LU81543A1 - CONTROLLED DIFFUSION SYSTEMIC INSECTICIDE COMPOSITIONS - Google Patents

Description

5 T 1 - AFR 111

CONTROLLED DIFFUSION SYSTEMIC INSECTICIDE COMPOSITIONS

The present invention relates to systemic insecticidal compositions making it possible to obtain a controlled diffusion of the active agent in water or in the soil, at the same time as the methods making it possible to obtain said compositions.

The compositions targeted by the present invention contain a polymeric support and a systemic insecticidal substance from the oxime carbamate family.

It is known to enclose active agents in a polymer matrix to allow slow diffusion in water or in the soil: algicidal compositions have thus been produced (ANON, Chem. Eng. News, 1972, 50, no. 23 , 68; CARDARELLI & BILLE, Rep. 1, Proj. 121, Creative Biol. Lab., Baberton, 1976 '), fungicides (Br. Amer.

3,278,371), nematicides (CARDARELLI & FELDMESSER, Proc. Control Rel. Pest. Symp., Dayton, 1975, 386), herbicides (YOUNG & NELSON,

Sp. Study 31.004.69 / 70, Dept, Army, Env. Hyg. Ag., 1969; BARNES &, WHITLAW, Proj. 31.004.69 / 70 Dept. Army Approx. Hyg. Ag., 1970; HARRIS & COLL., Weed Sci., 1973, 21, 318; SINCLAIR, Approx. Sei.

Tech.no 1., 1973,] _, 955; CARDARELLI, Control Rel. Pest. Formul., CRC Press., 1976) and molluscicides (CARDARELLI, Control Rel. Pest.

_ Formul., CRC Press., 1976).

. With regard to insecticides, this process is less used. Compositions are known comprising a polymer and dichlorvos (MILES & COLL., J. Agr. Food Chem., 1962, 10, 240) but these are intended for a release into the atmosphere of 4 - 2 - l ' insecticide agent which is volatile.

They are unusable in water and in the soil because this active substance is very easily and very quickly hydrolyzed. We have also described such compositions based on other organophosphorus compounds such as abate, chlorpyrifos, chlordane, naled , fenthion and malathion (Br. Amer. 3 590 119; CLEMENTS & ROGERS, Proc. 35th Ann. conf. Calif. Mosq. Control Ass., 1967, p. 109; WHITLAW & EVANS, J. · Econ. Entom ., 1968, _61, 889; SCHULTZ & COLL., Mosq. News, 1969, 29, 38; MILES & WOEHST, Pest. Formul. Res., Adv. Chem. Sériés, 1969, 86, 183; Mc DONALD & DICKENS , Mosq. News, 1970, 30, 563; NELSON & COLL., J. Econ. Entom., 1970, 63, 1870 and 1973, 33, 403; MILLER & COLL., Mosq. News, 1973, 33, 148; ROBERTS & COLL., Mosq.

News, 1973, 33, 155 and 165). None of these substances is of interest to carbamates for plants; the latter, on the contrary, are insecticidal agents acting from the roots of plants, spreading in all their vital parts and thus protecting them from attack by insects.

There are known compositions using aldicarb and a polyvinyl chloride support (STOCKES & COLL., J. Agr. Food Chem., 1973, 2JL, 103), but this substance is extremely toxic (LD 50 = 0, 9 mg / kg) which makes such compositions very dangerous and removes much of their interest. Aldicarb-based compositions are also known comprising a paper support and a polyethylene glycol coating (CIBA-GEIGY, Br.

* Brit. 1,477,261) but, in addition to their great toxicity, their industrial implementation is delicate, their use is difficult c in spreading machines and their application on the sites to be treated is difficult, particularly in the presence of wind.

