LU82279A1 - DEVICES FOR THE EMISSION OF INSECTICIDE VAPORS - Google Patents

Description

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Case 2- / AFR 114

DEVICES FOR THE EMISSION OF INSECTICIDE VAPORS

The present invention relates to formulating devices usable in or on a heating appliance and intended for the emission of insecticidal vapors.

It is known to use heat to evaporate insecticidal substances into the atmosphere, either through the combustion of a hydrocarbon gas (British patent 1366041), or through an electric bulb (French patents 921852 and 986269), or through to an electrical device specially designed for this use (British patents 1,379,782, 1,249,032 and 2,003,034; Spanish patent 245,083; French patents 1,092,141, 1,165,348 and 2,054,435; Italian patent 713,459).

The systems suitable for this use use solid compositions comprising one or more active substances impregnating a mass absorbent material; such compositions are described in the patents cited above and in various others (French patent 2201832; Japanese applications 7377020, 7466823 and 76133426).

These compositions generally comprise only one active substance.

However, it is often interesting to combine the action of several active substances because they can mutually reinforce their action or have different actions and thus form an association with a wider spectrum of effectiveness.

- 2 -

When it is necessary to combine several active substances, it naturally comes to mind to put them together in the same composition. The Applicant has discovered that the effectiveness of combinations of active substances is higher when these active substances are distributed separately and in a juxtaposed manner in the absorbent materials rather than in a mixture.

The invention therefore relates to a device intended for the emission of insecticidal vapors and usable in or on a heating device, characterized in that it consists of several different solid compositions juxtaposed each comprising an active substance on insects absorbed in a material absorbent mass, said active substance being, in at least one of the compositions, chosen from pyrethroids.

One or more of said compositions may optionally contain an inert adjuvant chosen from diluents, thickening agents, perfumes, synergists, dyes, stabilizers, attractants and insect repellents.

When all the compositions do not each contain an active substance chosen from pyrethroids, this can, for example, be chosen from synergists, insect repellents, insect attractants and known insecticidal compounds other than pyrethroids .

An insecticidal compound other than pyrethroid can be, for example, an organochlorine compound whose vapor pressure at 25 ° C is greater than 1.10 ^ torr or an organophosphorus compound whose vapor pressure at 25 ° C is greater than 5.10 ^ torr.

As nonlimiting examples of suitable organochlorine compounds, mention may be made of hexachlorocyclohexane and its gamma isomer known under the name of lindane, chlordane and heptachlor.

As nonlimiting examples of suitable organophosphorus compounds, it can. be cited dichlorvos, carbophenothion methyl, trichlormetafos-3, fenchlorphos, demethion, phorate, dëmëton-methyl, naled or dibrome, chlorthion, thiometon, dëmêton, chlorméphos, pirofos, acetofos-methyl, bromophos, dichlorfenthion, acetofos, mevinphos and, more generally, the compounds cited in French patent 2292430 of Ciba Geigy AG.

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Among the pyrethroids which can be used as active substance, there may be mentioned in particular the esters formed between a cyclopropanecarboxylic acid such as tetra-methyl-2,2,3,3 cyclopropane carboxylic acid, or chrysanthemic acid or acids (butano-2 , 2 or dibromo-2,2 or dichloro-2,2 or difluoro-2. ,, 2 ... vinyl) -3 dimethyl “2,2 cyclopropanecarboxyliques, in their racemic or resolved forms (d and / or 1, cis and / or trans) and the following alcohols: 3-ethyl-2-methyl-4-oxo-2-cyclopentene-ol 3-methyl-2-oxo-4-cyclopentene-2-ol methal'.-3-methyl-2-oxo-4 cyclopentene-2 ol crotyl-3 methyl-2 oxo-4 cyclopentene-2 ol (3-methyl-propene-2 yl) -3 methyl-2 oxo-4 cyclopentene-2 ol '(2-chloro allyl) -3 methyl-2 oxo-4 cyclopentene-2 ol (chloro-3 allyl) -3 methyl-2 oxo-4 cyclopentene-2 ol furfuryl-3 methyl-2 oxo-4 cyclopentene-2 ol phenyl-l propyne-2 ol (chloro-3 phenyl ) -l propyne-2 ol.

