NL8003995A - SYSTEMICALLY INSECTICIDE PREPARATION WITH REGULATED DIFFUSION AND METHOD FOR PREPARING THEREOF. - Google Patents

Description

!> \ -1- N.O. 29256

Controlled diffusion systemic insecticidal composition as well as a method of preparing the same.

The invention relates to systemic insecticidal preparations which make it possible to achieve a controlled diffusion of the active ingredient in water or in the soil, and a method for preparing such preparations.

The compositions contemplated according to the invention contain a polymeric carrier and a systemic insecticide belonging to the group of oxime carbamates.

It is known to enclose active substances in a polymeric matrix in order to allow slow diffusion in water or in the soil: in this way the preparation of algicidal preparations takes place (ANON, Chem. Eng. News, 1972, 50 , No. 25, 68; CARDARELLI & BILLE, Rep. 1, Proj.

121, Creative Biol. Lab., Baberton, 1976), fungicidal compositions (U.S. Pat. Nos. 3 * 269,900 and 3 * 278,371), nematicide preparations (CARDARELLI & PELDMESSER, Proc.

Control Rel. Plague. Symp., Dayton, 1975, 386), herbicidal compositions (U.S. Pat. Nos. 3 * 269 * 900 and 3,343,941; British Patent 1,502,441; Canadian Patent 846,785; Prans Patent 2,016,818; YOUNG & NELSON, Sp. Study 31 * 004.69 / 70, Dept. Army, Env. Hyg. Ag., 1969; BARNES & WHITLAW, Proj. 31 * 004.69 / 70, Dept. Army Env. Hyg. Ag., 1970; HARRIS et al., Weed Sci. , 1973, 21, 318; SINCLAIR, Env. Sci. Teehnol., 1973, Z> 955; CARDARELLI, 25 Control Rel. Pest. Pormul., CRC Press., 1976), Molluscicidal Preparations (CARDARELLI, Control Rel. Pest Pest. Pormul., CRC Press, 1976) and antibacterial preparations (U.S. Patent 4,007,258; Prans Patent 2,016,818).

With regard to the insecticides, these methods are less common. Compositions are known which contain a polymer and the dichlorvos (MILES et al., J. Agr.

Pood Chem., 1962, 10, 240), but these are for release into the atmosphere of the insecticide, which is volatile.

They are unusable in water and in the soil, because this active substance hydrolyses very easily and very quickly. Similar preparations have also been described at

O Λ Λ T ft ft C

λ -2- based on other organophosphorus compounds, such as azuiphos, bromophos, chlorpyrifos, demeton, diazinon, dimefox, dimethoate, fenitrothion, fenthion, malathion, mevinphos, monocrotophos, naled, parathion, temephos, and based on organochlorine compounds such as aldrin, dieldrin, endrin, heptachlor, isodrin, lindane, and methoxyclor (US Pat. Nos. 3 * 269,900 and 3 * 590,119; Canadian Patent 846,785; French Patent 2,016,818; CLEMENTS & ROGERS, Proc. 35tb Ann. Conf. Calif.

10 Mosq. Control. Ass., 1967, biz. 109; WHITLAW & EVANS, J. Econ. Entom., 1968, 61, 889; SCHULTZ et al., Mosq. News, 1969, 22, 38; MILES & WOEHST, Pest. Pormul. Bes., Adv. Cbem. Series, 1969, 86, 183; Mc DONALD & DICKENS, Mosq. News, 1970, jjSO, 563; NELSON et al., J. Econ. Entom., 1970, 63 * 15 1870 and 1973, 22> 403; MILLER et al., Mosq. News, 1973, 22, 148; ROBERTS "c.s., Mosq. News, 1973, 22> 155 and 165).

Aryl or heteroaryl carbamates, such as dioxacarb, isolan, dimetilan, carbofuran, and various substituted phenyl carbamates (U.S. Patent No. 3 * 269 * 900; British Patent No. 1,502,441; Canadian Patent No. 846,785; French Patent No. 2,016) have also been used. 818 and 2,279,336).

Neither of these substances exhibits the advantage of oxime, carbamates over plants, and they cannot be used in the compositions of the invention because their release in water or soil is far too low, such as on the band of one of the tests has been demonstrated. The oxime carbamates, on the other hand, diffuse very easily from the compositions according to the invention, while the oxime carbamates are moreover active via the roots of the plants and spread over all living parts thereof, thus protecting them from attack by insects.

Preparations are known in which aldicarb and a polymeric carrier are used (French Patent Specification 35 2,279 * 236; STOCKES et al., J. Agr. Food Cbem., 1973, 21, 103), but this substance is particularly toxic (DL ^ q = 0.9 mg / kg), making these preparations particularly dangerous and the benefit of which is largely eliminated. Aldicarb-based preparations are also known which comprise a paper carrier and a polyethylene glycol shell (nxqg * I * -5-) (CIBA-GEIGY, British Patent Specification 1,477,261) but apart from the major Its toxicity is not without danger to its industrial processing, its use on spreading machines is difficult and the application thereof to places to be treated is far from easy, especially when windy.

Granules which consist of a polymeric carrier and an oxime carbamate, such as methomyl CFrans patent 2,016,818) have also been used, but in this heterogeneous type of granules the action of the polymer is based on absorption and the amount to be incorporated therein is active. substance depending on the specific surface area of the polymer, so it must be porous, causing concentration restrictions and difficulties in controlling the release.