It has now been found by the Applicant that it is possible to produce compositions with a polyvinyl support containing an oxime carbamate much less toxic than aldicarb and that these compositions make it possible to obtain a diffusion of the said s - 3 - carbamate , in water or in the ground, at a controlled speed. The invention therefore relates to systemic insecticidal compositions constituted by a rigid or flexible homogeneous solid mass characterized in that it comprises; A - an insecticidal material, B - a polyvinyl chloride having a molecular mass greater than 10,000, C - a regulating agent chosen from hydrophobic diluents, hydrophilic diluents and pulverulent fillers, and in that the insecticidal material A consists with an oxime carbamate of formula: R ^ -y <j | = * = * N — 0 — CO — NH — CH3 (I) in which is chosen from the monovalent groups R'X- and R'-XC ( R ") (R '") - in which X represents a sulfur atom or a sulfonyl residue, R' represents an ethyl or methyl residue, R "represents a hydrogen atom or an ethyl or methyl residue and R” 'represents a hydrogen atom or an ethyl or methyl residue, R2 being chosen from ethyl, isopropyl, methyl and tert-butyl radicals.

- The systemic insecticide materials defined above are described, in particular, in patents of CIBA-GEIGY (FR 2 150 185; US 3 832 400), Consortium für Elektrochemische Industrie (US 3 816 532), Diamond Shamrock Corp. (US 3,875,232), Dupont de Nemours & Co (US 3,576,834; 3,639,633; 3,647,861) and Kumiai Chemical Industry Co. (JA 72.17,993).

Among these, there may be mentioned, for example, the best known below: S '- 4 - (N-methylcarbamoyloxyimino) -2-methylthio-2 ethane (METHOMYL) (N-methylcarbamoyloxyimino) -2 - methylthio- 3 butane (BÜTOCARBOXIME) (N-methylcarbamoyloxyimino) -2-methylsulfonyl-3 butane (BÜTOXYCARBOXIME) (N-methylcarbamoyloxyimino) -2-dimethyl-3,3 methylthio-1 butane (THIOFANOX).

The insecticide material which is preferred in the compositions - according to the invention is BÜTOCARBOXIME defined above.

The insecticide material A is preferably contained in an i Γ proportion by weight of between 5 and 50 parts per 100 parts of composition; better still, this proportion is between 10 and 40 parts.

Polyvinyl chloride B is preferably contained in a proportion by weight of 20 to 70 parts per 100 parts of composition; better still, this proportion is between 30 and 50 parts.

The addition of a regulating agent chosen from hydrophobic diluents, hydrophilic diluents and powder fillers makes it possible to vary, depending on their nature and quantity, the rate of release of the insecticidal material; this regulating agent must be chemically inert towards the insecticidal material. Hydrophobic diluents are chosen from compounds lacking hydrophilic function and known in the plastics industry as having plasticizing properties. These compounds are, for example, low molecular weight polymers, chlorinated paraffins and heavy esters.

This regulatory agent is preferably contained in a proportion by weight of 25 to 70 parts per 100 parts of composition; better still, this proportion is between 20 and 55 parts.

As examples of low molecular weight polymers, mention may be made of those originating from the homopolymerization or from the copolymerization of the following monomers: 5 - 5 - (1) Homopolymerization: vinyl acetate, isobutylene and chlorinated ethylene ;, (2) Copolymerization : acrylonitrile / butadiene, diethyl fumarate / butadiene, ethyl acrylate / butadiene, vinyl acetate / ethylene, vinyl acetate / ethyl acrylate, vinyl acetate / dimethyl maleate, vinyl acetate / allyl acetate, vinyl chloride / styrene, vinyl chloride / allyl chloride and vinyl chloride / vinyl acetate.

Mention may also be made of polyesters, preferably neutralized by esterification with an alkanol, such as those originating from the following condensations: glycerol / sebacic acid, glycerol / azelaic acid, glycerol / phthalic acid, propylene glycol / adipic acid and propylene glycol / acid Sebacic.

As examples of heavy esters, the following can be cited: (1) The monoesters formed between the alkanols and the alca-no'ic or alkenoic acids such as, for example, laurate, myristate, palmitate, stearate, undecanoate and oleate ethyl, isopropyl, butyl or isobutyl.

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

- 6 - (3) The 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) The diesters formed between cycloalkanols, substituted or unsubstituted alkyl, and dicarboxylated hydrocarbons such as, for example, dicyclohexyl phthalate and bis (methylcyclohexyl) phthalates.

(5) The diesters formed between the phenylalkanols and the dicarboxylated hydrocarbons such as, for example, dibenzyl sebacate.

