CH647386A5 - SYSTEMIC INSECTICIDE COMPOSITIONS WITH CONTROLLED DIFFUSION, METHOD FOR THE PRODUCTION AND USE THEREOF. - Google Patents

Description

The present invention relates to systemic insecticide compositions which allow controlled diffusion of the active ingredient in water or soil, and to methods of making these compositions.

The compositions provided by the present invention contain a polymeric carrier and a systemic insecticide substance from the group of oxime carbamates.

It is known to include active ingredients in a polymer matrix in order to allow slow diffusion in water or in the soil: in this way, algicides (anonym, Chem. Eng. News, 1972, 50, No. 23, 68; Cardarelli & Bille, Rep. 1, Proj. 121, Creative Biol. Lab., Baberton, 1976), fungicidal (US Patents 3,269,900 and 3,278,371), nematicidal (Cardarelli & Feldmesser, Proc. Control Rei. Pest. Symp., Dayton, 1975, 386), herbicidal (U.S. Patents 3,269,900 and 3,343,941; British Patent 1,502,441; Canadian Patent 846,785; French 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 & Coll., Weed Sei., 1973, 21, 318 ; Sinclair, Env. Sei. Technol., 1973, 7,955; Cardarelli, Control Rei. Pest, Formul., CRC Press., 1976), molluscicides (Cardarelli, Control Rei. Pest. Formul., CRC Press., 1976) and antibacterial (U.S. Patent 4,007,251; French Patent

2,016,818) compositions.

This method is used relatively little with regard to insecticides. Compositions are known which contain a polymer and dichlorvos (Miles & Coll., J. Agr. Food Chem., 1962, 10, 240), but these are designed to release a volatile insecticide into the atmosphere.

These compositions cannot be used in water and soil, since this active ingredient is hydrolyzed very easily and very quickly. Furthermore, such compositions have been based on other organophosphorus compounds such as azinphos, bromophos, chlorpyrifos, demetone, diazinon, dimefox, dimethoate, fenitrothion, fenthion, malathion, mevinphos, monocrotophos, naled, parathion, temephos and trichlorofon or on the basis of oranglor compounds, Dieldrin, Endrin, Hep-tachlor, Isodrin, Lindane and Methoxychlor (US Patents 3,269,900 and 3,590,119; Canadian Patent 846,785; French Patent 2,016,818; 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. Series, 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).

Aryl or heteroaryl carbamates such as dioxacarb, isolane, dimetilane, carbofuran and various substituted phenyl carbamates have also been used (U.S. Patent

3,269,900; British Patent 1,502,441; Canadian Patent 846,785; French Patents 2,016,818 and 2,279,336).

None of these substances is the same as plants of 5

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chem interest like the oxime carbamates; the former cannot be used in the compositions according to the invention, since they are released far too little in the water and in the soil, as shown in one of the tests. In contrast, the oxime carbamates diffuse very easily out of the compositions according to the invention; they also work from the roots of the plants, spread over all their living parts and thus protect them against insect attack.

Compositions using aldicarb and a polymeric carrier are known (French Patent 2,279,236; Stockes & Coll., J. Agr. Food Chem., 1973, 21.103), but this substance is extremely toxic (LD 50 = 0.9 mg / kg), which makes such compositions very dangerous and largely negates their advantages. Compositions based on aldicarb are also known, which comprise a paper support and a polyethylene glycol top layer (Ciba-Geigy, British patent

1 477 261), but besides their high toxicity their industrial execution is involved, their application in atomizing machines is difficult and the application to the places to be treated is not easy, especially under windy conditions.

Granules consisting of a polymeric carrier and an oxime carbamate such as methomyl (French patent 2 016 818) have also been used, but the polymer acts in this type of heterogeneous granulate by adsorption, and the amount of active substance which can be incorporated therein depends on the specific surface area of this polymer, that should therefore be porous; this leads to concentration restrictions and difficulties in regulating the levy.

The applicant has now found that it is possible to produce homogeneous compositions on a polyvinyl support which contain an oxime carbamate which is considerably less toxic than aldicarb and which compositions allow this carbamate to diffuse in water or soil at a controlled rate to obtain. The invention accordingly relates to systemic insecticide compositions which consist of a solid, homogeneous, hard or soft mass and

A - an insecticidal substance,

B - a polyvinyl chloride with a molecular weight above 10,000 and

C - contain a hydrophobic diluent which regulates the release of the insecticidal substance, which are characterized in that the insecticidal substance A consists of an oxime carbamate of the formula

Rj-Ç = N-O-CO-NH-ch3 (i)

R2

where Rt is a monovalent group of the formula R'X or R'-C-CCR ") (R '"), in which X represents a sulfur atom or a sulfonyl radical, R' represents a methyl or ethyl radical, and R 'and R '"independently of one another represent a hydrogen atom or a methyl or ethyl radical, and R2 represents a methyl, ethyl, isopropyl or tertiary butyl radical.