In accordance with the invention, it has now been found that it is possible to formulate homogeneous compositions with a vinyl polymer support containing an oxime carbamate which is much less toxic than aldicarb, and that these compositions allow diffusion of the carbamate in water or in the ground at a controlled rate. The invention is therefore directed to systemic insecticidal preparations consisting of a rigid or flexible homogeneous solid mass of 25 A - an insecticidal substance, B - a polyvinyl chloride with a molecular mass of more than 10,000.0 - a regulating agent belonging to the hydrophobic cutting agents, $ 0 D - optionally a regulating agent belonging to the hydrophilic excipients and powdered fillers, which compositions are characterized in that the insecticidal substance A consists of an oxime carbamate of the formula R — C = N — 0 — GO — RH —CEL ·> »0 E2 55 wherein a monovalent radical represents R'X or R, -XC (RM) (R" '), where X represents a sulfur atom or a sulfonyl group, R' an ethyl or methyl group, R " a hydrogen atom or a phthyne 95-4 ethyl or methyl group, and H, M denote a hydrogen atom or an ethyl or methyl group, and E2 represents an ethyl, isopropyl, methyl or tert-butyl group.

The above-defined systemic insecticidal substances are described in particular in the patents of CIBA-GEIGT (French Patent 2,150,185; U.S. Patent 3,832.4-00), Consortium für Electrochemical Industry (U.S. Patent 3,816,532), Diamond Shamrock Corp. (U.S. Patent No. 3,875,232), Dupont de Nemours & Co (U.S. Patents 3,576,834-, 3,639,633, and 3,64-7,861), and Kumiai Chemical Industry Co. (Japanese Patent Publication 72.17 993).

Of these, the following most well-known may be mentioned, for example: 2- (N-methylcarbamoyloxyimino) -2-methylthioethane (METHOMYL) 2- (N-methylcarbamoyloxyimino) -3-methylthiobutane (BUTOCARB-OXIME) 2- (N-methylcarb amoyloxyimino) -3-methylsulfonylbutane (BUTOXICARBOXIME) 2- (N-methylcarb amoyloxyimino) -3,3-dimethyl-1-methylthio-butane (THIOFANOX).

The preferred insecticidal substance in the compositions of the invention is the above-mentioned BUOCARB-25 OXIME. The insecticidal substance A is preferably present in an amount of 5 to 50 parts by weight per 100 parts by weight of the preparation, which amount is preferably between 10 and 4-0 parts by weight.

The polyvinyl chloride B is preferably present in an amount of 20 to 70 parts by weight per 100 parts by weight of the preparation, which amount is preferably between 30 and 50 parts by weight.

The addition of a regulating agent belonging to the hydrophobic extenders allows, depending on the nature and amount thereof, to adjust the release rate of the insecticidal substance, which regulating agent must be chemically inert to the insecticidal substance. The hydrophobic extenders are selected from the compounds which are free of a hydrophilic 4-0 function and are known in the plastics industry as 800 3995 materials with plasticizing properties. These compounds are, for example, low molecular mass polymers, chlorinated paraffins and heavy esters. This controlling agent is preferably included in an amount of 15 to 70 parts by weight per 100 parts by weight of the composition, which amount is preferably between 20 and 55 parts by weight.

As examples of low molecular mass polymers, mention may be made of the polymers obtained by homopolymerization or copolymerization of the following monomers: (1) Homopolymerization: vinyl acetate, isobutylene and chlorinated ethylene.

(2) Copolymerization: acrylonitrile / butadiene, diethylfumarate / butadiene, ethyl acrylate / butadiene, vinyl acetate / ethylene, vinyl acetate / ethyl acrylate, vinyl acetate / dimethyl maleate, vinyl chloride / allyl chloride, vinyl chloride / styrene. Also can be mentioned polyesters, preferably polyesters, which have been neutralized by esterification with an alkanol, such as the polyesters, obtained by condensation of the following components: glycerol / sebacic acid, glycerol / azelaic acid, glycerol / phthalic acid, propylene glycol / adipic acid and propylene glycol / sebacic acid.

As examples of heavy esters, the following may be mentioned: (1) Monoesters of alkanols and alkane and olefin carbon acids, such as, for example, ethyl, isopropyl, butyl or iso-butyl laurate, myristate, palmitate, - stearate, undecinoate and oleate.

(2) Diesters of alkanols and dicarboxylic hydrocarbons, such as dialkyl dipinate, for example dioctyl adipinate and dinonyla dipinate, dialkyl sebaccinate, for example dibutyl sebaccinate, dipentyl sebaccylate, dioctyl sebaccylate, dioctyl benzylate, dialioctyl acylate, for example dioctyl acetyl ) phthalate, bis (dodecyl) phthalate, bis (tridecyl) phthalate, bis (tetradecyl) phthalate and dicetyl phthalate.

40 (5) Diesters, whether or not through one or more alkyl groups

onA? A AR

-6- substituted phenols and dicarboxyhydrocarbons, such as diaryl phthalates, for example diphenyl phthalate and dicresyl phthalates.

(4) Diesters of cycloalkanols and dicarboxyhydrocarbons, which may or may not be substituted by one or more alkyl groups, such as, for example, dicyclohexyl phthalate and bis (methylcyclohexyl) phthalates.

(5) Diesters of phenyl alkanols and dicarboxy hydrocarbons, such as, for example, dibenzyl sebaccinate.

