DE3027167A1 - SYSTEMIC INSECTICIDE COMPOSITIONS WITH CONTROLLED DIFFUSION, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

P.O. Box 860245 8000 Munich 86

■ 5-

Lawyer file: 31 059

17th July 1980

Airwick AG
Basel, Switzerland

Systemic controlled diffusion insecticidal compositions, methods for their Manufacture and its use

f (089) 988272 telegrams: Bank accounts: Hypo-Bank Manchen 4410122850

988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

»88274 TELEX: B» yet Vereinsbink Munich 453100 (BLZ 70020270)

983310 0524560BERGd 030067/0776 P «'« * «* Some 65343-808 (BLZ 70010080)

2-12448 / AFR 111 / -

SYSTEMIC INSECTICIDE COMPOSITIONS WITH CONTROLLED DIFFUSION, METHOD FOR THEIR PREPARATION AND THEIR USE

The present invention relates to systemic insecticide compositions, which allow a controlled diffusion of the active ingredient in the water or in the soil, as well as processes for 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 to slow diffusion in the water or in the soil: In this way, algicides (anonymous, Chem. Eng. News, 1972, £ 0, No. 23, 68; CARDARELLI & BILLE, Rep. 1, Proj. 121, Creative Biol. Lab., Baberton, 1976), fungicidal (U.S. 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 Sci., 1973, 21, 318; SINCLAIR, env. May be. Technol., 1973, 7, 955; CARDARELLI, Control ReI. Pest. Formul., CRC Press., 1976), molluscicidal (CARDARELLI, Control ReI. Pest. Formul., CRC Press., 1976) and antibacterial (U.S. Patent 4,007,251; French Patent 2,016,818) Compositions generated.

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With regard to insecticides, this process is used relatively little. They are compositions "known that contain a polymer and dichlorvos (MILES & COLL., J. Agr. Food Chem., 1962, 10, 240) but these are intended to be a volatile insecticidal agent to release into the atmosphere.

Tm water and Eoden these compositions can not be used, since this drug is very light and very rapidly hydrolyzed. Furthermore, such compositions were based on other organophosphorus compounds such as azinphos, bromophos, chlorpyrifos? Demeton, Diazinon, Dimefox, Dimethoat, Fenitrothion, Fenthion, Malathion, Mevinphos, Monocrotophos, Naled, Parathion, Temephos and Trichlörfon or on the basis of organochlorine compounds such as Aldrin, Dieldrin, Endrin, Heptachlor, Isodrin, Lindane and Methenteoxychlor 3 269 described (US and Patenteoxychlor 3 269 900 and 3,590,119; Canadian Patent 846,785; French Patent 2,016,818; CLEMENTS & ROGERS, Proc. 35. 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. Fonaul. 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 ₅ 33, 148; ROBERTS & COLL., Mosq. News, 1973, 33, 155 and I65).

Also, aryl or heteroaryl carbamates such as dioxacarb, isolane, dimetilane, carbofuran and various have become substituted phenyl carbamates used (U.S. Patent 3,269,900; British Patent 1,502,441; Canadian Patent 846,785; French patents 2 OI6 and 2 279 336).

None of these substances is of the same interest to plants as the oxime carbamates; the former are not usable in the compositions according to the invention, because they are released far too little in the water and in the soil, as shown in one of the experiments. the

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Oxime carbamates, on the other hand, diffuse very easily from the compositions according to the invention out; in addition, they work from the roots of the plants, they spread over all their living parts and protect them against insect attack.

Compositions using aldicarb and a polymeric carrier are known (French U.S. Patent 2,279,236; STOCKES & COLL., J. Agr. Food Chem., 1973 »21, 103)> however, this substance is extremely toxic (LD 50 = 0.9 mg / kg), what such. Compositions makes it very dangerous and largely negates its advantages. There are also compositions based on Aldicarb known, which has a paper backing and a polyethyleneglycol top layer (CIBA-GEIGY, British Patent 1,477,261), but is beyond their high toxicity Their industrial implementation is complicated, their application in atomizing machines is difficult and application on the areas to be treated is not easy, especially in windy conditions.