(3-fluoro-phenyl) -l propyne-2 ol (trifluoromethyl-3 phenyl) -l propyne-2 ol (thienyl-2) -1 propyne-2 ol (furyl-2) -l propyne-2 ol phenyl-4 butene -2 ol (3-methylphenyl) -4 butene-2 ol (2-methylphenyl) -4 butene-2 ol (2,3-dimethylphenyl) -4 butene-2 ol (2-methoxyphenyl) -4 butene -2 ol - (2-chloro-phenyl) -4 butene-2 ol (3-chloro-phenyl) -4 butene-2 ol (2,3-dichloro phenyl) -4 butene-2 ol (bromo-3 phenyl) -4 butene-2 ol, phenyl-4 butyne-2 ol (furyl-2) -4 butyne-2 ol (thienyl-2) -4 butyne-2 ol methyl-5 hexene-5 yne-2 ol methyl-5 hexadiene- 2,5 ol - 4 - dimethyl-5j6 heptene-5 yne-2 ol 2-methyl benzyl alcohol 3-methyl alcohol benzyl 4-methyl alcohol benzyl 2,3-dimethyl alcohol benzyl 2,4-dimethyl benzyl alcohol 2-dimethyl alcohol , 5 benzyl 2,6-dimethyl alcohol benzyl 3,4-dimethyl alcohol benzyl 3,5-dimethyl alcohol benzyl 2,4,6-trimethyl alcohol benzyl 4-allyl benzyl benzyl 4-allyl-2,6-dimethyl benzyl methallyl alcohol -4 benzyl alcohol '(butene-3 yl) -4 benzyl alcohol vinyl-4 benzyl alcohol cyano-4 benzyl alcohol trifluoromethyl-4 benzyl alcohol nitro-4 benzyl alcohol methyl-3 furfuryiic alcohol methyl-5 furfuryiic alcohol 3,5-dimethyl furfuryiic alcohol dimethyl-4,5 furfuryiic alcohol allyl-5 furfuryiic 5-propargyl furfuryic alcohol (2-methyl furyl-3) alcohol methyl alcohol (2,5-dimethyl furyl-3) methyl alcohol (2,4-trimethyl furyl-3) methyl alcohol (5-allyl furyl-3) methyl - alcohol (5-allyl-2-methyl-furyl-3) methyl alcohol (methyl-2-propargyl-5 furyl-3) methyl.

- 5 - té trahydroph talimidomé thano1 (benzyl-5 £ uryl-3) methanol (alphacyanobenzyl-5 furyl-3) methanol (alphamethynylbenzyl-5 furyl-3) methanol phenoxy-3 benzyl alcohol phenoxy-3 alphacyanobenzyl alcohol phenoxy-3 alphamethynylbenzyl

These esters include in particular the substances known under the names of allethrin, bioallethrin, S-bioallethrin, kinin, furethrin, dimethrin, benathrin, kadethrin, prothrin (or furamethrin), proparthrin, tetramethrin, resmethrin, bioresmethrin, phenothrin, pheniorine permethrin, biopermethrin, cypermethrin, bromethrine, decamethrin and fluorethrin.

The synergists when there is at least one in one of the compositions, are chosen from benzodioxoles, polychlorinated ethers and N-alkyl-5-dicarboximides-2,3.

Suitable benzodioxoles are, for example, safrole, isosafrole, cyano-5-benzodioxole-1,3, 5-ethynyl-benzodioxole-1,3, 5-hydroxymethyl-benzodioxole-1,3, cyanomethyl- 5 1,3-benzodioxole, 5,6-dichloro-1,3 benzodioxole, 5-chloro-6 cyano-6 benzodioxole-1S, 5-bromo-6-cyano-1,3-benzodioxole, 5-chloro-6 cyanomethyl benzodioxole-1,3, chloro-5 hydroxy-6 benzodioxole-1,3, chloro-5 hydroxymethyl-6 benzodioxole-1,3, chloro-5 ethynyl-6 benzodioxole-1,3 ,.