(6) Diesters of alkane diols and monocarboxyhydrocarbons, such as, for example, the diisobutyric acid ester of 2,2,4-trimethylpentane-1,3-diol.

(7) Triesters of phenols and phosphoric acid, which may or may not be substituted by one or more alkyl groups, such as, for example, triphenyl phosphate, tris (4-tert-butylphenyl) phosphate and tri-crephophates.

(8) (Priests of alkanols and phosphoric acid, such as, for example, trioctyl phosphate.

The hydrophilic excipients, which act as an additional regulating agent, may be present in an amount of 0 to 50 parts by weight per 100 parts by weight of the composition. They are selected from water-miscible, water-soluble or dispersible compounds which are physically compatible with insecticidal substance A, polyvinyl chloride and hydrophobic excipient.

As examples of the hydrophilic extenders, the following may be mentioned: (1) Polymers and copolymers of vinyl alcohol, such as polyvinyl alcohol and vinyl alcohol / vinyl acetate copolymer.

(2) Polyvinylpyrrolidones.

(3) Alkane diols, such as 2,2-dimethylpropane-1,3-diol, propylene glycol, butylene glycol and 2,2-diethylpropane-1,3-diol.

(4) Polyalkane diols, such as polyethylene glycols, polypropylene glycols and polybutylene glycols.

(5) Alkane triols, such as glycerol and monoesters thereof with alkane or alkene carboxylic acids.

(.6) Esters of low molecular weight aliphatic hydroxy acids and alkanols, such as trimethyl, triethyl, tripropyl and tributyl citrates.

40 (7) Condensation products of epoxypropane or epoxyethane on 800 3 9 95 • * -7- starters, such as alkylphenols, for example butyl, hexyl, heptyl, octyl, nonyl and dodecylphenols, fatty alcohols, such as decanol, dodecanol, tetradecanol , hexadecanol, octa-decanol and octadecenol and vegetable oils, such as palm-5 oil, groundnut oil, coconut oil, rapeseed oil, soybean oil and castor oil.

The powdery fillers are selected from the water-inert fillers or, in contrast, from the water-soluble or dispersible fillers depending on whether one wishes to slow or accelerate the diffusion rate of the active substance.

As an example of powdered fillers can be mentioned: carbon black, powders of rocks, such as slate, clay, marble, kaolin, talc, pebble or atapulgite, organic salts, such as magnesium, zinc, calcium and sodium acetates, propionates, citrates, adipinates, maleinates, sebaceinates, palmitates and stearates, inorganic salts such as calcium and magnesium silicates and carbonates as well as sodium or potassium chlorides, sodium or calcium sulfates, potassium nitrate and potassium or ammonium phosphates, while mention may also be made of the sodium and calcium salts of alkylarylsulfonic acids, cellulose and derivatives. thereof, such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, earboxymethyl cellulose, glycides such as cereal flours, starch, dextrin and sugars, amino acids such as glutamic acid, casein and protein hydrolysis products as well as various organic and inorganic pigments as known to those skilled in the art.

The compositions of the invention have the appearance of rigid or flexible compact, homogeneous solid masses, the shape of which is not critical. The shape can be, for example, the shape of a plate, sheet, tape, tube, ring or grain.

The structure of the mass from which the composition is made is also not critical, which structure can for instance be a compact, fibrous, cavity-like or sponge-like structure.

When the compositions of the invention have been contacted with the soil or with water, they release 30% of the insecticidal substance very regularly over a period ranging from about 2 to 200 days.

The yield of the compositions according to the invention based on the total amount of the insecticidal substance contained in the preparation is excellent, since the apparent total amount of the insecticidal substance is released over a somewhat longer period of time.

The compositions of the invention can be prepared by various methods.

According to a first method, a mechanical mixture of the ingredients is processed at room temperature using powdered polyvinyl chloride. Depending on the mixing ratios of the components, a dry powder or a flowing paste, a so-called "plastisol" is obtained. The dry powder is processed into a homogeneous solid mass by molding, extrusion, injection molding or casting, as in the case of a conventional powdered plastic material In the case of a flowing paste, it is heated until gelation occurs and a homogeneous solid mass is obtained by cooling. The diffusion rate of the active substance does not appreciably vary as a function of the temperature and / or the duration of heating.

According to a second method, the components A, B and C of the preparation are dissolved in a volatile solvent, in which the powdered fillers, if present, are also included, if they can be kept in a suspended state by stirring. On evaporation of the volatile solvent, which can take place at a slightly elevated temperature and under a somewhat reduced pressure, the mixture assumes a solid state, whereby a homogeneous mass is obtained, in which only a small amount of the solvent remains.

According to a third method, the polyvinyl chloride 35 is dispersed in the form of a sol in the mixture of constituents B and C, which has been preheated. A homogeneous solid mass is then obtained by cooling.

According to a fourth method, the components A and C are incorporated in vinyl chloride or a liquid prepolymer of 4-0 this compound. After addition of a catalyst -9-, a polymerization is then carried out according to methods known to those skilled in the art.

According to a fifth method, a solid mass of the polyvinyl chloride, which optionally has the desired form of the finished preparation ", is introduced into a liquid mixture of the constituents A + C. The constituent O can be wholly or partly from the outset. polyvinyl chloride are present.If the preparation must contain a powdery filler, it can be included in the polyvinyl-10 chloride in advance.The active substance A and the adjuvant C, when this adjuvant is mixed with the active substance, penetrate the mass of the polyvinyl chloride, which penetration takes a time inversely proportional to the temperature at which this treatment is carried out.