The systemic insecticidal substances defined above are in particular in patents of Ciba-Geigy (France

2,150,185; USA 3 832 400), the consortium for the electrochemical industry (USA 3 816 532), Diamond Shamrock Corp. (U.S. 3,875,232), Dupont de Nemours & Co (U.S. 3,576,834, 3,639,633 and 3,647,861) and Kumiai Chemical Industry Co., (Japan 72.17 993).

The following are the best known, for example:

647 386

2-N-methylcarbamoyloxyimino-2-methylthioethane

(Methomyl)

2-N-methylcarbamoyloxyimino-3-methylthio-butane

(Butocarboxime) 2-N-methylcarbamoyloxyimino-3-methylsulfonyl-butane

(Butoxycarboxime) 2-N-methylcarbamoyloxyimino-3,3-dimethyl-

I-methylthio-butane (Thiofanox).

The butocarboxime defined above is preferred as an insecticidal substance in the compositions according to the invention. Insecticidal substance A is preferably present in a proportion by weight of between 5 and 50 parts per 100 parts of composition; this proportion is particularly preferably between 10 and 40 parts.

The polyvinyl chloride B is preferably present in a proportion by weight of 20 to 70 parts per 100 parts of composition; this proportion is particularly preferably between 30 and 50 parts.

The addition of a hydrophobic diluent makes it possible, depending on the type and amount thereof, to vary the rate at which the insecticidal substance is released; this diluent should therefore be chemically inert to the insecticide. The hydrophobic diluents are selected from compounds which have no hydrophilic function and are known in the plastics industry to have plasticizing properties. Such compounds are, for example, low molecular weight polymers, chlorinated paraffins and higher esters.

The diluent is preferably present in a proportion by weight of 15 to 70 parts per 100 parts of composition; this proportion is particularly preferably between 20 and 55 parts.

Examples of low molecular weight polymers are those which are obtained by homopolymerization or copolymerization of the following monomers:

(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 / dimethylmaleiate, vinyl acetate / allyl acetate, vinyl chloride / styrene, vinyl chloro-chloride / allyl chloride / allyl chloride / Vinyl acetate.

Polyester which has been neutralized by esterification with an alkanol, such as those obtained by the following condensations, glycerol / azelaic acid, glycerol / phthalic acid, propylene glycol / adipic acid and propylene glycol / sebacic acid may also be mentioned as preferred.

The following are examples of higher esters:

(1) Monoesters formed from alkanols and alkanoic acids or alkenes, such as, for example, ethyl, isopropyl, butyl or isobutyl laurate, myristate, palmitate, stearate, undecanoate and oleate.

(2) Diesters formed from alkanols and hydrocarbons with two carboxyl groups, such as, for example, dialkyl adipates such as dioctyl adipate and dinonyl adipate, dialkylse bacinates such as dibutyl sebacinate, dipentyl sebacinate and diocytyl sebacinate, dialkylazelainate such as dioctyl benzylateate, dioctyl benzylate date, cyl phthalate, bis-undecyl phthalate, bis-dodecyl phthalate, bis-tridecyl phthalate, bis-tetradecyl phthalate and dicetyiphthalate.

(3) Diesters formed from optionally alkyl-substituted phenols and hydrocarbons with two carboxyl groups, such as, for example, diaryl phthalates such as diphenyl phthalate and dicresyl phthalates.

(4) From optionally alkyl-substituted cycloalkanols and hydrocarbons with two carbocyl groups ge3

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647386

formed diesters such as dicyclohexyl phthalate and bis (methylcyclohexyl) phthalate.

(5) Diesters formed from phenylalkanols and hydrocarbons with two carboxyl groups, such as dibenzyl sebacinate.

(6) Diesters formed from alkanediols and hydrocarbons with a carboxyl group, such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

(7) Triesters formed from optionally alkyl-substituted phenols and phosphoric acid, such as, for example, triphenyl phosphate, tris (4-tert-butylphenyl) phosphate and tricresyl phosphate.

(8) Triesters formed from alkanols and phosphoric acid, such as trioctyl phosphate.

Other hydrophilic diluents with a weight fraction of up to 50 parts per 100 parts of composition can also be present as additional regulating agents. They are selected from water-miscible, soluble or dispersible compounds which are physically compatible with insecticide A, polyvinyl chloride and the hydrophobic diluent.

The following are examples of such hydrophilic diluents:

(1) Polymers and copolymers of vinyl alcohol such as polyvinyl alcohol and the polyvinyl alcohol / polyvinyl acetate copolymer.

(2) polyvinyl pyrrolidones.

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

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

(5) Alkanetriols, such as glycerol, and their monoesters formed with alkanoic or alkenoic acids.