Suitable polychlorinated ethers are, for example, octachloro-1,1,1, 2,6,7,7,7 oxa-4 heptane and hexachloro-l, 1,2,6,7,7 oxa-4 heptadiene-1,6.

Suitable 2,3-N-alkylnorbornene-2,3-dicarboximides are, for example, those in which the alkyl residue is an isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methyl butyl, isohexyl, 2-methyl hexyl, ethyl- 2 butyl or isodecyl.

’-6-.

The insect attractants, when there is at least one in one of the compositions, are chosen from all those known to a person skilled in the art such as, for example, fruit flavors, caramel, cheese flavors , meat, amino acids, pollen extracts, thymol, skatole, indole, engenol, paraformaldehyde, hexamethylene tetramine, ammonium carbamate, aliphatic amines, papain, pancreatin, aliphatic acids, vanillin, 3-chloro-3-methyl-butene-1, 1-chloro-3-methyl-butene-2 and heavy alkenes containing 20 to 27 carbon atoms such as (cis) -tricosene-9 .

Insect repellents, when there is at least one in one of the compositions, are, for example, dialkyl succinates, malleates and fumarates, alkyl mandelates, Ν, Ν-dialkylbenzamides and toluamides, cyclopropane earbonamides, alkanoyl-1 to hexahydrobenzofurans, alkanoates of dioxa-3,6 decyl, citronellal and its dialkylacetals and alkylhexane-diols.

The diluents, when there is at least one in one of the compositions, are chosen from liquid or solid organic compounds having a solvent power with respect to the insecticidal compound. The diluents used preferably have a vapor pressure at least equal to that of the active substance which accompanies it; better still, this vapor pressure is higher than that of the active substance.

Among the suitable diluents, mention may in particular be made of those chosen from the following chemical families: 1) The monoesters formed between the alkanols and the monocarboxylated hydrocarbons such as, for example, alkyl acetates such as those of hexadecyl or octo -decyl, butyra'tes and alkyl isobutyrates such as those of dodecyle, tetradecyl, hexadecyle or octadecyle, alkyl hexanoates, alkyl octanoates, alkyl decanoates, laurates, undecanoates, undecênoates and alkyl myristates such as those of hexyl, octyl, decyl or dodecyl, palmitates oleates and alkyl stearates such as those of propyl, butyl, isobutyl, amyl, of hexyl or octyl and alkyl benzoates, phenylacetates and phenylpropionates such as those of hexyl, octyl, decyl or dodecyl.

2) The diesters formed between the alkanols and the dicarboxylated hydrocarbons such as, for example, dialkyl adipates such as dioctyl adipate, dinonyl adipate, didecyl adipate and didodecyl adipate, dialkyl sebacates such as dibutyl sebacate, dipentyl sebacate? dioctyl sebaçate, didecyl sebaçate, dialkyl azelates such as dioctyl azelate and dideeyl azelate, dialkyl phthalates such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis (undecyl) phthalate, bis (dodecyl) phthalate, bis (tridecyl) phthalate, bis (tetradecyl) phthalate and diketyl phthalate.