According to a variant of this method, the mass of the polyvinyl chloride and the components A + 0 are placed in a container which is impermeable to the said mixture and whose internal volume is adjusted in such a way that the liquid mixture is maximized comes into contact with the surface of the mass of the polyvinyl chloride. The penetration then takes place during the course of storage, so that the package contains a composition according to the invention when it is opened for use.

The advantage of the preparations according to the invention is illustrated by the following tests:

Test 1: Use is made of a polyvinyl chloride mass plasticized with dibutyl phthalate, of which the plasticizer content is about 36% by weight.

This mass was extruded into a tube, the external and internal contours of which were lenticular in cross section. The external dimension was 28 mm at a maximum thickness of 3 mm and a length of 45 mm. The internal dimension between the walls was 20 mm. Such a mass had a weight of 7 * 65 g. Before sealing, these masses formed a unit in which, as an airtight bag, one of the following liquids was enclosed (expressed in grams), depending on the case: «on19 95 -10-

ü? abel A

Preparation IA IB IG

pure butocarboxime 5 5 »5 2.5 dibutyl phthalate - 1.5 2.5

After storage for one month at a temperature of 40 ° G, the closed pads were opened to release in each case a mass, the homogeneous composition of which was as follows (expressed in weight percentages):

label B

Preparation IA IB IC

butocarboxime 59.5 27.7 19.8 polyvinyl chloride 58.7 38.7 38.7 dibutyl phthalate 21.8 33.6 41.5

Test 2: Polyvinyl chloride in fine powder form intended for use in plastisol was used, which was mixed with technical butocarboxime with a purity of 83% and di-octyl phthalate in the following mixing ratios: 10 technical butocarboxime: 20 wt% polyvinyl chloride: 40 wt .% dioctyl phthalate: 40 wt.%

The resulting flowable paste was poured into petri dishes up to a thickness of 2 mm, which petri dishes were placed in ovens at regular temperatures for periods of 5 to 50 minutes and at temperatures of 115 to 155 ° C. In each case, a homogeneous plastic mass was obtained, the active substance contents of which, as determined by analysis, were as follows, expressed in the percentage of pure active substance:

label G

Duration of the 115 ° G 120 ° G 125 ° G 150 ° G 155 ° C

heating _ _ _ _ _ 5 minutes 16.6 16.6 16.6 16.7 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 50 minutes 16.7 16.7 16.8 16.8 16.8 800 3 9 95 -11-

From the above analyzes it can be established that only the volatile impurities are lost in the processing technique in the course of heating. Test 5: Three sets of $ A, 3B and 30 of the compositions of the invention were prepared using the method described for Test 2 at a temperature of 125 ° C over a period of 15 minutes.

The preparations thus obtained were in the form of discs with a diameter of 52 mm and a thickness of 12 mm and had the following composition (expressed in weight percent):

Table D

Preparation 5A 5B 50 technical butocarboxime 10 20 40 polyvinyl chloride 45 40 50 dioctyl phthalate 45 40 50 weight of each disc 8.53 9 * 19 7 * 80 (grams)

The disks formed in this way were each suspended in a vessel filled with water, after which the amount of the active substance released into the water was periodically measured.

The table below shows the quantities determined in this way (percentage of the active substance diffused, based on the amount of active substance included in the preparation, the diffused active substance being expressed in milligrams):

Table E

Moment of 3A 5B 5C

measurements% mg% mg% mg 5th day 12 102 15 211 19 595 9th day 16 157 18 295 25 774 20th day 24 206 26 429 57 1160 51st day 56 309 41 676 53 1647 114th day 49 417 54 881 56 2068 194th day 61 518 65 1068 77 2412

Trial 4; Discs 4A, 4B and 4C were used, as described for Run 3 *, which discs successively had the same composition.

These disks were each placed in sand, the water content of which was about 20%, while the percentages of diffused active substance were measured periodically.

5 The results of the measurements are summarized in the table below.

Dabei F

Moment of 4A 4B 40 measurements% mg% mg% 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 42 365 47 869 51 1604

Test 5: A preparation of the following composition was prepared: technical butocarboxime 20% by weight polyvinyl chloride 40% by weight 10 dioctyl phthalate 40% by weight

The process described in Experiment 2 was used (15 minutes at 125 ° C) to obtain 90 mm diameter disks, the thickness of which was different, however.

Table G

Preparation 5A 5B 50 5D 5E

thickness, mm 12357 weight, gram 6.8 13.8 20.9 34.8 48.9 These discs were each placed in sand, the water content of which was approximately 20%, after which the percentages of diffused active substance were measured periodically.

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

800 3 9 95 -13-Tab el Η

Moment of 5A__5B 50 5D__5E

measurement% mg% mg% mg% mg% mg 8th day 19.2 260 13.2 364 9.0 375 8.4 523 7.8 763 15th day 37.1 505 25.7 709 19.7 824 16.8 II70 14.4 1407 22nd day 54.5 741 37.1 1024 28.7 1200 24.5 1705 21.0 2054 29th day 65.2 887 46.7 1289 56.5 1526 30.5 2123 25.7 2515 60th day 80.8 1100 62.9 1736 51.5 2153 43.7 3040 35.1 3433 90th day 89.8 1220 76.6 2115 67.0 2800 55.9 3890 45.3 4430

Test 6: The procedure of Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 6A to 6D, which were in the form of discs with a diameter of 90 mm and a thickness of 1.5 mm ( the numbers indicate 5 spraying weights):

Table I

Preparation 6A 6B 60 6D

technical butocarboxime 20 20 20 20 polyvinyl chloride 60 50 40 30 dioctyl phthalate 20 30 40 50 weight, gram 13.83 13.75 13.76 13.56

The disks were each placed in sand, the water content of which was about 20%, after which the percentage of active substance diffused and the weight thereof were periodically measured.