Granules were also used, which consist of a polymeric carrier and an oxime carbamate such as Methomyl (French patent 2 016 818), but in this type of heterogeneous granulate the polymer acts by adsorption, and the amount of active ingredient that can be stored therein depends on the specific surface area of this polymer, which is why should be porous; this leads to concentration restrictions and difficulties in regulating the Submission.

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

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O ₁ .

A - an insecticidal substance,

B - a polyvinyl chloride with a molecular weight over 10,000,

C - one selected from hydrophobic diluents Regulating agents and

D - optionally an additional one selected from hydrophilic diluents and powdery fillers Contain regulating agents, and which are characterized in that the insecticidal substance A from a Oxime carbamate of the formula

R C = N 0 CO NH CH, (I)

¹ I ³

R ₂

where R, among monovalent groups R ¹ X- and R'-XC (R ") (R '"), in which X is a sulfur atom or a sulfonyl radical, R' is an ethyl or methyl radical, R "is a hydrogen atom or an ethyl or methyl radical and R '"represents a hydrogen atom or an ethyl or methyl radical, and Rp is selected from ethyl, isopropyl, methyl and tert-butyl radicals.

The systemic insecticidal substances defined above are in particular in the patents of CIBA-GEIGY (FRANCE

2 150 185; USA 3 832 400), the Electrochemical Consortium Industrie (USA 3 8I6 532), Diamond Shamrock Corp. (USA 3 875 232), Dupont de Nemours & Co (USA

3,576,834, 3,639,633 and 3,647,861) and Kumiai Chemical Industry Co. (JAPAN 72.17 993).

For example, the following are best known:

2-N-methylcarbamoyloxyimino-2-methylthio-ethane (METHOMYL) 2-N-Methylcarbamoyloxyimino-3-methylthio-butane (BUTOCARBOXIM) 2-N-Methylcarbamoyloxyimino-3-diethylsulfonyl-butane

(BUTOXYCARBOXIM)

2-N-methylcarbamoyloxyimino-3,3-dimethyl-1-methylthio-butane

(THIOFANOX).

The BUTOCARBOXIM defined above is used in the Compositions as an insecticidal substance

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preferred. The insecticidal substance A is preferably between 5 and 50 parts per 100 parts of composition present weight percentage; this proportion is particularly preferably between 10 and 40 parts.

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

The addition of a regulating agent selected from among hydrophobic diluents makes it possible, depending on their nature and amount to vary the rate of release of the insecticidal substance; this regulating agent is supposed to therefore be chemically inert to the insecticide substance. The hydrophobic diluents are under compounds which do not have a hydrophilic function and are known in the plastics industry for having have plasticizing properties. Such compounds are, for example, low molecular weight polymers, chlorinated Paraffins and higher esters.

This regulating agent is preferably in a proportion by weight of 15 to 70 parts per 100 parts of composition before; this proportion is particularly preferably between 20 and 55 parts.

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

(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.

Furthermore, polyesters neutralized by esterification with an alkanol may be mentioned, such as obtained by the following condensations: glycerine / sebacic acid, glycerine / azelaic acid, glycerine / phthalic acid,

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Propylene glycol / adipic acid and propylene glycol / sebacic acid. The following are examples of higher esters:

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

(2) From alkanols and hydrocarbons with two carboxyl groups formed diesters such as dialkyl adipates such as dioctyl adipate and dinonyl adipate, dialkyl sebacates such as dibutyl sebacate, dipentyl sebacate and dioctyl sebacate, dialky azelainate such as dioctyl azelainate, and Dialkyl phthalates such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis-undecyl phthalate, bis-dodecyl phthalate, Bis-tridecyl phthalate, bis-tetradecyl phthalate and dicetyl phthalate.

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

(4) From optionally alkyl-substituted cycloalkanols and diesters formed with hydrocarbons having two carboxyl groups such as dicyclohexyl phthalate and bis (methylcyclohexyl) phthalate.

(5) Diesters formed from phenylalkanols and hydrocarbons having two carboxyl groups such as Dibenzyl sebacate.

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

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

(8) Triesters formed from alkanols and phosphoric acid, such as, for example, trioctylphosphax.

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The hydrophilic diluents acting as additional regulating agents can be added in a weight proportion of 0 to 50 parts per 100 parts of the composition are present. They are miscible, soluble or dispersible in water and with the insecticidal substance A, the polyvinyl chloride and the hydrophobic diluent are selected physically compatible compounds.