3) Diesters formed between phenols, substituted or unsubstituted alkyls and dicarboxylated hydrocarbons such as, for example) diaryl phthalates such as diphenyl phthalate and dicresyl phthalates, 4) Diesters formed between cycloalkanols, alkylsubstituted or unsubstituted substituted, and dicarboxylated hydrocarbons such as, for example, dicyclohexyl phthalate, bis (methylcyclohexyl) phthalates, bis (trimethylcyclohexyl) phthalates and bis (tetramethylcyclohexyl) phthalates, 5) The diesters formed between phenylalkanols and dicarboxylated hydrocarbons such as, for example, dibenzyl sebacate. dibenzyl azelate and bis (phenylpropyl) sebacates, 6) The diesters formed between the alkanediols and the monocarboxylated hydrocarbons such as, for example, 2,2,4 trimethyl diisobutyrate, 1,3) triesters formed between phenols, substituted or unsubstituted alkyls, and phosphoric acid such as, for example, triphenyl phosphate, tris phosphate (4-terbutylphenyl) and tricresyl phosphates, 8) Triesters formed between alkanols and phosphoric acid such as, for example, trioctyl phosphate, tridecyl phosphate and tricodecyl phosphate, 9) Polyalkylene glycols such as, for example, polyethylene glycols and polypropylene glycols, -δ- 10) Fatty alcohols, for example, hexadecanol, octadecanol and octadecene-9 ol, 11) Fatty acids such as, for example, lauric, myristic, palmitic, stearic and oleic acids, 12) Alkanes containing at least 18 atoms of carbon, like, for example, the o ctadecane, eicosane, docosane and tetracosane, and their mixtures known as petrolatum oil, paraffin oil, heavy oil, diesel, fuel oil, road oil, valve oil, fuel oil, petrolatum, petrolatum, gatsch, paraffin, microwax, ozocerite and ceresin, 13) Alkanones containing at least eighteen carbon atoms such as, for example, caprinone, laurone, myristone, palmitone and stearone, 14) Alkenones containing at least eighteen carbon atoms such as, for example, heneicosadiene-1.20 one-11 and oleone.

The thickening agents are, for example, metal salts of fatty acids, such as aluminum or magnesium mono-, di- and tri-stearates, or salts of fatty acids and amines, such as dioleate 'hexadecylaminopropylene-amine, octadecyl-aminopropylene-amine or octadecenylaminopropylene-amine, or modified montmorillonites, such as ammonium salts of dimethyldi- (heavy alkyl) -bentonite.

The stabilizers, when there is at least one in one of the compositions, are chosen from all those known to those skilled in the art such as, for example, phenolic compounds such as resorcinol, pyrogallol, hydroquinone, 2-tertiobutyl-4-methoxyphenol and 2,6-ditertiobutyl-4-methyl-phenol, bisphenolic compounds such as bis (hydroxyphenyl) ethane, bis (hydroxyphenyl) methane, bis (hydroxyphenyl) propane, bis (tertiobutyl-3 5-ethyl-2-hydroxyphenyl) methane and bis (tert-butyl-3-hydroxy-4-phenyl) methane and 0,0-dialkyl (hydroxybenzyl) phosphonates such as 3,5-hydroxy (3,5-ditertiobutyl-benzyl) 0,0-diethyl phosphonate.

• * ·! *! - 9 - to

The absorbent mass materials can be chosen from cellulose paper and cardboard composed of wood fibers, cereal fibers, alfa fibers, cotton fibers, waste paper, asbestos fibers, fibers of glass, wool fibers and / or polymeric fibers and among the terracotta, sintered aluminas and non-stretched porcelain.

The material constituting the bulk material can also contain fillers chosen from organic powders, mineral powders, pigments, dyes and binders.

Mass materials can adopt all known forms such as those of plates and blocks.

The plates can be any round, oval, square, rectangular, triangular, or polygonal, their total surface area being as few as a few square centimeters as several square decimetres and their thickness can vary from 0.1 to 6 millimeters.

The blocks can be cubic, prismatic, cylindrical, of elliptical cross section or any polyhedral, their total surface being able to vary from a few square centimeters only to several square decimetres.

A solid composition according to the invention is obtained by impregnating the absorbent mass material with the liquid mixture of the other constituents of the composition (active substance and optionally adjuvants). The impregnation can be done by pouring the liquid mixture onto the absorbent material or by soaking the latter in the liquid, the soaking possibly being followed by a wringing; this operation can be mechanized by using, for example, a metering pump or a constant rate spray boom; it is also possible to use a roller wringer with a pressure adjusted so as to allow the retention of liquid in the desired proportion; you can also use a centrifugal wringer at a set speed for the same purpose.

An industrially interesting method of impregnation consists, for example, in the use of strips of great lengths, impregnated continuously and then cut to the desired dimensions. Impregnation can also be carried out by placing the absorbent material under vacuum in the presence of the liquid mixture.