(6) Esters formed from aliphatic hydroxy acids and lower alkanols, such as trimethyl, triethyl, tripropyl and tributyl citrate.

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

The powdered fillers are selected from those which are inert to water or are otherwise soluble or dispersible in water, depending on whether one wishes to slow down or accelerate the rate of diffusion of the active ingredient.

Powdery fillers include carbon black, rock flours such as those made from slate, clay, marble, kaolin, talc, silica or attapulgite, organic salts such as magnesium, zinc, calcium and sodium acetate, -propionate, -ci-tread, -adipate, - maleate, sebacinate, palmitate and stearate, inorganic salts such as calcium and magnesium silicate and carbonate and such as sodium or potassium chloride, sodium or calcium sulfate, potassium nitrate and potassium or ammonium phosphate; furthermore, the sodium or calcium salts of alkylarylsulfonic acids, cellulose and their derivatives such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, carbohydrates such as cereal flour, starch, dextrin and the sugars, amino acids such as glutamic acid, casein and protein hydrolyzates as well as various, the expert known organic or inorganic pigments.

The compositions according to the invention are in the form of solid, homogeneous, compact, hard or soft masses, the shape of which is not critical. For example, they can be in the form of plates, sheets, tapes, tubes, rods or granules.

The structure of the mass representing the composition is also not critical; this structure can be compact, fibrous, cellular or spongy, for example.

If the compositions according to the invention come into contact with the soil or with water, they release 50% of the insecticidal substance in a very regular manner over a period varying between about 2 and 200 days. The efficiency of the compositions according to the invention with respect to the total amount of the insecticidal substance contained in the composition is excellent, since after a more or less long period practically all of the insecticidal substance is released.

The compositions according to the invention can be produced by several processes.

According to a first process, the components are mechanically mixed using powdered polyvinyl chloride at room temperature. Depending on the proportions of the components, a dry powder or a flowable paste is obtained, i.e. a "plastisol". The dry powder is converted into a solid, homogeneous mass by pressing, extruding, spraying or pouring, as in the case of a conventional powdered plastic. In the case of a flowable paste, the mixture is heated until it gels and then a solid, homogeneous mass is obtained after cooling; the rate of diffusion of the active substance hardly changes with the temperature and / or the duration of the heating.

According to a second process, constituents A, B and C of the composition are dissolved in a volatile solvent, it being possible for the pulverulent fillers which may be present to be kept in suspension by stirring. After evaporation of the volatile solvent, which can take place at more or less elevated temperature and more or less reduced pressure, the mixture solidifies and a homogeneous mass is obtained which retains only a small proportion of solvent.

According to a third method, the polyvinyl chloride is dispersed in the sol state in the previously heated mixture of constituents A and C. A solid, homogeneous mass is obtained on cooling.

According to a fourth method, components A and C are introduced into vinyl chloride or a liquid prepolymer of this compound. After addition of a catalyst, polymerization is carried out according to methods known to the person skilled in the art.

According to a fifth method, a solid mass of polyvinyl chloride, which may have the shape desired for the finished composition, is introduced into the liquid mixture of components A + C. Component C may initially be wholly or partly in polyvinyl chloride. If the composition is to contain a powdery filler, this is first introduced into the polyvinyl chloride. The active ingredient A and the auxiliary C, if the latter is mixed with the active ingredient, penetrate into the polyvinyl chloride composition; this penetration requires a time which is inversely proportional to the temperature at which this step is carried out.

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

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647 386

The following experiments demonstrate the importance of the compositions according to the invention.

Trial 1:

A polyvinyl chloride composition plasticized with dibutyl phthalate is used, the plasticizer content of which is approximately 36% by weight. This mass is formed by extrusion into a tube, the outer and inner contours of which are lenticular in cross section; the outer width is 28 mm and the greatest thickness is 3.2 mm over a length of 45 mm; the width of the inner walls is 20 mm; such a mass weighs 7.65 grams. These masses are individually enclosed in a sealed bag, which was evacuated before closing and each contains one of the following liquids (quantities in grams):

Table I

Composition 1A 1B IC

Butocarboxime, pure 5 3.5 2.5

Dibutyl phthalate - 1.5 2.5

After storage for one month at a temperature of 40 ° C, the bags are opened, each of which provides a mass of the following homogeneous composition (percentages by weight):

Table II

composition

1A

1B

IC

Butocarboxime

39.5

27.7

19.8

Polyvinyl chloride

38.7

38.7

38.7

Dibutyl phthalate

21.8

33.6

41.5

Trial 2:

Finely powdered polyvinyl chloride is used for plastisol purposes and mixed with 83% pure technical butocarboxime and dioctyl phthalate in the following proportions:

Butocarboxime, technical: 20% by weight

Polyvinyl chloride: 40% by weight

Dioctyl phthalate: 40% by weight

The liquid paste obtained is poured to a thickness of 2 mm in petri dishes and placed in thermostatic drying ovens at temperatures varying between 115 and 135 ° C. for periods varying between 5 and 30 minutes. In all cases, a homogeneous plastic mass is obtained, and the active substance contents determined by analysis are noted as a percentage of pure active substance as follows.