The following are examples of hydrophilic thinning agents:

(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) Polyalkanediolef such as polyethylene glycols, polypropylene glycols and polybutylene glycols.

(5) Alkanetriol? Such as glycerin, and their with alkanoic acids or alkenoic acids formed monoesters.

(6) From aliphatic hydroxy acids and lower alkanols esters formed, 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 decanol, 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 powdery fillers are selected from those which are inert to water or otherwise are soluble or dispersible in water, depending on whether the rate of diffusion of the active ingredient is slowed down or want to accelerate.

As powdery fillers kiss »rock flour such as those made of slate, clay, marble, kaolin, talc, Silicic acid or attapulgite, organic salts such as magnesium, zinc, calcium and sodium acetate, propionate, citrate,

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-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 Called calcium sulfate, potassium nitrate and potassium or ammonium phosphate; furthermore are 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 flours, starch, dextrin and the sugars, Amino acids such as glutamic acid, casein and protein hydrolysates as well as various organic ones known to the person skilled in the art or called inorganic pigments.

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

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

When the compositions according to the invention with the soil or come into contact with water, they give 50% of the insecticide on a very regular basis over a period of time varying between about 2 and 200 days. Of the Efficiency of the compositions according to the invention with reference to the total amount of that contained in the composition Insecticidal substance is excellent because, after a more or less long period of time, practically all of it Insecticidal substance is released.

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

According to a first method, one proceeds in such a way that the constituents are made using powdery Polyvinyl chloride mechanically mixed at room temperature. Depending on the proportions of the constituents, one obtains a dry powder or a flowable paste i.e. a

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"Plastisol". The dry powder is obtained by pressing, extruding, injecting or pouring as in the case of a usual one powdered plastic into a solid homogeneous Mass transferred. In the case of a flowable paste, the mixture is heated until it gels and then after the Cooling a solid homogeneous mass; the rate of diffusion of the active ingredient hardly changes with temperature and / or the duration of the heating.

The constituents are dissolved according to a second method A, B and C of the composition in a volatile solvent, with any powdery Fillers can be kept in suspension by stirring. After evaporation of the volatile solvent, whatever can take place at a more or less elevated temperature and more or less reduced pressure solidifies the mixture, 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 one Mixture of components A and C. A solid, homogeneous mass is obtained on cooling.

According to a fourth process, components A and C are brought into vinyl chloride or a liquid prepolymer this connection. After the addition of a catalyst, a polymerization is known to the person skilled in the art Methods carried out.

According to a fifth method, you bring a solid mass of polyvinyl chloride, which may be the for the finished composition has the desired shape, into the liquid mixture of the components A + C. Of the Component C can initially be wholly or partly in the polyvinyl chloride. Should the composition contain a powdery filler, this is first introduced into the polyvinyl chloride. Of the Active ingredient A and the excipient C, if the latter with the active ingredient is mixed, penetrate into the polyvinyl chloride mass; this penetration requires a time

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which is inversely proportional to the temperature at which this stage is carried out.

According to a variant of this process, the polyvinyl chloride composition and the components A + C are added a container serving as packaging, which is impermeable to this mixture and its internal volume on it is matched, the liquid mixture with the largest possible surface of the polyvinyl chloride in contact bring to. Penetration takes place during the storage time, and the packaging contains one according to the invention Composition at the moment when it is opened for use.

The following experiments demonstrate the importance of the compositions according to the invention. Experiment 1 ; A polyvinyl chloride composition which has been plasticized with dibutyl phthalate and whose plasticizer content is about 36% by weight is used. This mass is formed into a tube by extrusion, its outer and inner contours. are lenticular in cross-section; the outside width is 28 mm and the greatest thickness is 3.2 ram 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 tight bag, which has been evacuated before closing and contains one of the following liquids (quantities in grams):
Table I.

composition IA IB IC Butocarboxim, pure
Dibutyl phthalate 5 3.5
1.5 2.5
2.5

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

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Table II

Composition IA 5 IB 7th IC ,8th Butocarboxim 39 7 ' 27 7th 19th , 7 Polyvinyl chloride 38, 8th 38, 6th 38 , 5 Dibutyl phthalate 21 33, 41