- 10 - Impregnation can also be carried out automatically by a machine comprising one or more injection syringes and a conveyor belt making the absorbent materials to be impregnated beneath them. It is also possible to use a solution of the liquid mixture in a volatile solvent, the latter then being evaporated.

The solid compositions constituting the device are preferably two in number or three. They can be simply placed close to each other without physical means of joining or, on the contrary, constitute a united whole.

When the device is a single unit, the solid compositions can be bonded by any known means such as an adhesive, a cement or a stapling, nailing, embedding or metallic or plastic crimping system.

The device can also consist of a single absorbent mass material in which the active ingredients chosen have been absorbed, separately, and each in a separate zone, possibly accompanied by an inert adjuvant.

In this case, an area of the bulk material can be left without impregnation so as to constitute a separation between the active materials; it is also possible to establish in this zone, an impenetrable barrier by means of a prepreg with a material having the function of eliminating the absorbent state of the conventional material.

A barrier can thus be formed, for example, by means of a vegetable, animal, paraffinic or isoparaffinic wax, deposited in the liquid state at the place where the barrier must be produced; the wax is absorbed in the liquid state and forms, after cooling, an impassable separation for the active ingredients.

Another material which can be used to make a barrier consists, for example, of an alkaline silicate in concentrated aqueous solution and then dried.

Likewise, a solution of natural or synthetic resin in a volatile solvent can be used which is then removed by drying.

'- 11 -

A particularly advantageous method consists in creating the insitu barrier using a polymerizable material chosen from monomers, prepolymers and combinations of compounds capable of reacting with each other to give polymeric resins.

As monomers of interest, it may be mentioned, in particular, styrene, methyl acrylate, ethyl acrylate, dimethyl, diethyl, dipro-pyle and dibutyl maleates and cyanacrylic esters.

The prepolymers are chosen, for example, from polyesters such as those formed between dicarboxylic acids, such as adipic, sebacic, azelaic, maleic, phthalic or tetrahydrophthalic acids, and polyols such as, ethylene and propylene glycols, polyethylene and polypropylene glycols, glycerol and pentaerythrol.

When a monomer or a prepolymer is used, it is possible to favorably add thereto an accelerator and / or a polymerization catalyst at the time of the treatment of the absorbent bulk material or, better still, bring this accelerator and / or catalyst separately to the zone treated before, during or after treatment.

Mention may in particular be made, as accelerator, of the cobalt or vanadium salts and the dialkylanilines; as polymerization catalyst, there may be mentioned in particular the carboxylic peracids / their esters and their salts and the acyl, alkyl, cumene or ketone.

To promote the polymerization, it is also possible to operate at a temperature higher than the ambient such as, for example, between 40 and 80 ° C. during the treatment or to subject the treated area to this temperature after the treatment. It is also possible to subject the treated area to infrared radiation, ultra violet radiation, ultrasound, microwaves or gamma rays.

Of course, combinations of several prepolymers or prepolymer (s) and monomer (s) can be used to give particular characteristics to the polymers formed.

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As associations of compounds capable of reacting with one another, there may be mentioned, in particular, those leading to the formation of epoxy, epoxy-ester and epoxy-phenolic type resins, those leading to the formation of aminoresins such as urea-formaldehyde or melamine resins -formol and those leading to the formation of polyurethane resins.

The mixing of these compounds can be done just before application to the absorbent mass material; it is also possible to deposit each of the compounds at the same time or in turn on said material so as to allow the mixture to be carried out in situ.

The devices according to the invention have the advantage, with equal quantities of materials and under the same heating conditions, of providing insecticidal vapors more effective than those emitted by known devices in which the active substances used are mixed in one composition.

A particular feature of the devices according to the invention is that it makes it possible to choose, for each of the solid compositions, an evaporation surface in relation to the active substance present and therefore to allow the quantity, evaporated of each of the active substances, to be adjusted separately.

Another particular feature of the devices according to the invention is to allow, using a suitable heating appliance, heating of each of the solid compositions to a different temperature in relation to the active substance present and therefore to allow, here too, to regulate separately the amount of substance evaporated from each of the active substances.