(6) The diesters formed between the alkanediols and the monocarboxylated hydrocarbons such as, for example, 2,2,4,4-trimethyl diisobutyrate-1,3-pentanediol.

(7) The triesters formed between phenols, substituted or unsubstituted alkyls, and phosphoric acid such as, for example, triphenyl phosphate, tris (terbutyl-4-phenyl) phosphate and tricresyl phosphates.

(8) The triesters formed between the alkanols and phosphoric acid such as, for example, trioctyl phosphate.

The hydrophilic diluents are chosen from compounds which are miscible, soluble or dispersible in water and which are physically compatible with the insecticidal material A, polyvinyl chloride and, when present, the hydrophobic diluent.

As examples of hydrophilic diluents, the following can be cited: - 7 - (1) Polymers and copolymers of vinyl alcohol such as polyvinyl alcohol and the polyvinyl alcohol / polyvinyl acetate copolymer.

(2) Polyvinylpyrrolidones.

% (3) Alkanediols such as 2,2-dimethyl-1,3-propanediol, propylene-glycol, butylene-glycol, 2,2-diethyl-propanediol-1,3.

(4) Polyalkanediols such as polyethylene glycols, polypropylene glycols and polybutylene glycols, (5) Alkane triols, such as glycerol, and their mono-esters formed with alkanoic or alkenoic acids.

(6) Esters formed between aliphatic hydroxy acids and light alkanols such as trimethyl, triethyl, tripropyl and tributyl citrates.

(7) The condensation products of propylene or ethylene oxide on alkylphenols, such as butyl, hexyl, heptyl, octyl, nonyl and dodecyl-phenols, on fatty alcohols, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and octadecenol, and on vegetable oils, such as palm, peanut, coconut, rapeseed, soybean and castor oil.

The pulverulent fillers are chosen from those inert with respect to water or, on the contrary, from those soluble or dispersible in water depending on whether it is desired to slow down or accelerate the rate of diffusion of the active material.

- 8 -

As examples of pulverulent fillers, it can be cited, carbon black, rock powders like those of slate, clay, marble, kaolin, talc, silica or atapulgite, organic salts like acetates, propionates, citrates, adipates, maleates, sebacates, palmitates and stearates of magnesium, zinc, calcium and sodium, mineral salts such as calcium and magnesium silicates and carbonates and such as sodium or potassium chlorides , sodium or calcium sulfates, potassium nitrate and potassium or ammonium phosphates; it may also be mentioned the sodium or calcium salts of alkylarylsulfonic acids, cellulose and its derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carbohydrates such as cereal flours, starch, dextrin and sugars, amino acids such as glutamic acid, casein and protein hydrolysates and the various organic or mineral pigments known to those skilled in the art.

The compositions according to the invention are presented in homogeneous, compact, rigid or flexible solid masses, the shape of which is not critical. This can be, for example, that of plates, sheets, ribbons, tubes, rods or granules.

- The structure of the mass constituting the composition is not, either, critical; 'this structure can be for example, compact, fibrous, alveolar or spongy.

When placed in contact with the ground or water, the compositions according to the invention release 50% of insecticidal material, very regularly, in a period varying between approximately 2 and 200 days. The yield of the compositions according to the invention relative to the total amount of insecticidal material included in the composition is excellent since almost all of the insecticidal material is released after a more or less long time.

The compositions according to the invention can be prepared according to several methods.

According to a first method, a mechanical mixing of the constituents is carried out at ambient temperature using a powdered polyvinyl chloride. Depending on the proportions of the constituents, a dry powder or a fluid paste, called "plastisol", is obtained.

The dry powder is transformed into a homogeneous solid mass by molding, extrusion, injection or casting as in the case of an ordinary plastic material in powder. In the case of a fluid paste, it is heated to gelification and, by cooling, it results in a homogeneous solid mass; the diffusion rate of the active material does not vary appreciably as a function of the temperature and / or the duration of the heating.