Experiment 2:

Finely powdered polyvinyl chloride is used for plastisol purposes and this is mixed with 83% pure technical butocarboxime and dioctyl phthalate in the following proportions:
Butocarboxim, technical: 20 % by weight
Polyvinyl chloride: 40% by weight
Dioctyl phthalate: 40 % by weight

The resulting liquid paste is poured into Petri dishes to a thickness of 2 mm and these are placed for between 5 and 30 minutes varying periods of time in thermostatic drying cabinets at between 115 and 135 ° C Temperatures. In all cases a “homogeneous plastic mass is obtained, and the active substance determined by analysis Contents are noted as the percentage of pure active ingredient as follows.

Table III

Heating time 115 ^U C 120 ⁰ C 125 ° C 130 ⁰ 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 establish that only the volatile impurities in the technical material have been lost in the course of the heating process. Experiment 3 : Three series 3A, 3B and 3C compositions according to the invention are produced according to the procedure described in Experiment 2 with heating at 125 ^° C. for 15 minutes.

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The compositions so produced have the Shape of discs 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 Butocarboxim, technical
Polyvinyl chloride
Dioctyl phthalate 10
45
45 20th
40
40 40
30th
30th Weight of the slices, each
(Gram) 8.53 . 8.19 7.80

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

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

Table V

Measured by 3A % mg 3B % mg 3C % mg 5 days
9 days
20 days
51 days
114 days
194 days 12th
16
24
36
49
61 102
137
206
309
417
518 13th
18th
26th
41
54
65 211
295
429
676
881
1068 19th
25th
37
53
56
77 593
774
1160
1647
2068
2412

Experiment 4 ; Disks 4A, 4B and 4C are used which are similar to those described in Experiment 3 and each have the same composition.

These discs are each placed in sand with a water content of around 20% and the measured from time to time Percentage of active ingredient diffused.

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The measurement results are compiled in the table below.

Table VI

Measured by 4A % mg 4B % mg 4C 14th
31
42
51 mg 20 days
51 days
114 days
194 days 11
22nd
34
43 93
188
292
365 13th
27
38
47 237
496
695
869 440
967
1317
1604

Experiment 5 ; The following composition is produced (data in percent by weight): butocarboxime, technically 20 polyvinyl chloride 40

Dioctyl phthalate 40

The procedure is as described in experiment 2. (I5 minutes at 125 ⁰ C) and receives discs of 90 mm diameter having different thicknesses.:

Table VII

Compositions 5A 5B 8th 5C 9 5D 8th 5E 9 Thickness in mm 1 2 3 5 7th Weight in grams 6.8 13, 20, 34, 48,

These discs are each placed in sand with a water content of around 20% and the measured from time to time Percentage of active ingredient diffused.

The measurement results are compiled in the table below.

Table VIII

Measured according to 5A % mg 5B % mg 5C % mg 5D % mg 5E % mg 19.2 260 13.2 364 9.0 375 8.4 525 7.8 763 8 days 37.1 505 25.7 709 19.7 824 16.8 1170 14.4 1407 15 days 54.5 741 37.1 1024 28.7 1200 24.5 1705 21.0 2054 22 days 65.2 887 46.7 1289 36.5 I526 30.5 2123 25.7 2515 29 days 80.8 1100 62.9 1736 51.5 2153 43.7 3040 35.1 3433 60 days 89.8 1220 76.6 2II5 67.0 2800 55.9 3890 45.3 4430 90 days

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Experiment 6:

For making the following compositions 6a to 6D, which are in the form of discs with a diameter of 90 mm and a thickness of 1.5 H, proceed as in experiment 2 (15 minutes at 125 ° C) (data in percent by weight):

Table IX

Compositions 6A 6B 6C 6D Butocarboxim, technical
Polyvinyl chloride
Dioctyl phthalate 20th
60
20th 20th
50
30th 20th
40
40 Ul UJ IV)
O O O Weight (gram) 13.83 13.75 13.76 13.56

The discs are each placed in sand with a water content of about 20% and the measured from time to time Percentage of diffused active ingredient with simultaneous determination of weight.