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 mins

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 analyzes also make it possible to determine that only the volatile impurities in the technical material have been lost in the course of the heating.

20 Experiment 3:

Three rows 3A, 3B and 3C compositions according to the invention are produced by the procedure described in experiment 2, with heating to 125 ° C. for 15 minutes.

25 The compositions thus produced have the shape of disks with a diameter of 32 mm and a thickness of 12 mm and are composed as follows (data in percent by weight):

Table IV

Compositions

3A

3B

3C

Butocarboxime, technical

10th

20th

40

Polyvinyl chloride

45

40

30th

Dioctyl phthalate

45

40

30th

Weight of the slices, each (gram) 8.53 8.19 7.80

40

The slices produced in this way are each suspended in a water-filled vessel and from time to time the amount of active ingredient passed into the water is measured.

The values recorded in this way are summarized in the table below (percent diffused active ingredient, based on the active ingredient incorporated into the composition, and weight of the diffused active ingredient in milligrams).

Table V

Measured by

3A

3B

3C

%

mg

%

mg

%

mg

5 days

12

102

13

211

19th

593

9 days

16

137

18th

295

25th

774

20 days

24th

206

26

429

37

1160

51 days

36

309

41

676

53

1647

114 days

49

417

54

881

56

2068

194 days

61

518

65

1068

77

2412

Experiment 4:

Disks 4A, 4B and 4C are used, which are similar to those described in the content of about 65% and measures Prosuch 3 from time to time, and each have the same percentage of diffused active ingredient.

have composition. The measurement results are in the table below

These slices are put together in sand with a was-put together.

647 386

6

Table VI

Measured by

4A

4B

4C

%

mg

%

mg

%

mg

20 days

11

93

13

237

14

440

51 days

22

188

27th

496

31

967

114 days

34

292

38

695

42

1317

194 days

43

365

47

869

51

1604

Experiment 5:

The following composition is prepared (data dioctyl phthalate 40

in percent by weight): The procedure is as described in experiment 2 (15 minutes

Butocarboxim, technically 20 at 125 ° C) and receives discs with a diameter of 90 mm

Polyvinylchloride 40 15 different thicknesses:

Table VII

Compositions

5A

5B

5C

5D

5E

Thickness in mm

1

2nd

3rd

5

7

Weight in grams

6.8

13.8

20.9

34.8

48.9

These slices are each laid in sand with a water. The measurement results in the table below are approx. 20% and measure the pro from time to time.

percentage of diffused active ingredient.

Table VIII

Measured by

5A

5B

5C

5D

5E

%

mg

%

mg

%

mg

%

mg

%

mg

8 days

19.2

260

13.2

364

9.0

375

8.4

525

7.8

763

15 days

37.1

505

25.7

709

19.7

824

16.8

1170

14.4

1407

22 days

54.5

741

37.1

1024

28.7

1200

24.5

1705

21.0

2054

29 days

65.2

887

46.7

1289

36.5

1526

30.5

2123

25.7

2515

60 days

80.8

1100

62.9

1736

51.5

2153

43.7

3040

35.1

3433

90 days

89.8

1220

76.6

2115

67.0

2800

55.9

3890

45.3

4430

Experiment 6:

To prepare the following compositions 6A and 1.5 mm thick, the procedure is as in Experiment 2 to 6D, in the form of disks 90 mm in diameter (15 minutes at 125 ° C.) (data in percent by weight):

Table IX

Compositions

6A

6B

6C

6D

Butocarboxim, tech

niche

20th

20th

20th

20th

Polyvinyl chloride

60

50

40

30th

Dioctyl phthalate

20th

30th

40

50

Weight (grams)

13.83

13.75

13.76

13.56

The slices are placed in sand with a weight of water.

content of about 20% and measures the pro- 55 from time to time. The measurement results are summarized in the table below, percentage of diffused active ingredient with simultaneous determination.

Table X

Measured by

6A

6B

6C

6D

%

mg

%

mg

%

mg

%

mg

8 days

0.4

11

8.4

231

18.0

495

19.8

537

15 days

3.0

83

15.0

412

32.8

890

37.7

1023

22 days

6.6

183

22.8

628

45.5

1251

55.7

1512

29 days

9.0

249

26.9

740

54.5

1501

67.7

1835

60 days

17.9

495

41.3

1137

71.0

1954

86.8

2355

90 days

25.1

693

54.5

1497

81.1

2232

98.0

2659

7

647 386

Experiment 7:

To prepare the following compositions 7A and 7B, which are in the form of disks 90 mm in diameter and 2 mm in thickness, the procedure is as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight): s

Table XI

Compositions 7A 7B

10th

Butacarboxim, technical 20 20

Polyvinyl chloride 40 40

Dioctyl phthalate 35 20

Tris-2-butoxyethyl phosphate 5 20

Weight (grams) 13.63 13.52 15

The slices are each suspended in a water-filled container and the percentage of diffused active substance is measured from time to time. 20th

The results are summarized in the table below.