According to a second method, the constituents A, B and C of the composition are dissolved in a volatile solvent, the pulverulent fillers, when they are present, which can be kept in suspension by stirring. After evaporation of the volatile solvent, which can be done at a higher or lower temperature and below; at a more or less reduced pressure, the mixture solidifies and one results in a homogeneous mass retaining only a small part of the solvent.

According to a third process, polyvinyl chloride is dispersed, in the sol state, in the mixture of constituents B. and = C previously heated. By cooling, a homogeneous solid mass is obtained.

According to a fourth method, the constituents A and C are introduced into vinyl chloride or into a liquid semi-polymer of this compound. Polymerization is carried out according to methods known to those skilled in the art after addition of a catalyst.

According to a fifth method, a solid mass of polyvinyl chloride, possibly having the desired shape for the final composition, is placed in the liquid mixture of the constituents A + C. All or part of the constituent C can be found initially in the polyvinyl chloride. If the composition must contain a. pulverulent filler, this is initially incorporated in polyvinyl chloride. The active material A and the adjuvant G, when the latter is mixed with the active material, penetrate into the mass of polyvinyl chloride; this penetration requires a time which is inversely proportional to the temperature at which the operation takes place.

According to a variant of this process, the mass of polyvinyl chloride and the constituents A + C are introduced into a container serving as packaging, impermeable to said mixture, the internal volume of which is adapted so that the liquid mixture is in contact with the maximum surface area of the mass of polyvinyl chloride. The penetration takes place during the storage period and the packaging contains a composition according to the invention when it is opened for use.

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

- 11 -

Experiment 1: A mass of polyvinyl chloride plasticized with dibutyl phthalate and whose plasticizer content was close to 36% by weight was used. This mass was shaped, by extrusion, into a tube whose external and internal contours of the cross section were lenticular; the external width was 28 mm and its greatest thickness was 3.2 mm for a length of 45 mm; the width of the interior walls was 20 mm; the weight of such a mass was 7.65 grams.

Such masses were unitarily enclosed in a sealed bag emptied of air before it closed and containing, as the case may be, one of the following liquids (quantities in grams):

Table I

Composition 1Δ IB lCc

Pure butocarboxime 5 3.5 2.5

Dibutyl phthalate - 1.5 2.5

After storage for one month at a temperature of 40 ° C., the sachets were opened to deliver, in all cases, a mass whose composition, homogeneous, was as follows (percentages by weight):

Table II

Composition IA IB IC

Butocarboxime 39.5 27.7 19.8

Polyvinyl chloride 38.7 38.7 38.7

Dibutyl phthalate 21.8 33.6 41.5 - 12 -

Experiment 2: Polyvinyl chloride in fine powder was used for plastisol, which was mixed with technical butocarboxime, titrating 83% purity, and dioctyl phthalate in the following proportions:

Technical butocarboxime: 20% by weight Polyvinyl chloride: 40% by weight Dioctyl phthalate: 40% by weight

The fluid paste obtained was poured into Petri dishes to a thickness of 2 mm and these were placed in temperature-controlled ovens for periods varying between 5 and 30 minutes and at temperatures varying between 115 and 135 ° G.

In all cases, a homogeneous plastic mass was obtained and the active ingredient contents, determined by analysis, were noted as follows in percentages of pure active ingredient.

Table III

Heating time 115 ° C 120 ° C 125 ° C 130 ° C 135 ° C

5 minutes 16.6 16.6 16.6 16.6 16.7 10 minutes 16.6 16.7 16.7 16.7 16.7 15 minutes 16.7 16.7 16.7 16.7 16, 7 20 minutes 16.7 16.7 16.7 16.7 16.7 30 minutes 16.7 16.7 16.8 16.8 16.8

These same analyzes made it possible to establish that only the volatile impurities of the technical material had been lost during the heating.

Experiment 3: Three series 3A, 3B and 3C of compositions according to the invention were prepared using the method described in experiment 2, operating at 125 ° C for 15 minutes.

The compositions thus prepared had the form of discs with a diameter of 32 mm and a thickness of 12 mm and were constituted as follows (values in percentages by weight):

Table IV

Compositions 3A 3B 3C

Technical butocarboxime 10 20 40

Polyvinyl chloride 45 40 30

Dioctyl phthalate 45 40 30

Weight of each disc 8.53 8 ^ 19 7.80 (grams)

The discs thus produced were each suspended in a vase filled with water and, periodically, the amount of active material passed through the water was measured.