The advantage of the devices according to the invention is illustrated by the experiments which follow.

... / ...

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Experiment 1

Two devices 1-A and 1-B were prepared having the same total surface and using the same absorbent mass material. The device 1-A consisted of two different compositions 1-A 'and 1-A "juxtaposed and assembled by metal staples; the device 1-B consisted of a single homogeneous composition containing all the constituents of the compositions 1-A 'and 1-A ".

^ The details of these devices are specified below: ~ t. rr ^ 1-A ’

Allethrin 50 mg - 50 mg

Tetramethrin - 50 mg 50 mg Dioctyl sebacate 75 mg - 75 mg

Stabilizer (a) - 20 mg ’20 mg, Cellulose 880 mg 1760 mg 2640 mg

Surface 714 mm2 1428 mm2 2142 mm2

Length 34 mm 42 mm 63 mm

Width 21 mm 34 mm 34 mm

Thickness 3 mm 3 mm 3 mm (a) (4-hydroxy-ditertiobutyl-3,5 benzyl) 0,0-diethyl phosphonate.

The devices thus prepared were each placed on the appropriate part of an electrical appliance having a heated surface of 35 x 64 mm supplied by an alternating current of 255 volts so as to reach a temperature of 200 ° C.

The devices thus equipped * with their device were each placed in a 28 m3 room maintained at 25 ° C and 100 house flies were dropped in the room.

After 45 minutes, the number of dead or supine flies was counted in each room.

The result of these counts was as follows: 1-A: 65 1-B: 43 - 14 -

Experiment 2

The procedure was as in experiment 1 by preparing the devices 2-A and 2-B; the device 2-A was composed of two different compositions 2-A 'and 2-A "obtained by the impregnation of each of the two parts of a cellulose cardboard separated by a linear impregnation of a polyester prepolymer catalyzed by a peroxide; device 1-B consisted of a single homogeneous composition containing all of the constituents of compositions 2-A 'and 2-A ". The details of these devices are specified below:

2-A 2-B

2 = Â ’2-Ä"

Bioallethrin 40 mg - 40 mg d-Phenothrin - 60 mg 60 mg

Butyl stearate 40 mg - 40 mg

Cellulose 880 mg 1760 mg 2640 mg

Surface 646 mm2 1,394 mm? 2040 mm?

Length 34 mm 41 mm 60 mm

Width 19 mm 34 mm 34 mm

Thickness 3 mm 3 mm 3 mm

The devices thus prepared were each placed on the appropriate part of an electrical appliance having a heated surface of 35 x 64. mm supplied by an alternating current of 225 volts so as to reach a temperature of 160 ° C.

The devices thus equipped with their device were each placed in a 28 m3 room maintained at 25 ° C and 100 house flies were dropped in the room.

After 30 minutes, the number of dead or supine flies was counted in each room. The result of these counts was as follows 2-A: 38 2-B: 21

The results of these experiments show that the insecticidal efficacy of a device, in which the compositions are separated, is greater than that of J *. ™ Air., ---, · *, · "_________ 4 .______ _______ 4-i4 _____ 4- _ _____ ------------- „„ „4„

Claims (23)