Table XII

Measured by

7A

7B

%

mg

%

mg

2 days

12

323

20th

512

5 days

50

1330

53

1450

12 days

74

2025

83

2273

Table XIII

Compositions 8A 8B

Butocarboxime, technical 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) 30% polyvinyl acetate hydrolyzed to polyvinyl alcohol with a viscosity of 98 centipoise in 4% aqueous solution at 20 ° C.

You hang the slices in a water-filled container and measure the percentage of active ingredient that has passed into the water from time to time.

The measurement results are summarized in the table below.

Table XIV

Measured by

8A

8B

%

mg

%

mg

5 days

18.2

615

17.5

670

31 days

53.2

1800

46.4

1770

93 days

81.4

2750

66.3

2530

173 days

98.2

3320

82.4

3145

Experiment 8:

To prepare the following compositions 8A and 8B, which are in the form of disks of 32 mm in diameter and 12 mm in thickness, the procedure is as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight):

Experiment 9:

To prepare the following compositions 9A to 9F, which are in the form of disks 90 mm in diameter and 2 mm in thickness, the procedure is as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight):

Table XV

Compositions

9A

9B

9C

9D

9E

9F

Butocarboxime, technical

20th

20th

20th

20th

20th

20th

Polyvinyl chloride

37

37

34

34

30th

30th

Dioctyl phthalate

37

37

34

34

30th

30th

PVA polymer (a ')

6

-

12

-

20th

-

PVA polymer (a ")

-

6

12

20th

Weight (grams)

13.60

13.57

13.58

13.60

13.63

13.63

(a ') 50% polyvinyl acetate hydrolyzed to polyvinyl alcohol with a viscosity of 98 centipoise in 4% aqueous solution at 20 ° C.

(a ") 70% polyvinyl acetate hydrolyzed to polyvinyl alcohol with a viscosity of 88 centipoise in 4% aqueous solution at 29 ° C.

The slices are each filled with water. The measurement results are in the table below

Take a hold and measure the percentage dif- compiled from time to time.

well-founded active ingredient.

Table XVI

Measured by

9A

9B

9C

9D

9E

9F

%

mg

%

mg

%

mg

%

mg

%

mg

%

mg

2 days

15

410

22

590

16

440

27th

736

18th

496

33

897

5 days

28

755

30th

817

29

782

48

1314

34

924

61

1668

12 days

49

1340

51

1390

53

1445

77

2090

63

1712

91

2473

647 386 B

Trial 10:

To prepare the following compositions 10A and 2 mm thick, the procedure is as in Experiment 2 to 10E, in the form of disks 90 mm in diameter (15 minutes at 125 ° C.) (data in percent by weight):

Table XVII

Compositions

10A

10B

10C

10D

10E

Butocarboxime, technical

20th

20th

20th

20th

20th

Polyvinyl chloride

40

40

40

40

40

Dioctyl phthalate

35

35

30th

20th

20th

Polyethylene glycol 400

5

-

10th

20th

Ethyl triethylene glycol

-

5

20th

-

Weight (grams)

13.57

13.51

13.61

13.32

13.50

The slices are each hung in a water-filled container. The measurement results are summarized in the table below and from time to time the percentage diffused is compiled.

Active ingredient. 20th

Table XVIII

Measured by

10A

10B

10C

10D

10E

%

mg

%

mg

%

mg

%

mg

%

mg

2 days

11

295

13

353

13

354

13

341

40

1045

3 days

17th

466

-

-

19th

512

-

-

87

2354

5 days

26

714

43

1160

33

904

46

1230

100

2690

12 days

48

1308

64

1707

56

1532

71

1886

Experiment 11:

The following compositions IIA and 11B, which are in the form of disks 90 mm in diameter and 2 mm in thickness, are prepared as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight).

Table XIX

Compositions IIA IIB

Butocarboxime, technical 20 20

Polyvinyl chloride 40 40

Dioctyl phthalate 35 20

Tributyl citrate 5 20

Weight (grams) 13.68 13.59

The slices are each suspended in a water-filled container and the percentage of diffused active substance is measured from time to time.

The measurement results are summarized in the table below.