The table below summarizes the values thus recorded (percentages of active ingredient released relative to the active ingredient introduced into the composition and weight of active ingredient released in milligrams).

- 14 -

Table V

Measurement deadlines _3A__3B_ 3C

% mg% mg% mg 5th day 12 102 13 211 19 593 9th day 16 137 18 295 25 774 20th day 24 206 26 429 37 1160 51st day 36 309 41 676 53 1647 114th day 49 417 54 881 56 2068 194th day 61 518 65 1068 77 2412

Experiment 4: Disks 4A, 4B and 4C were used such as * those described in Experiment 3 and having the same compositions respectively.

These discs were each placed in sand, the water content of which was close to 20% and, periodically, the percentages of active material diffused were measured.

The results of the measurements are collated in the table below.

Table VI

1 1.11 'M "—'1' ...............> '" [' '”-

Timeframe for measurements _4A__4B 4C_ Z · mg Z mg Z mg 20th day 11 93 13 237 14 440 51st day 22 188 27 496 31 967 114th day 34 292 38 '695 42 1317 194th day 43 365 47 869 51 1604 - 15 -

Experiment 5: A composition was prepared as follows (values in percentages by weight):

Technical butocarboxime 20

Polyvinyl chloride 40

Dioctyl phthalate 40: The method described in experiment 2 was used (15 minutes at 125 ° C); discs were obtained, with a diameter of 90 mm, varying by their thickness:

Table VII

Compositions 5A 5B 5C 5D 5E

Thickness in mm 1 2 3 5 7

Weight in grams 6.8 13.8 20.9 34.8 48.9

These discs were each placed in sand, the water content of which was close to 20%, and periodically the percentages of active material diffused were measured.

The results of the measurements are collated in the table below.

Table VIII

Deadlines for measurements 5A 5B 5C 5D 5E

ΓΞΓ% mg% mg% mg% mg • 8th day 19.2 260 13.2 364 9.0 375 8.4 525 7.8 763 15th day 37.1 505 25.7 709 19.7 824 16.8 117 014 , 4 1407 22nd day 54.5 741 37.1 1024 2847 1200 24.5 170 521.0 2054 29th day 65.2 887 46.7 1289 36.5 1526 30.5 222 325.7 2515 60th day 80.8 1100 62 .9 1736 51.5 2153 43.7 304035.1 3433 90th day 89.8 1220 76.6 2115 67.0 2800 55.9 389045.3 4430 - 16 -

Experiment 6: The operation was carried out as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 6A to 6D which were in the form of discs 90 mm in diameter "and 1.5 mm in diameter. thickness (values in percentages by weight):

Table IX

Compositions 6Δ 6B 6C 6D

Technical butocarboxime 20 20 20 20

Polyvinyl chloride 60 50 40 30

Dioctyl phthalate 20 30 40 50

Weight (grams) 13.83 13.75 13.76 13.56

The discs were each placed in sand, the water content of which was close to 20% and, periodically, the percentages of active material released were measured as well as their weight.

The results of the measurements are collated in the table below. Paintings

Deadlines for 6A__6B__6C__6D_ measurements% mg% mg% mg% mg 8th day 0.4 11 8.4 231 18.0 495 19.8 537 15th day 3.0 83 15.0 412 32.8 890 37.7 1023 22nd day 6.6 183 22.8 628 45.5 1251 55.7 1512 29th day 9.0 249 26.9 740 54.5 1501 67.7 1835 60th day 17.9 495 41.3 1137 71.0 1954 86, 8 2,355 90th day 25.1 693 54.5 1,497 81.1 2,232 98.0 2,659 - 17 -

Experiment 7: The procedure was as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 7 A and 7B which were in the form of discs 90 mm in diameter and 2 mm thick ( percentages by weight):

Table XI

Compositions 7A 7B

"