10 The results of the measurement are summarized in the table below.

Table J

Moment of 6A 6B 60 6D

the measurement% mg% mg% mg% mg i 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 2355 90th day 25.1 693 54.5 1497 81.1 2232 98.0 2659 800 3 9 95

Test 7: The procedure of Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 7A and 7B, which were in the form of discs with a diameter of 90 mm and a thickness of 2 mm (the numbers indicate 5% by weight):

Table K.

Preparation 7A 7B

technical butoearboxime 20 20 polyvinyl chloride 40 40 dioctyl phthalate 35 20 tris (2-butoxyethyl) phosphate 5 20 weight, gram 13 * 63 13 »52

The disks were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically.

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

Table L

Time of measurements _ £ A_ 7B_ -. gg— JL mS ......

2nd day 12 323 20 512 5th day 50 1330 53 14-50 12th day 74-2025 83 2273

Test 8: The procedure as indicated in Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 8A and 8B, which were in the form of discs with a diameter of 32 mm and a thickness of 12 mm ( the 15 numbers indicate weight percentages):

Table M

Preparation 8A 8B

technical butoearboxime 40 40 polyvinyl chloride 25 25 dioctyl phthalate 25 25 P7A copolymer (a) 10 polyethylene glycol 400 - 10 weight, gram 8.45 9.54 (a) Polyvinyl acetate, which was hydrolyzed to 30% polyvinyl alcohol and had a viscosity of 98 cP an 800 39 95 -15- 4% solution in water "big 20 ° C.

The disks were each suspended in a water-filled vessel, while the percentages of active substance eaten off the water were periodically measured.

5 The results of the measurements are summarized in the table below.

Table N

Time of measurements 8A_ 8B_ _% mg% mg 5th day 18.2 615 17.5 670 51st day 53.2 1800 46.4 1770 93th day 81.4 2750 66.3 2530 173rd day 98.2 3320 82.4 3145

Test 9: The procedure as indicated under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 9A to 9F, which are in the form of discs with a diameter of 90 mm and a thickness of 2 mm owned (the numbers indicate percentages by weight):

Table 0

Preparation_9A 9B 90 9D 9E 9? technical butocarb oxime 20 20 20 20 20 20 polyvinyl chloride 37 37 34 34 30 30 dioctyl phthalate 37 37 34 34 30 30 FVA copolymer (a ') 6 12 20 PVA copolymer (a ") - 6 12 20 weight, gram 13.60 13 .57 13.58 13.60 13.63 13.63 (a ') Polyvinyl acetate, which was 50% hydrolyzed to polyvinyl alcohol and exhibited a viscosity of 98 cP in a 4% aqueous solution at 20 ° C.

(A ”) Polyvinyl acetate, which was hydrolyzed 70% to polyvinyl alcohol and exhibited a viscosity of 88 cP as a 4% aqueous solution at 20 ° C.

The disks were each placed in a vessel filled with water, while the percentages of diffused active substance were measured periodically.

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

800 3 9 95

-16-Tab el P

Moment of 9A 9B 9C 9D 9E 9E

the measurements% mg% mg% mg% mg% mg% ms 2nd day 15 410 22 590 16 440 2? 736 18 496 53 897 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

Test 10: The procedure as described under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 10A to 10E, which were in the form of discs with a diameter of 90 mm and a thickness of 2 mm (the 5 numbers indicate weight percentages):

Table Q,

Preparation 10A 10B 10E 10D 10E

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 ethyl triethylene glycol 5 - 20 weight, gram 13.57 13.51 13.61 13.32 13.50

The disks were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically,

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

Table S

Moment of 10A 10B 10C 10D 1QE

the measurements ^ mg% mg% mg _% mg mg 2nd day 11 295 1 3 353 1 3 354 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? 1 1886

Test 11: The procedure as indicated under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 11A and 11B, which were in the form of discs with a diameter of 90 mm and a thickness of 2 mm -15 ten (the numbers indicate percentages by weight).

800 39 95 -17-

Table_S '

Preparation 11A 11Β technical butocarboxime 20 20 polyvinyl chloride 40 40 dioctyl phthalate 35 20 tributyl citrate 5 20 weight, gram 13 »68 13» 59

The disks were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically.

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

label 0?

Moment of the 11A

___ _7o mg _yb mg 2nd day 13 350 20 550 5th day 49 1350 32 1430 12th day 74 2030 76 2080

Test 12: The procedure as indicated under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 12A to 12P, which are in the form of discs with a diameter of 90 mm and a thickness of 2 mm Were -10 (the numbers indicate percentages by weight):

Table U

Preparation 12A 12B 12C 12D 12E 12P

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 on the cob 6 - 12 - 20 g flour - 6 - 12 30 weight, gram 1 ^ 5 Ί3β0 13 £ 4 1356 13 ^ 0 13.52

The disks were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically.