Table XX

Measured by

IIA

IIB

%

mg

%

mg

2 days

13

350

20th

550

5 days

49

1350

52

1430

12 days

74

2030

76

2080

Experiment 12:

To prepare the following compositions 12A to 12F, which are in the form of disks 90 mm in diameter and 2 mm in thickness, the procedure is as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight):

Table XXI

Compositions

12A

12B

12C

12D

12E

12F

Butocarboxime, technical

20th

20th

20th

20th

20th

20th

Polyvinyl chloride

37

37

34

34

30th

25th

Dioctyl phthalate

37

37

34

34

30th

25th

Corn cobs

6

12

-

20th

Wheat starch

-

6

-

12

-

30th

Weight (grams)

13.55

13.60

13.64

13.56

13.70

13.52

65

The slices are hung in a water-filled container. The measurement results are in the table below and measure the percentage of diffused from time to time.

Active ingredient.

9

Table XXII

647 386

Measured by

12A

12B

12C

12D

12E

12F

%

mg

%

mg

%

mg

%

mg

%

mg

%

mg

2 days

16

427

17th

467

16

431

19th

512

16

436

43

1170

3 days

-

-

20th

545

-

-

26

703

-

-

52

1410

5 days

36

980

30th

822

43

1167

41

1117

52

1418

80

2158

12 days

61

1660

53

1438

70

1914

79

2151

96

2636

100

2690

Trial 13:

To prepare the following compositions 13A and 2 mm thick, the procedure is as in Experiments 2 to 13F, in the form of disks 90 mm in diameter (15 minutes at 125 ° C.) (data in percent by weight):

Table XXIII

Compositions

13A

13B

13C

13D

13E

13F

Butocarboxime, technical

20th

20th

20th

20th

20th

20th

Polyvinyl chloride

37

37

34

34

30th

30th

Dioctyl phthalate

37

37

34

34

30th

30th

Methyl cellulose

6

12

20th

20th

Carboxymethyl cellulose sodium salt

-

6

-

12

-

Weight (grams)

13.56

13.55

13.56

13.49

13.61

13.48

The slices are hung in a water-filled container. The measurement results are in the table below and measure the percentage of diffused from time to time.

Active ingredient. 30th

Table XXIV

Measured by

13A

13B

13C

13D

13E

13F

%

mg

%

mg

%

mg

%

mg

%

mg

%

mg

2 days

13

347

15

412

15

400

25th

680

17th

463

43

1163

3 days

-

22

602

-

-

33

888

54

1452

5 days

37

1006

36

971

39

1052

43

1155

65

1772

87

2346

12 days

60

1636

53

1432

70

1906

79

2126

100

2706

100

2679

Experiment 14:

The following compositions 14A and 14B, which are in the form of disks 90 mm in diameter and 45 mm in thickness, are prepared as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight):

50

Table XXV

Compositions 14A 14B

Butocarboxime, technical

20th

20th

Polyvinyl chloride

37

25th

Dioctyl phthalate

37

15

Casein

6

40

Weight (grams)

13.56

13.76

The slices are each suspended in a water-filled container and the percentage of diffused active substance is measured from time to time.

The measurement results are summarized in the table below.

Table XXVI

Measured by

14A

14B

%

mg

%

mg

2 days

13

350

16

446

5 days

35

943

43

1191

12 days

56

1510

80

2213

Experiment 15:

The following compositions 15A and 15B, which are in the form of disks 90 mm in diameter and 2 mm in thickness, are prepared as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight):

Table XXVII

Compositions 15A 15B

Butocarboxime, technical 20 20

Polyvinyl chloride 50 34

Dioctyl phthalate 30 34

PVA polymer (a ") - 12

(a ") 70% polyvinyl acetate hydrolyzed to polyvinyl alcohol with a viscosity of 88 centipoise in 4% aqueous solution at 20 C."

647 386

10th

The slices are cut into four equal quarters, each weighing around 3.5 grams. The quarters are placed in the open field at a depth of 7.5 centimeters in stony clay clay soil. The average amount of rain measured during the test period was 3.15 millimeters per day. From time to time a quarter is removed from the soil and the remaining amount of butocarboxin is measured by analysis to determine the amount diffused into the soil.

The measurement results are summarized in Table 5 below.

Table XXVIII

Measured by

15A

15B

%

mg

%

mg

8 days

5

36

21st

150

15 days

9

62

40

278

25 days

12

85

59

414

36 days

19th

130

71

495

50 days

26

184

83

579

64 days

31

218

-

-

71 days

-

92

646

78 days

39

276

94

660

Experiment 16:

Seven rows 16A to 16G of the compositions according to the invention are prepared by heating to 125 ° C. under the procedure described in experiment 2 for 15 minutes.