The measurement results are compiled in the table below.

Table X

Measured by 6A % mg 6B % mg 6C % mg 6D % 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 I25I 55.7 I512 29 days 9.0 249 26.9 740 54.5 I5OI 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

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

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Table XI

7A 7B Compositions 20th 20th Butocarboxim, technical 40 40 Polyvinyl chloride 35 20th Dioctyl phthalate 5 20th Tris-2-butoxyethyl phosphate 13.63 13.52 Weight (gram)

You hang the slices in a water-filled vessel and measure the percentage from time to time diffused active ingredient.

The results are compiled in the table below.

Table XII

Measured by 7A % mg 7B % mg 2 days
5 days
12 days 12th
50
74 323
1330
2025 20th
53
83 512
1450
2273

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

Table XIII

Compositions ÖA 8B Butocarboxim, technical 40 40 Polyvinyl chloride 25th 25th Dioctyl phthalate 25th 25th PVA-'copolymer (a) 10 - Polyethylene glycol 400 - 10 Weight ^ gramsj

(a) Polyvinyl acetate hydrolyzed to 30% to polyvinyl alcohol with a viscosity of 98 centipoise in 4% aqueous solution at 20 ^° C.

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- ns—

You hang the slices in a water-filled vessel and measure the percentage from time to time Active ingredient transferred to water.

The measurement results are compiled in the table below.

Table XIV

Measured by 8A % mg 8B % mg 5 days
31 days
93 days
173 days 18.2
53.2
81.4
98.2 615
1800
2750
3320 17.5
46.4
66.3
82.4 670
1770
2530
3145

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

Table XV

Compositions 9A 9B 6th 9C 9D 9E 9F Butocarboxim, technical 20th 20th 13.57 20th 20th 20th 20th Polyvinyl chloride 37 37 34 34 30th 30th Dioctyl phthalate 37 37 34 34 30th 30th PVA polymer (a ¹ ) 6th - 12th - 20th - PVA polymer (a ») - - 12th - 20th Weight (gram) 13.60 13.58 13.60 13.63 13.63

(a ¹⁾ To 50% to polyvinyl alcohol hydrolyzed polyvinyl acetate having a viscosity of 98 centipoises in a 4% aqueous solution at 2O ⁰ C.

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

The slices are placed in a water-filled vessel and the percentage is measured from time to time diffused active ingredient.

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- ι? -

The measurement results are compiled in the table.

Table XVI

below

Gemes
sen after 9A % mg 9B % mg 9C 440
782
1445 9D % mg 9E % mg 9F % mg 2 days
5 days
12 days 15th
28
49 410
755
1340 IVJl UJ IV)
HO IV) 590
817
1390 % mg 27
48
77 736
1314
2090 18th
34
63 496
924
1712 33
61
91 897
1668
2473 16
29
53

Experiment 10:

For the production of the following compositions 10A to 10E, which are in the form of discs of 90 mm Diameter and 2 mm thickness are available, proceed as in experiment 2 (15 minutes at 125 ° C) (data in percent by weight) :

Table XVII

Compositions 1OA 1OB IOC IOD 1OE Butocarboxim, technical 20th 20th 20th 20th 20th Polyvinyl chloride 40 40 40 40 40 Dioctyl phthalate 35 35 30th 20th 20th Polyethylene glycol 400 5 - 10 - 20th Ethyl triethylene glycol - 5 - 20th - Weight (gram) 13.57 13.51 13.61 13.32 13.50

You hang the slices in a water-filled vessel and measure the percentage from time to time diffused active ingredient.

The measurement results are compiled in the table below.

Table XVIII

Measured
after 1OA 9 & mg 1OB % mg IOC % mg IOD % mg 1OE % mg 2 days
3 days
5 days
12 days 11
17th
26th
48 295
466
714
1308 13th
43
64 353
1160
1707 13th
19th
33
56 354
512
904
1532 13th
46
71 341
1230
1886 40
87
100 1045
2354
2690

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'Jtib

Experiment 11 : To produce the following compositions 11A and HB, which are in the form of discs 90 mm in diameter and 2 mm thick, the procedure is as in Experiment 2 (15 minutes at 125 ° C.) (data in percent by weight).