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

AÖ0 3 9 95

-18-Tab el V

Moment of 12A 12B 12C 12D 12E 12P

the measurements _% _ mg% _ mg% _ mg% _ mg% _ mg% mg 2nd day 16 4-27 17 4-67 16 4-31 19 512 16 4-36 4-3 1170 3rd day - - 20 54 -5 - 26 703 - - 52 14-10 5th day 36 980 30 822 4-3 1167 4-1 1117 52 14-18 80 2158 12th day 61 1660 53 14-38 70 1914- 79 2151 96 2636 100 2690

Test 13: The procedure as indicated under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 13A to 13P, which were in the form of discs with a diameter of 90 mm and a thickness of 2 mm 5 (the numbers indicate percentages by weight):

Table W

Preparation 13A 13B 130 13D I3E 13? technical buto-carboxime 20 20 20 20 20 20 polyvinyl chloride 37 37 34 34-30 30 dioctyl phthalate 37 37 34- 34-30 30 methyl cellulose 6 - 12 20 sodium salt of carboxymethyl cellulose - 6-12-20 weight, grams 13.56 13.55 13.56 13.49 13.61 13.48

The discs were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically,

The results of the measurements are summarized in the table below:

Table X.

Moment of 13A 13B 130 13D 13E 13P

the measurements __% SS JÉ mg Jo mg 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 5th day 37 1006 36 971 39 1052 43 1155 65 1772 87 2346 12th day 60 1636 53 1432 70 1906 79 2126 100 2706 100 2679 800 3 9 95 -19-

Test 14: The procedure as indicated under test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 14A and 14B, which are in the form of discs with a diameter of 90 mm and a thickness of 2 mm 5 are wrong (the numbers indicate weight percentages):

Table I

Preparation 14A 14B

technical butocarboxime 20 20 polyvinyl chloride 57 25 dioctyl phthalate 37 15 casein 6 40 weight, gram 13.56 13.76

The discs were each suspended in a vessel filled with water, while the percentages of diffused active substance were measured periodically.

The results of the measurements are summarized in the 10 tables below.

Table Z

Moment of the 14A 14B

metinSei1 J> mg _% mg 2nd day 13 350 16 446 5th day 35 943 43 1191 12th day 56 1510 80 2213

Test 15i The procedure as described under Test 2 (15 minutes at 125 ° C) was followed to prepare the following preparations 15A and 15B, which are in the form of discs with a diameter of 90 mm and a thickness of 2 mm. (the numbers indicate percentages by weight):

Table AA

Preparation 15A 15B

technical butocarboxime 20 20 polyvinyl chloride 50 34 dioctyl phthalate 30 34 PVA copolymer (a ”) - 12 (a") Polyvinyl acetate hydrolyzed 70% to polyvinyl alcohol and a viscosity of 88 cP in 4% aqueous solution at 20 ° C.

800 3 9 95 -dö-

The disks were cut into four equal quarters, each weighing about 3.5 g. Each quarter was applied in the open field in stony wet clay soil at a depth of 7 cm. The average rainfall 5 during the trial period was 5 * 15 mm per day. Periodically, a quarter was removed from the soil, after which the residual amount of butocarboxime was measured by analysis to determine the amount diffused in the soil.

10 The results of the measurements are summarized in the table below.

Table BB

Time of measurements 15A 15B

_ _% mg _% mg 8th day 5 36 21 150 15th day 9 62 40 278 25th day 12 85 59 414 56th day 19 130 71 495 50th day 26 184 83 579 64th day y \ 218 - 71st day - - 92 646 78th day 59 276 94 660 B.C.

Experiment 16: Seven series of preparations 16A to 16G

prepared according to the invention using the methods described under test 2, i.e. for 15 minutes at 125 ° C.

The preparations prepared in this manner were in the form of discs with a diameter of 19 mm and a thickness of 2 mm and showed the following composition (the numbers indicate percentages by weight): 800 3 9 95 -21-

Label GC

Preparation _16A 16B 160 16D 16E 16P Λβ & technical buto 20 20 20 - 20 20 20 po carlo oxime polyvinyl chl o- 58 38 38 38 38 38 38 ride dioctyl phthalate 42 di octyl adipinate - 42 - - ίο 10 dioctylsebacci- - 42 - - tricresyl phosphate - 42 - triethyl citrate ---- 32 - tributyl citrate _ 32 - tris (2-butoxy - - - - _ _ 42 ethyl) phosphate average weight 13.29 13.16 13.25 13.45 13 .42 13.57 13.03 per slice (grams)

The disks obtained in this way were each placed in sand, the water content of which was about 16.7%, after which the percentages and the weight of the diffused active substance were measured periodically.

5 The results of the measurements are summarized in the table below.

gabel PD

9th day 35th day 60th day% mg% mg% mg 16A 18.1 480 52.1 1385 62.1 1650 16B 24.1 635 51.7 1360 65.0 1710 160 26.4 700 48.1 1275 60.0 1590 16D 13.8 370 35.3 950 46.7 1255 16E 22.0 590 43.4 1165 47.1 1265 163? 25.1 680 54.9 1490 66.5 1805 16G 52.4 1365 82.3 2145 89.8 2340

Experiment 17: Three series of preparations 17A, 17B and 170 according to the invention were prepared using the procedure as indicated under experiment 2 by heating at a temperature of 125 ° C for 10 minutes. The preparations prepared in this way were in the form of discs with a diameter of 90 mm and a thickness of 2 mm and 800 3 9 95 -22- showed the following compositions (the numbers indicate percentages by weight):

gabel EE

Preparation 17A 17B 170 butacarboxime 20 - methomyl - 20 - thiophanox 20 polyvinyl chloride 38 38 38 dioctyl phthalate 42 42 42 average weight per 13 »95 13.84 13.93 disk (gram)

The disks obtained in this way were each placed in sand, which had a water content of about 16.7% -3, after which the percentages and weight of the diffused active substance were measured periodically.