The compositions thus produced have the shape of disks with a diameter of 90 mm and a thickness of 2 mm 25 and are composed as follows (data in percent by weight):

Table XXIX

Butocarboxime, technical

Polyvinyl chloride

Dioctyl phthalate

Dioctyl adipate

Dioctyl sebacinate

Tricresyl phosphate

Triethyl citrate

Tributy director

T ris-2-butoxyethyl phosphate

Average slice weight (grams)

16A

16B

16C

16D

16E

16F

16G

20 38 42

20 38

20 38

20 38

20 38

20 38

20 38

42

10th

10th

13.29

13.16

42

42

32

32

13.25 13.45 13.42 13.57

42

13.03

The slices produced in this way are placed in sand with a water content of approximately 16.7% and the percentage and weight of diffused active substance are measured from time to time.

The measurement results are summarized in the table below.

Table XXX

to

9 days%

mg

35 days%

mg

60 days%

mg

16A

18.1

480

52.1

1385

62.1

1650

16B

24.1

635

51.7

1360

65.0

1710

16C

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

16F

25.1

680

54.9

1490

66.5

1805

16G

52.4

1365

82.3

2145

89.8

2340

Experiment 17:

Three rows 17A, 17B and 17C of compositions according to the invention are produced by the procedure described in experiment 2, with heating to 125 ° C. for 15 minutes.

The compositions thus produced have the shape of disks with a diameter of 90 mm and a thickness of 2 mm and are composed as follows (data in percent by weight):

Table XXXI

17A 17B 17C

Butocarboxime

20th

Methomyl

-

20th

-

Thiofanox

-

-

20th

Polyvinyl chloride

38

38

38

Dioctyl phthalate

42

42

42

Average

Disc weight (grams) 13.95 13.84 13.93

65 The slices produced in this way are placed in sand with a water content of about 16.7% and the percentage and weight of diffused active substance are measured from time to time.

11

647 386

The measurement results are summarized in the table below.

Table XXXII

to

9 days

35 days

60 days

5

%

mg

%

mg

%

mg

17A

0.6

17th

2.3

64

5.1

142

17B

24.7

685

52.4

1450

. 65.6

1760

17C

4.5

125

17.0

475

21.7

605 io

Experiment 18:

Seven rows 18A to 18G of compositions are made according to the procedure described in Experiment 2 (15 minutes at 125 ° C) using insecticide substances outside the scope of the invention.

The compositions thus produced have the shape of disks with a diameter of 90 mm and a thickness of 2 mm and are composed as follows (data in percent by weight):

Table XXXIII

18A

18B

18C

18D

I8E

18F

18G

Carbaryl (b) 20 -

Chlorpyrifos (c) - 20

Diazinon (d) - -

Fenthion (e) - -

Malathion (f) - -

Naled (g) - -

Temefos (h) - -

Polyvinyl chloride 38 38

Dioctyl phthalate 42 42

Average slice weight (grams) 13.95 13.38

20th

38 42

20th

38 42

20th

38 42

20th

38 42

13.98 13.94 14.02 13.86

20 38 42

13.96

(b) N-Methylcarbamic acid-a-naphthyl ester.

(c) 0.0-Diethyl-0- (3,5,6-trichloropyridyl-2) thiophosphate.

(d) 0.0-Diethyl-0- (2-isopropyl-6-methyl-pyrimidinyl-4) thiophosphate.

(e) 0,0-Dimethyl-0- (3-methyl-4-methylthiophenyl) thiophosphate. (0 0.0-Dimethyl-S- [1,2-bis (ethoxycarbonyl) ethyl] dithiophosphate.

(g) 0.0-Dimethyl-0- (1,2-dibromo-2,2-dichloroethyl) phosphate.

(h) 0.0,0'0'-tetramethyl-0.0 '- (thiodiphenylenediyl-4,4') - bis- (thiophosphate); this substance is often referred to as "Abate".

The slices produced in this way are each placed in sand with a water content of approximately 16.7% and the amounts of active substance diffused are measured after 9 days, 35 days and 60 days.

In no case and after none of the elapsed times is an active ingredient release in excess of 0.05% of the amount used.

Trial 19:

After the procedure described in experiment 2, heating to 125 ° C. for 15 minutes, a composition according to the invention is prepared with the following constituents:

Butocarboxim: 35.3%

Polyvinyl chloride: 35.0%

Dioctyl phthalate: 19.8%

PVA polymer (a '"): 9.9%

(a "') 88% hydrolysed to polyvinyl alcohol with a viscosity of 18 centipoise in 4% aqueous solution at 20" C.

This composition is formed into 4 mm thick plates, which are cut to give cube-shaped grains with an edge length of 4 mm.

The grains are buried near the foot of rose favorites of the Red Favorite variety planted in a pebble clay soil in the Vienne department, France. Three doses are used: 30.45 and 67 40 grams per rose bush. The rose bushes are poured three times a week with 6 liters of water each. After 15 days, the rose bush leaves are subjected to grinding and extraction in order to determine their insecticidal substance content. The following contents can be determined: 45 30 gram dose = 35 ppm

45 gram dose = 60 ppm

67 gram dose = 75 ppm

It also shows that these contents are sufficient to prevent aphids from multiplying on the plants.