Table XIX

HA HB Compositions 20th 20th Butocarboxim, technical 40 40 Polyvinyl chloride 35 20th Dioctyl phthalate Ul 20th Tributyl citrate 13.68 13.59 Weight (gram)

You hang the slices in a water-filled one And measures the percentage of diffused active ingredient from time to time.

The measurement results are summarized in the table below.

Table XX

Measured by HA mg HB "% mg 2 days
5 days
12 days % 350
1350
2030 20th
52
76 550
1430
2080 13th
49
74

Experiment 12:

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

Table XXI

Compositions 12A 12B 20th 12D 12E 12F Butocarboxim, technical 20th 20th 34 20th 20th 20th Polyvinyl chloride 37 37 34 34 30th 25th Dioctyl phthalate 37 37 12th 34 30th 25th Corn on the cob 6th - - - 20th - Wheat starch - 6th 13.64 12th - Weight (gram) 13.55 13.60 13.56 13.70 13.52

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You hang the slices in a water-filled vessel and measure the percentage from time to time diffused active ingredient.

The measurement results are compiled in the table below.

Table XXII

Gemes
sen after 12A % mg 12B % mg 12C 16
43
70 mg 12D % mg 12E % mg 12F % mg 2 days
3 days
5 days
12 days 16
36
61 427
980
1660 17th
20th
30th
53 467
545
822
1438 431
1167
1914 19th
26th
41
79 512
703
1117
2151 16
52
96 436
1418
2636 43
52
80
100 1170
1410
2158
2690

Experiment 13 ; To produce the following compositions 13A to 13F, which are in the form of discs 90 mm in diameter and 2 mm thick, the procedure is as in Experiment 2 (15 minutes at 125 ° C) (data in percent by weight):

Table XXIII

Compositions 13A 13B 13C 13D 13E 13F Butocarboxim, 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 6th - 12th - 20th - Carboxymethyl cellulose sodium salt - 6th - 12th - - 20th Weight (gram) 13.56 13.55 13.56 13.49 13.61 13.48

You hang the slices in a water-filled vessel and measure the percentage from time to time diffused active ingredient.

The measurement results are compiled in the table below.

030067/0776

Table XXIV

Gemes
sen after 13A % mg 13B \% mg 13C mg 13D mg 13E % mg 13F % mg 2 days
3 days
5 days
12 days 13th
37
60 347
1006
1636 22nd
36
53 412
602
971
1432 T 400
1052
1906 Hit 680
888
1155
2126 17th
65
100 463
1772
2706 43
54
87
100 1163
1452
2346
2679 15th
39
70 25th
33
43
79

Trial 14 ; To produce the following compositions 14A and 14b, which are in the form of discs with a diameter of 90 mm and a thickness of 2 mm, the procedure is as in Experiment 2 (15 minutes at 125 ^° C.) (data in percent by weight):

Table XXV

Compositions 14A 14B Butocarboxim, technical
Polyvinyl chloride
Dioctyl phthalate
Casein 20th
37
37
6th 20th
25th
15th
40 Weight (gram) 13.56 13.76

The slices are each hung in a water-filled one And measures the percentage of diffused active ingredient from time to time.

The measurement results are in the below Table compiled.

Table XXVI

Measured by 14A ,% mg % mg 2 days
5 days
12 days 13th
55
56 350
943
I5IO IS
43
80 44ο "
1191
2213

Experiment 15: present in the form of discs of 90 mm diameter and 2 mm in thickness to prepare the following compositions I5A and I5B, the procedure is as in Experiment 2 (I5 minutes at 125 ⁰ C) (percentages by weight):

030067/0778

Table XXVII 15A 15B 20th 20th Compositions 50 34 Butocarboxim, technical 30th 34 Polyvinyl chloride - 12th Dioctyl phthalate PVA polymer (a ")

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

The slices are cut into four equal quarters, each weighing about 3 »5 grams. One brings the quarters in the open field at a depth of 7 »5 centimeters in stony 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 taken from the soil, and the remaining Butocarboximmen ^ e measured by analysis to determine those in the Determine the amount diffused in the soil.

The measurement results are compiled in the table below.

Table XXVIII

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

Trial 16 ; Seven rows 16A to 16G of compositions according to the invention are prepared according to the procedure described in Experiment 2 with heating at 125 ° C. for 15 minutes.