The results of these measurements are summarized in the table below.

gabel EF

9th day 35th day 60th day% mg% mg% mg 17A 0.6 17 2.3 64 5.1 142 17B 24.7 685 52.4 1450 65.6 1760 170 4.5 125 17.0 475 21.7 605

Test 18: Seven sets of preparations 18A to 180 were prepared using the procedure as indicated in Test 2 (15 minutes at 125 ° C) using insecticides outside the scope of the invention.

The preparations prepared in this manner were in the form of discs of 90 mm in diameter and 2 mm in thickness and exhibited the following compositions (the numbers indicate percentages by weight): 800 3 9 95 -23-

Table GG

Preparation 18A 18B 18C 18D 18E 18P 18G

cart aryl (b) 20 chlorpyrifos (c) - 20 diazinon (d) .- - 20 - fenthion (e) --- 20 --- malathion (f) ---- 20-- naled (g) --- --20- temepiios (h) - _ 20 polyvinyl- 38 38 38 38 38 38 38 38 chloride dioctyl phthalate 42 42 42 42 42 42 42 42 average 13.93 13.38 13.98 13.94 14.02 13.86 13.96 weight per disc (gram) (b) cx-naphthyl N-methyl carbamate (c) 0- (3,5,6-trichloro-2-pyridyl) -0,0 O-diethylthiophosphate (d) 0- (2- n-propyl-6-methyl-4-pyrimidinyl) -0,0-diethylthio-phosphate 5 (e) 0- (3-methyl-4-methylthiophenyl) -0,0-dimethylthiophosphate (f) S - / "1, 2-bis (ethoxycarbonyl) ethyl 7-0,0-dimethyldithio-phosphate (g) 0- (1,2-dibromo-2,2-dichloroethyl) -0,0-dimethylphosphate (h) 0.0 '- (thiodiphenylene- 4,4'-diyl) -0,0,0 ', 0'-tetramethyl-10 bis (thiophosphate), this substance is often referred to as "Abate".

The disks formed in this way were each placed in sand, which had a water content of about 16.7%, after which the amounts of diffused active substance were measured after 9 days, 35 days and 60 days.

In each of the cases and at each time of measurement, it was not possible to find an active substance release of more than 0.05% of the amount used. Test 19: A preparation according to the invention was prepared using the method described in Test 2 by heating at a temperature of 125 ° C for 15 minutes using the following ingredients: 800 3995 -dfie-

Butocarboxime 35 »3%

Polyvinyl chloride 35 »0%

Bioctyl Phthalate 19 »8% PYA Copolymer (a" ') 9 »9% 5 (a"') Polyvinyl acetate which was hydrolyzed 88% to polyvinyl alcohol and a viscosity of 18 cP in a 4% aqueous solution at showed a temperature of 20 ° C.

Bit preparation was formed into 4 mm thick plates which were cut in such a way as to obtain 4 mm dice-shaped granules.

The grains were located near the base of rose bushes of the Red variety. Favorite, 15 of which were in clayey siliceous soil in the Yienne department in France.

Three doses were used: 30 g, 45 g and 67 g per rose bush. Each week, each rose bush was poured three times with 6 liters of water each. After 15 days, the leaves of the rose bushes were crushed and extracted to determine the insecticide content. In addition, the following contents could be determined in this way:

Bosis of 30 g 34 ppm 25 Bosis of 45 g 60 ppm

Bosis of 67 g 75 ppm

In addition, these levels were found to be sufficient to prevent the proliferation of aphids on the plants.

Test 20: The following six formulations 20A to 20F according to the invention were prepared using the procedure as indicated under Test 2 by heating at a temperature of 125 ° C for 15 minutes using the following ingredients (the numbers indicate 35 percentages): 800 3 9 95 -25-

Isabel HH

Preparation 20A 20B 20C 20D 20E 20E

technical buto 35.3 23.5 14.7 35.3 23.5 14.7 cartoxime polyvinyl chloride 38.8 45.9 51.2 35.0 35.0 35.0 dioctyl phthalate 35.9 30.6 34, 1 19.8 27.7 33.5 solubilized - - - 9.9 13.8 16.8 corn starch (i) (i) Starch modified by carboxymethylation and pre-gelatinization.

These preparations were formed into 4 mm thick plates, which were then cut in such a way as to obtain 4 mm dice-shaped grains.

The granules of each preparation were spread on the surface of the soil in pots with a diameter of 11 cm, in which one plant of the species Hibiscus rosasinensis 10 grew each time. After spreading, the grains were slightly covered with soil and each jar was poured with 1 liter of water. According to the calculation, the amount of each preparation corresponded to 50 mg butocarboxime per jar: 2QA and 20D: 167 mg 15 20B and 20E: 250 mg 20C and 203? : 400 mg

The plants were infested with aphids of the species Myzus persicae, after which the insecticidal activity was measured periodically for 35 days. 20 plants per preparation were used each time.

The recorded results are summarized in the table below and expressed in percentages of dead insects based on the number established on the first day. The values reported are averages determined for each case on a number of five plants.