Trial 20:

Following the procedure described in experiment 2, heating to 125 ° C. for 15 minutes, the following compositions 55A to 20F according to the invention are prepared with the following constituents (data in percent by weight):

Table XXXIV

20A

20B

20C

20D

20E

20F

Butocarboxime, technical

35.3

23.5

14.7

35.3

23.5

14.7

Polyvinyl chloride

38.8

45.9

51.2

35.0

35.0

35.0

Dioctyl phthalate

25.9

30.6

34.1

19.8

27.7

33.5

Solubilized corn starch (i)

-

-

-

9.9

. 13.8

16.8

(i) Starch modified by carboxymethylation and pasting.

647 386

12

These compositions are formed into 4 mm thick plates, which are cut to give cube-shaped grains with an edge length of 4 mm.

The grains from the compositions are each sprinkled on the surface of the earth in 11 cm pots

20A and 20D: 20B and 20E: 20C and 20F:

The plants are infected with Myzus per-sicae aphids and the insecticidal activity is measured from time to time over 35 days. 5 plants per composition are used.

The recorded results are shown in the

Diameters, each containing a plant of the species Hibiscus rosasinen-sis; after sprinkling, cover the grains thinly with soil and then pour with one liter of water per pot; the amount of composition is calculated in each case so that it corresponds to 50 mg butocarboxime per pot:

167 mg 250 mg 400 mg

10th

summarize the table and express it as a percentage of dead insects based on the number noted on the first day; the values given represent the 15 average obtained for each composition across the 5 plants:

Table XXXV

Measured by

20A

20B

20C

20D

20E

20F

3 days

55

59

49

57

86

69

7 days

71

76

69

79

95

89

12 days

76

75

62

82

91

90

16 days

93

84

79

90

96

94

20 days

90

79

77

89

95

90

24 days

93

80

85

85

93

95

28 days

87

79

74

77

82

74

35 days

79

74

72

69

79

67

40

45

50

55

60

65

Claims (9)

647386 2nd PATENT CLAIMS 1. Systemic insecticidal compositions consisting of a solid, homogeneous, hard or soft mass and A - an insecticidal substance, B- a polyvinyl chloride with a molecular weight above 10,000 and C - contain a hydrophobic diluent which regulates the release of the insecticide, characterized in that the insecticidal substance A from an oxime carbamate of the formula R! -C = N-O-CO-NH-CH3 (I) r2 where ri is a monovalent group of the formula r'x or r'-xc (r ") (r" ') - in which x represents a sulfur atom or a sulfonyl radical, r' represents a methyl or ethyl radical and r "and r '"independently of one another represent a hydrogen atom or a methyl or ethyl radical, and r2 represents a methyl, ethyl, isopropyl or tertiary butyl radical. 2. Compositions according to claim 1, characterized in that the diluent C is selected from low molecular weight polymers, chlorinated paraffins and higher esters. 3. Compositions according to claim 1, characterized in that they contain an additional regulating agent, which is a hydrophilic diluent selected from water-miscible, soluble or di-dispersible polymers, polyols and esters and polyoxyalkylated products. 4. A process for the preparation of the compositions according to claim 1, characterized in that a powdery polyvinyl chloride B is used, which is mixed mechanically at room temperature with components A and C to form a dry powder or a flowable paste, which or which subsequently Pressing, spraying or pouring or by heating to the gelation temperature of the mixture is converted into a solid homogeneous mass. 5. The method according to claim 4, characterized in that the constituents A, B and C are dissolved in a volatile solvent and this is then evaporated at elevated temperature or reduced pressure. 6. The method according to claim 4, characterized in that the polyvinyl chloride is dispersed in the sol state in the previously heated liquid mixture of components A and C and the mixture is allowed to cool after obtaining a homogeneous dispersion. 7. The method according to claim 4, characterized in that the components A and C are introduced in vinyl chloride or a prepolymer of this compound and then, after adding a catalyst, the mixture is polymerized. 8. The method according to claim 4, characterized in that a solid mass of polyvinyl chloride of the shape desired for the finished composition in the liquid component A, which optionally contains component C, if this is not already contained in the polyvinyl chloride, and that all Liquids can penetrate into the polyvinyl chloride mass for a period inversely proportional to the temperature. 9. The method according to claim 8, characterized in that the components A and C are introduced into an impermeable packaging container, the internal volume of which is adapted to bring the liquid mixture into contact with the largest possible surface of the solid polyvinyl chloride composition, and then the packaging closes and then stores so long that it no longer contains any free liquid at the end of the storage period.