Technical butocarboxime 20 20

Polyvinyl chloride 40 40

Dioctyl phthalate 35 20

Tris phosphate (2-butoxyethyl) 5 20

Weight (grams) 13.63 13.52

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below. Table XII

, Timelines of measurements _7A__7B_% mg% _jmg 2nd day 12 323 20 512 5th day 50 1330 53 1450 12th day 74 2025 83 2273

Experiment 8: The procedure was as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 8A and 8B which were in the form of discs 32 mm in diameter and 12 mm thick (values in percentages by weight): - 18 -

Table XIII

Compositions 8A 8B

Technical butocarboxime 40 40

Polyvinyl chloride 25 25

Dioctyl phthalate 25 25

PVA copolymer (a) 10

Polyethylene glycol 400 - 10

Weight (grams) 8.45 9.54 (a) Polyvinyl acetate hydrolyzed to 30% polyvinyl alcohol and having a viscosity of 98 centipoises in 4% solution in water at 20 ° C.

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient passed through the water were measured.

The results of the measurements are collated in the table below.

Table XIV

Timeframe of measurements _§A__8B_% mg% mg 5th day 18.2 615 17.5 670 31st day 53.2 1800 46.4 1770 93rd day 81.4 2750 66.3 2530 173th day 98.2 3320 82.4 3145

Experiment 9: The procedure was as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 9A to 9F which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight): ”- 19 -

Table XV

Compositions 9A 9B 9C 9D 9E 9F

Technical butocarboxime 20 20 20 20 20 20

Polyvinyl chloride 37 37 34 34 30 30

Dioctyl phthalate 37 37 34 34 30 30

PVA polymer (a1) 6 12 20 -

PVA polymer (a ") - 6 - 12 20

Weight (grams) 13.60 13.57 13.58 13.60 13.63 13.63 (a ') Polyvinyl acetate hydrolyzed to 50% in polyvinyl alcohol and having a viscosity of 98 centipoises in 4% solution in l at 20 ° C.

(a ") Polyvinyl acetate hydrolyzed to 70% in polyvinyl alcohol and having a viscosity of 88 centipoises in 4% solution in water at" 20 ° C.

The discs were each placed in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

- The results of the measurements are collated in the table below.

Table XVI

Deadlines 9A 9B 9C 9D 9E 9F

measurements% mg% mg% mg% mg% mg% mg 2nd day 15 410 22 590 16 440 27 736 18 496 33 897 5th day 28 755 30 817 29 782 48 1314 34 924 61 1668 12th day 49 1340 51 1390 53 1445 77 2090 63 1712 91 2473 - 20 -

Experimentation. 10: The operation was carried out as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 10Δ to 10E which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight):

Table XVII

Compositions 10A 10B IOC 10D 10E

.11 I ------ ,,, 1. ,,, 1. —I '"' ·

Technical butocarboxime 20 20 20 20 20

Polyvinyl chloride 40 40 40 40 40

Dioctyl phthalate 35 35 30 20 20

Polyethylene glycol 400 5 - 10 - 20

Ethyltriethylene glycol - 5 20

Weight (grams) 13.57 13.51 13.61 13.32 13.50

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below. Table XVIII

Deadlines of 10A__10B__10C__10D__10E

measurements% mg% mg% mg% mg% mg 2nd day 11 295 13 353 13 354 13 341 40 1045 3rd day 17 466 - - 19 512 - 87 2354 5th day 26 714 43 1160 33 904 46 1230 100 2690 12th day 48 1308 64 1707 56 1532 71 1886

Experiment 11: The procedure was as in experiment 2 (15 minutes at 125 ° C.) to prepare compositions 11A and 11B

- 21 - following which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight).

Table XIX

11Δ 11B compositions

Technical butocarboxime 20 20

Polyvinyl chloride 40 40, Dioctyl phthalate 35 20

Tributyl citrate 5 20

Weight (grams) 13.68 13.59

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below. Table XX

Timing of measurements _11A__11B_% mg% mg 2nd day 13 350 20 550 5th day 49 1350 52 1430 12th day 74 2030 76 2080

Experiment 12: The operation was carried out as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 12A to 12F which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight):

Table XXI

- 22 -

Compositions 12Δ 12B 12C 12D 12E 12F

Technical butocarboxime 20 20 20 20 20 20

Polyvinyl chloride 37 37 34 34 30 25

Dioctyl phthalate 37 37 34 34 30 25

Corn round 6 12 20 -

Wheat starch - 6 - 12 - 30

Weight (grams) 13.55 13.60 13.64 13.56 13.70 13.52

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below.