1. Device, intended for the emission of insecticidal vapors and usable in or on a heating device, characterized in that it consists of several different solid compositions juxtaposed each comprising an active substance on insects absorbed in a mass absorbent material, said active substance being, in at least one of the compositions, chosen from pyrethroids. „2. Device according to claim 1 characterized in that the solid compositions are two or three in number. 3. Device according to any one of claims 1 and 2 characterized in that at least one of the solid compositions contains an inert adjuvant chosen from diluents, thickening agents, perfumes, syner-gists, dyes, stabilizers, attractants and insect repellents. 4. Device according to any one of claims 1 to 3 characterized in that in each of the solid compositions, the active substance is chosen from pyrethroids. 5. Device according to any one of claims 1 to 3 characterized in that in one of the solid compositions, the active substance is chosen from synergists, insect attractants, insect repellents and insecticide compounds other than pyrethroids. 6. Device according to claim 5 characterized in that the active substance is an insecticidal compound chosen from organochlorine compounds of which - * —6 the vapor pressure at 25 ° C is greater than 1.10 torr and organophosphorus compounds whose vapor pressure at 25eC is greater than 5.10 ^ torr. •. · / ... - 16 - 7. Device according to any one of claims 116 characterized in that at least one of the solid compositions contains a pyrethrinoid chosen from the esters of chrysanthemic acid or of acid (2,2-butano vinyl) - 3-2,2-dimethyl-cyclopropane-carboxylic acid or (2,2-dibromo-vinyl) -3-2,2-dimethyl-cyclopropane-carboxylic or (2,2-dichloro-vinyl) -3 dimethyl acid -2,2 cyclopropane-carboxylic or (2,2-difluoro-vinyl) -3-2,2-dimethyl-cyclopropane-carboxylic or tetramethyl-2,2,3,3 cyclopropane-carboxylic acid in their forms racemic or resolved. h '8, Device according to claim 7 characterized in that the pyrethronoid is chosen from the substances known under the names of allethrin, bioallé-thrine, S-bioallethrin, cinerin, furethrin, dimethrin, benathrin, kadethrin, prothrin proparthrin, tetramethrin, resmethrin, bioresmethrin, phenothrin, d-phenothrin, permethrin, biopermethrin, cypermethrin, bromethrine, demcamethrin and fluorethrin. 9. Device according to any one of claims 1 to 8 characterized in that the pyrêthrinoide is present in a proportion of between 2 and 15 percent of the total weight of the composition which contains it. 10. Device according to any one of claims 1 to 9 characterized in that the absorbent mass material is chosen from cellulose paper and cardboard composed of wood fibers, cereal fibers, alfa fibers, fibers of cotton, waste of old paper, asbestos fibers, glass fibers, wool fibers and / or polymeric fibers and among the terracotta, sintered aluminas and non-stretched porcelain. 11. Device according to any one of claims 1 to 10 characterized in that the absorbent mass material is a plate whose thickness is between 0.1 and 6 millimeters. 12. Device according to any one of claims 1 to 11 characterized in that the solid compositions are simply placed one against the other without physical means of attachment. > - 17 - " 13. Device according to any one of claims 1 to 11 characterized in that the solid compositions are joined together by a bond chosen from adhesives, cements and stapling, nailing, embedding or metallic or plastic crimping. 14. Device according to any one of claims 1 to 11 characterized in that the compositions consist of a single absorbent mass material in which each of the active substances, optionally accompanied by an inert adjuvant, is absorbed on a different part from the surface. '15. Device according to Claim 14, characterized in that the different impregnated surfaces are separated by a zone free of active substance. 16. Device according to claim 15 characterized in that the free zone of active substance is impregnated with a material having the function of eliminating the absorbent state of the bulk material. 17. Device according to claim 16 characterized in that said material "is chosen from waxes, alkali silicates, natural resins and polymeric synthetic resins. 18. Device according to claim 17 characterized in that said material is a polymeric resin formed in situ from a polymerizable material chosen from monomers, prepolyraers and associations of compounds capable of reacting with each other to give polymeric resins . 19. Device according to claim 18 characterized in that the polymerizable material is a monomer chosen from styrene, acrylic esters, maleic esters and cyanacrylic esters. AT 20. Device according to claim 18 characterized in that the polymerizable material is a prepolymer chosen from polyesters formed between dicarboxylic acids and polyols. * - 18 - ι * · 21. Device according to claim 18 characterized in that the polymerizable material is a combination of compounds chosen from those leading to the formation of resins of the epoxy, epoxy-ester, epoxy-phenolic, urea-formaldehyde, melamine-formaldehyde and polyurethane type. . 22. Method for combating insects, by emitting insecticidal vapors, using a heating device and characterized in that it uses a * device consisting of several different solid compositions juxtaposed each comprising an active substance on the insects absorbed in an absorbent mass material, said active substance being, in at least one of the compositions, chosen from pyrethroids. 23. The method of claim 22 using a device as defined by any one of claims 2 to 21. M