800 3 9 95 -26-

Table II

Moment of 20A 20B 200 20D 20E 2QF

the measurements _ _ _ _ _ _ 5th day 55 59 4-9 57 86 69 7th day 71 76 69 79 95 89 12th day 76 75 62 82 91 90 16th day 95 84 79 90 96 94 20th day 90 79 77 89 95 90 24th day 93 80 85 85 93 95 28th day 87 79 74 77 82 74 35th day 79 74- 72 69 79 67 800 1995

Claims (19)

1. Systemic insecticidal composition consisting of a rigid or flexible homogeneous solid mass of A - an insecticidal substance, 2. A composition according to claim 1, characterized in that it contains the insecticidal substance A in an amount of 5 to 50 parts by weight per 100 parts by weight of the preparation. 3. A composition according to claim 1 or 2, characterized in that it contains the insecticidal substance A in an amount of 10 to 40 parts by weight per 100 parts by weight of the preparation. 4. A composition according to any one or more of the preceding claims, characterized in that it contains the polyvinyl chloride B in an amount of 20 to 70 parts by weight per 100 parts by weight of the preparation. Preparation according to one or more of the preceding claims, characterized in that it contains the polyvinyl chloride B in an amount of 30 to 50 parts by weight per 100 parts by weight of the preparation. 5 - a polyvinyl chloride with a molar mass of more than 10,000, 0. a regulating agent belonging to the hydrophobic excipients, D - optionally, an additional regulating agent belonging to the hydrophilic excipients and powder fillers, characterized, that the insecticidal substance A consists of an oxime carbamate of the formula R-0-I-0-G 0-NH-GEU 3% in which a monovalent residue S'X- or R'-X-OCSOCH "1) -15, wherein X represents a sulfur atom or a sulfonyl group, R 'represents a methyl or ethyl group and R "and R" * each independently represent a hydrogen atom or a methyl or ethyl group and R represents a methyl, ethyl, isopropyl or tert.butyl group. Preparation according to one or more of the preceding claims, characterized in that it contains the controlling agent 800 3 9 95 -αο agent G in an amount of 15 to 70 parts by weight per 100 parts by weight of the preparation. 7. A composition according to any one or more of the preceding claims, characterized in that it contains the controlling agent C in an amount of 20 to 55 parts by weight per 100 parts by weight of the preparation. 8. A composition according to any one or more of the preceding claims, characterized in that the insecticidal substance A is 2- (N-methylcarbamoyloxyimino) -2-methylthioethane, 2- (N-methylcarbamoyloxyimino) -3-methylthiobutane, 2- (N-methylcarbamoyloxyimino) -2-methylsulfonylbutane and / or 2- (N-methylcarbamoyloxyimino) -5,3-dimethyl-1-methyl-thiobutane. 9. A composition according to any one or more of the preceding claims, characterized in that the insecticidal substance is 2- (N-methylcarbamoyloxyimino) -3-methylthiobutane. 10. A composition according to any one or more of the preceding claims, characterized in that the controlling agent C consists of one or more polymers with a low molar mass, chlorinated paraffins and / or heavy esters. 11. A composition according to any one or more of the preceding claims, characterized in that it comprises a hydrophilic excipient as an additional regulating agent consisting of one or more water-miscible, water-soluble or dispersible polymers, polyols and / or esters and / or from one or more polyoxalkylation products. Preparation according to one or more of the preceding claims, characterized in that the preparation 30 has any shape in the form of a rigid or flexible, compact, homogeneous solid mass. 13. A process for preparing a preparation according to any one or more of the preceding claims, characterized in that the polyvinyl chloride B in powder form is mechanically mixed at ambient temperature with the components A and O of the preparation to form a dry powder or a flowing paste, which is then converted into a homogeneous solid mass by molding, injection molding or casting or by heating to the gelation temperature of the mixture. 800 3 9 95 -29- Process for preparing a preparation according to one or more of claims 1 to 12, characterized in that the components A, B and 0 are dissolved in a volatile solvent, which is then heated at a temperature which is increased to a greater or lesser degree and / or evaporates under reduced pressure. 15. Process for preparing a preparation according to one or more of claims 1 to 12, characterized in that the polyvinyl chloride is dispersed in the form of a sol in the preheated liquid mixture of components B and C and that after obtaining a homogeneous dispersion, allow the mixture to cool. 16. Process for preparing a preparation according to one or more of claims 1 to 12, characterized in that the components A and O are incorporated in vinyl chloride or a prepolymer of this compound and then after addition of a catalyst a polymerization of the mixture. Method for preparing a preparation according to one or more of claims 1 to 12, characterized in that a solid mass of polyvinyl chloride in the desired form is introduced into the liquid component A, which optionally it contains component C, if it is not already present in the polyvinyl chloride and allows all liquids to penetrate into the polyvinyl chloride mass for a period inversely proportional to the temperature. 18. Process according to claim 17, characterized in that the constituents A + 0 are introduced into a container serving as packaging, which is impermeable to said constituents A + C and whose internal volume is adapted to maximize the liquid mixture with contacting the solid mass surface of the polyvinyl chloride, after which the package is closed and then stored for a sufficient period of time so that it will no longer contain any free liquid at the end of the storage period. A method for controlling insects, characterized in that a preparation according to one or more of claims 1 to 12 is used as a systemically acting insecticidal preparation in water or in the soil and thus a release of the active creates dust by controlled diffusion. *** # 800 3 9 95