Table XXII

Deadlines 12A 12B 12C 121) 12E 12Γ of measurements% mg% mg Z mg% mg Z mg% mg 2nd day 16 427 17 467 16 431 19 512 16 436 43 1170 3rd day - 20 545 26 703 - - 52 1410 5th day 36 980 30 822 43 1167 41 1117 52 1418 80 2158 Day 12 61 1660 53 1438 70 1914 79 2151 96 2636 10C 2690

Experiment 13: The operation was carried out as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 13A to 13F which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight): - 23 -

Table XXIII

Compositions 13A 13B 13C 13D 13E 13F

Technical butocarboxime 20 20 20 20 20 20

Polyvinyl chloride 37 37 34 34 30 30

Dioctyl phthalate 37 37 34 34 30 30 Methylcellulose 6 - 12 - 20 -

Sodium salt

Carboxymethylcellulose - 6 - 12 - 20

Weight (grams) 13.56 13.55 13.56 13.49 13.61 13.48

The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below. Table XXIV

Deadlines 13A 13B 13C 13D 13E 13F

des j "" 'J ^ - ”" Γ "- measures% mg Z mg%, mg Z mg% mg% mg 2nd day 13 347 15 412 15 400 25 680 17 463 43 1163 - 3rd day - - 22 602 - 33 888 - - 54 1452 Day 5 37 1006 36 971 39 1052 43 1155 65 1772 87 2346 Day 12 60 1636 53 1432 70 1906 79 2126 L00 2706 100 2679

Experiment 14: The operation was carried out as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 14A and 14B which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight):

Table XXV

- 24 -

Compositions 14A 14B

Technical butocarboxime 20 20

Polyvinyl chloride 37 25

Dioctyl phthalate 37 15

Casein 6 40

Weight (grams) 13.56 13.76

The discs were hung, each in a vase filled with water and, periodically, the percentages of active ingredient released were measured.

The results of the measurements are collated in the table below. Table XXVI

Timing of measurements _14A__14B_% mg% mg 2nd day 13 350 16 446 5th day 35 943 43 1191, 12th day 56 1510 80 2213

Experiment 15: The operation was carried out as in experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 15A and 15B which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight): - 25 -

Table millet __

Compositions 15A 15B

Technical butocarboxime 20 20

Polyvinyl chloride 50 34

Dioctyl phthalate 30 34

PVA polymer (a ") 12 (a") polyvinyl acetate hydrolyzed to 70% in polyvinyl alcohol and having a viscosity of 88 centipoises in 4% solution in water at 20 ° C.

The discs were cut into four equal quarters, each weighing around 3.5 grams.

Each quarter was placed, in the open field, in stony loam-clay soil at a depth of 7.5 centimeters. The average rainfall during the experimental period was 3.15 millimeters per day.

Periodically, a quarter was removed from the soil and the amount of butocarboxime remaining was measured by analysis to find out the amount released into the soil.

9

The results of the measurements are collated in the table below.

♦

Table XXVIII

- 26 -

Deadlines for measures _15 A___15B

% mg% mg. 8th day 5 36 21 150 15th day 9 62 40 278 25th day 12 85 59 414 36th day 19 130 71 495 50th day 26 184 83 579 64th day 31 218 - - 71st day - - 92 646 78th day 39 276 94 660

Claims (17)

