31), respectively. Each mixture was heated to 80"C to fuse and thoroughly mix them with each other.

The melt mixture was spread onto a glass plate and cooled and solidified. Then, the solid was ground and sieved to 1000 to 297 pm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 3 Forty parts of NEXPOL PE-68 (supra) and 50 parts of PEG-6000 were added to 10 parts of Compound Nos. (2), (3) and (31), respectively. Each mixture was heated to 800C to fuse and thoroughly mix them with eacn other. The melt mixture was spread onto a glass plat and cooled and solidified. Then, the solid was groura and sieved to 1000 to 297 Vm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 4 Five parts of SORPOL 355LSA (surfactants, manufactured by Toho Chemical Co., Ltd.) and PEG-6000 were added to 10, 20, 30 and 40 parts of Compound No.

(31) to make up 100 parts, respectively. Each mixture was heated to 800C to fuse and thoroughly mix them with each other. The melt mixture was spread onto a glass plate and cooled and solidified. Then, the solid was ground and sieved to 1000 to 297 çm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 5 Twenty 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 were added to 10 parts of Compound Nos. (2), (3), (4), (5), (6) and (29), respectively. Each mixture was heated to 800C to fuse and thoroughly mix them with each other. The melt mixture was spread onto a glass plate and cooled and solidified.

Then, the solid was ground and sieved to 1000 to 297 pm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 6 Sixty parts of PEG-1000, PEG-4000, PEG-20000, NEXPOL PE-68 (supra), NEWPOL PE-78 (supra), NEWPOL PE-88 (supra) or NEWPOL PE-108 (supra) were added to 10 parts of Compound No. (3), 20 parts of HISOL SAS-296 (supra) and 10 parts of SORPOL 3598 (supra). Each mixture was heated to 800C to fuse and thoroughly mix them with each other. The melt mixture was spread onto a glass plate and cooled and solidified. Then, the solid was ground and sieved to 1000 to 297 Vm to give an emulsifiable pesticidal solid composition in a granular form.

Preparation Example 7 Ninety parts of PEG-20000 were added to 10 parts of Compound No. (3). The mixture was heated to 800C to fuse and thoroughly mix them with each other.

After the melt mixture was cooled to about 50"C, the mixture was sprayed in a chamber cooled to -5 C and solidified to give an emulsifaible pesticidal solid composition in a granular form.

Preparation Example 8 Eighty parts of PEG-6000 were added to 20 parts of Compound No. (1) and the mixture was heated to 800C to fuse and thoroughly mix them with each other. The melt mixture was spread onto a glass plate and cooled and solidIfied. Then, the solid was ground and sieved to 1000 to 5 m to give an emulsifiable pesticidal solid compo sition in a granular form.

Preparation Example 9 Sixty parts of PEG-6000 were added to 10 parts o wound No. (3), 10 parts of HISOL SAS-296 (supra) and D -r-s of SORPOL 3598 (supra) and the mixture was heated to SO0C to fuse and thoroughly mix them with each other.

After 15 parts of lactose, urea or Glauber's salt were added to the melt mixture to disperse, the dispersion was spread onto a glass plate and cooled and solidified.

Then, the solid was ground and sieved to 1000 to 297 pm to give an emulsifiable pesticidal solid composition in a granular form.

Comparative Example 1 Ninety parts of PEG-6000 powders were added to 10 parts of Compound Nos. (31), (33) and (34), respectively. Each mixture was attempted to thoroughly mix in a mortar with a pestle. However, the resulting mixture was extremely sticky so that any fluidizable product was not obtained.

Comparative Example 2 Sixty parts of PEG-20000 powders were added to 10 parts of Compound No. (3), 20 parts of HISOL SAS-296 (supra) and 10 parts of SORPOL 3598 (supra). The mixture was attempted to thoroughly mix in a mortar with a pestle. However, the resulting mixture was extremely sticky so that any fluidizable product was not obtained.

Comtarative Example 3 After 15 parts of lactose, urea or Glauber's salt ere added to 10 parts of Compound No. (3), 10 parts of HISOL SAS-296 (supra), 5 parts of SORPOL 3598 (supra) and 60 parts of PEG-6000 powders, the mixture was attempted to thoroughly mix in a mortar with a pestle. However, the resulting mixture was extremely sticky so that any fluidizable product was not obtained.

Test Example 1 Hundred milligrams of each of the emulsifiable pesticidal solid compositions in a granular form produced in Preparation Examples 1, 2 and 3 were charged in 250 ml glass stoppered cylinders, each of which contained 100 ml of 30 hard water (53.4 ppm hard water as CaO).

Inversion of the cylinder was repeated 30 times at a rate of once per 2 seconds to emulsify. The granules were fully dissolved in all of the compositions. Then, each cylinder was kept for 15 minutes in a thermostat at 20"C to examine stability of the emulsion. In any case, isolated oil cream was hardly observed.

Test Example 2 One gram of each of the emulsifiable pesticidal solid compositions in a granular form produced in Preparation Examples 4, 5 and 6 was charged in 250 ml glass stoppered cylinders, each of which contained 100 ml of 30 hard water. Inversion of the cylinder was repeated 30 times at a rate of once per 2 seconds to emulsify.

The granules were fully dissolved in all of the compositions. Then, each cylinder was kept for 2 hours in a thermostat at 200C to examine stability of the emulsion.

In any case, isolated oil cream was hardly observed.

Test Example 3 One gram of each of the emulsifiable pesticidal solid composition in a granular form produced in Preparation Example 9 was charged in 250 ml glass stoppered cylinders, each of which contained 100 ml of 30 hard water. Inversion of the cylinder was repeated 30 times at a rate of once per 2 seconds to emulsify.

The granules were fully dissolved in all of the compositions. Then, each cylinder was kept for 2 hours in a thermostat at 200C to examine stability of the emulsion.

In any case, isolated oil cream was hardly observed.

Reference Example Acute toxicity test was performed to determine LD50 value by orally administering the emulsifiable pestlcidal solid composition in accordance with the present invention, produced in Preparation Example 8, to ICE strain male and female mice of 6 week old.

With respect to an emulsifiable concentrate having a conventional formulation [The emulsifiable concentrate was prepared by mixing 20 parts of Compound No. ,), 10 parts of SORPOLs 3005X (surfactants, manu factred by Toho Chemical Co., Ltd.) and 70 parts of sie3;, LD50 value was also determined in a similar manner.

The results are shown in the table below.

LD50 value (mg/kg) Male Mouse Female Mouse Preparation Example 8 1330 944 Conventional emulsifiable 514 510 concentrate The emulsifiable pesticidal solid compositions in accordance with the present invention are excellent preparations showing good flowability and having properties enabling to easy handling. In addition, the emulsifiable solid compositions can readily be emulsified when diluted with water.

Claims (4)

CLAIMS:

1. A process for preparing an emulsifiable pesticidal solid composition which comprises heating and melting (a) a pesticide having a melting point of not higher than 700C, and (b) at least one water soluble polymer which is in a solid form at room temperature and is selected from the group consisting of polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, in the presence of or absence of (c) a surfactant, a solvent and/or a water soluble carrier, and solidifying the resulting mixture.

2. A process according to claim 1, wherein the said water soluble polymer is present in an amount within a range of from 50 to 90 wt% inclusive based on the total weight of the composition.

3. A process according to claim 1 or claim 2, which process is substantially as herein described and exemplified.

4. An emulsifiable pesticidal solid composition whenever produced by a process according to any preceding claim.