1. Systemic insecticide composition consisting of a rigid or flexible homogeneous solid mass characterized in that it comprises: A - an insecticide material,. B - a polyvinyl chloride having a molecular mass greater than 10 000, C - a regulating agent chosen from hydrophobic diluents, hydrophilic diluents and pulverulent fillers, and in that the insecticidal material A consists of an oxime carbamate of formula: r1-c = no-co-nh-ch3 (I) * 2 in which is chosen from monovalent groups R'X -and R'-XC (R ") (R" ') - in which X represents a sulfur atom or an aulfonyl residue, R 'represents a methyl or ethyl residue, R ”and R”' independently of one another represent a hydrogen atom or a methyl or ethyl residue, R ^ being chosen from methyl, ethyl isopropyl and tert-butyl residues. 2. Composition according to claim 1, characterized in that it contains the insecticidal material A in a proportion by weight of between 5 and 50 parts per 100 parts of composition. 1 Composition according to Claim 2, characterized in that it contains the insecticidal material A in a proportion by weight of between 10 and 40 parts per 100 parts of composition. - 28 - 4. Composition according to any one of claims 1 to 3, characterized in that it contains polyvinyl chloride B in a proportion by weight of 20 to 70 parts per 100 parts of composition. 5. Composition according to claim 4, characterized in that it contains polyvinyl chloride B in a proportion by weight of 30 to 50 parts per 100 parts of composition. 6. Composition according to any one of claims 1 to 5 characterized in that it contains the regulatory agent C in a proportion by weight of 15 to 70 parts per 100 parts of composition. 7. Composition according to claim 6, characterized in that it contains the regulating agent C in a proportion by weight of 20 to 55 parts per 100 parts of composition. 8. Composition according to any one of claims 1 to 7, characterized in that the insecticide material A is chosen from (N-methylcarbamoyloxyimino) -2 2-methylthioethane, (N-methylcarbamoyloxyimino) -2-methylthio-3ane , (N-methylcarbamoyloxyimino) -2 methylsulfonyl-3 butane, and (N-methylcarbamoyloxyimino) -2 dimethyl-3,3 methylthio-1 butane. ^ 9. Composition according to claim 8, characterized in that the insecticidal material is (N-methylcarbamoyloxyimino) -2 methylthio-3 butane. 10. Composition according to any one of claims 1 to 9, characterized in that the regulatory agent is chosen from hydrophobic diluents, hydrophilic diluents and pulverulent fillers. - 29 - 11. Composition according to claim 10, characterized in that the regulating agent is chosen from polymers of low molecular mass, chlorinated paraffins and heavy esters. 12. Composition according to any one of claims 1 to 11, characterized in that it is in the form of a solid, homogeneous, compact, rigid or flexible mass of any shape. 13. Process for preparing a composition according to any one of claims 1 to 12, characterized in that the powdered vinyl chloride B is mechanically mixed at room temperature with the compounds A and C of the composition to obtain a powder dry or a fluid paste which is then transformed into a homogeneous solid mass by molding, injection or casting or by heating until the gelling temperature of the mixture. 14. Method for preparing a composition according to any one of claims 1 to 12, characterized in that the constituents A, B and C are dissolved in a volatile solvent which is then evaporated at a more or less high temperature or under pressure scaled down. 15. Process for the preparation of a composition according to any one of claims 1 to 12, characterized in that vinyl chloride is dispersed in the sol state in the 'liquid mixture of constituents B and C beforehand heated and in that after obtaining a homogeneous dispersion, the mixture is allowed to cool. 16. Process for the preparation of a composition according to any one of claims 1 to 12, characterized in that the constituents A and C are introduced into vinyl chloride or into a semi-polymer of this compound and that the mixture is then polymerized after addition of a catalyst ... 17. Method for preparing a composition according to one of claims 1 to 16, characterized in that a solid mass of polyvinyl chloride having the desired shape for the final composition is placed in the liquid component A which optionally contains component C if this is not already contained in polyvinyl chloride and in that all liquids are allowed to penetrate into the mass of polyvinyl chloride for a period of time inversely proportional to the temperature. 18. Method according to claim 17, characterized in that the constituents A + C are introduced into a container serving as packaging, impermeable to the said constituents A + C, the internal volume of which is adapted so that the liquid mixture is in contact with the maximum surface area of the solid mass of polyvinyl chloride, the packaging then being closed and then stored for a sufficient time so that it no longer contains free liquid at the end of the storage period. 19. Use of a composition according to any one of claims 1 to 12, as a systemic insecticide composition making it possible to obtain a controlled diffusion of the active agent in water or in the soil. FO 7.1 ROZ / cb *