030087/0776

The compositions thus prepared are in the form 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 XXIX

16A 13.29 16B 16C 16D 16E 16F 16G Butocarboxim, technical 20th 20th 20th 20th 20th 20th 20th Polyvinyl chloride 38 38 38 38 38 38 38 Dioctyl phthalate 42 - - - - - - Dioctyl adipate - 42 - - 10 10 - Dioctyl sebacate - - 42 - - - - Triceryl phosphate - - - 42 - - - Triethyl citrate - - - - 32 - - Tributyl citrate - - - - - 32 - Tris-2-butoxyethyl-phosph ₍ has - - - - - - 42 Average 13-6 13.25 13.45 13.42 13.57 13.03 Slice weight (grams)

The discs produced in this way are each placed in sand with a water content of about 16.7% and measured from From time to time the percentage and weight of active ingredient diffused.

The measurement results are compiled in the table below.

Table XXX

after 9 days mg 35 days mg 60 days mg 16A % 480 % 1385 % I65O 16B 18.1 635 52.1 1360 62.1 1710 16C 24.1 700 51.7 1275 65.0 1590 16D 26.4 370 48.1 950 60.0 1255 16E 13.8 590 35.3 1165 46.7 1265 16F 22.0 680 43.4 1490 47.1 I8O5 16G 25.1 1365 54.9 2145 66.5 2340 52.4 82.3 89.8

030067/0778

νίΓ

Experiment 17 : Three series 17A, 17B and 17C of compositions according to the invention are produced according to the procedure described in the experiment with heating at 125 ^° C. for 15 minutes.

The compositions so produced have the Shape of discs 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 Butocarboxim 20th - - yiethomyl - 20th - Thiofanox - - 20th Polyvinyl chloride 38 38 38. Dioctyl phthalate 42 42 42 Average s Slice weight (grams) 13.95 13.84 13.93

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

The measurement results are compiled in the table below.

Table XXXII

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

Experiment 18:

One sets seven rows 18A to 18G of

Compositions according to the procedure described in Experiment 2 (15 minutes at 125 ^° C.) using insecticide substances which are outside the scope of the invention.

The compositions thus prepared are in the form of disks with a diameter of 90 mm and a thickness of 2 mm

030067/0776

-YES-

-YYY ₁ -

and are composed as follows (data in percent by weight):

Table XXXIII

18A 18B 18C 18D 18E 18F 18G Carbaryl (b) 20th - - - - - - Chlorpyrifos (c) - 20th - - - - - Diazinon (d) - - 20th - - - - Fenthion (s) - - - 20th - - - Malathion (noun) - - - - 20th - - Naled (g) - - - - - 20th - Temefos (h) - - - - - - 20th Polyvinyl chloride 38 38 38 38 38 38 38 Dioctyl phthalate 42 42 42 42 42 42 42 Average before s
Pane weight
(Gram) 13.95 13.38 13.98 13.94 14.02 13.86 13.96

(b) N-methylcarbamic acid a-naphyllate.

(c) 0, O-diethyl-0- (3,5,6-trichloro-pyridyl-2) -thiophosphate.

(d) 0, O-diethyl 0- (2-isopropyl-6-methyl-pyrimidinyl-4) thiophosphate.

(e) 0,0-Dimethyl-0- (3-methyl-4-methylthiophenyl) thiophosphate.

(f) 0, O-dimethyl-S- [1,2-bis- (ethoxycarbonyl) -ethyl] -dithiophosphate .

(g) 0, O-dimethyl-O- (1,2-dibromo-2,2-dichloroethyl) phosphate. (h) 0,0,0 ', O'-tetramethyl-O.O'-thiodiphenylenediyl ^^') -bis- (thiophosphate); this substance is often referred to by the name "Abate".

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

In no case and after none of the elapsed times is an amount in excess of 0.0596 of the amount used Release of active substance detectable.

030067/0776

—35—

Experiment 19 : Using the procedure described in Experiment 2 with heating at 125 ° C. for 15 minutes, a composition according to the invention is produced with the following ingredients:

Butocarboxim: 35.3%

Polyvinyl chloride: 35.0%

Dioctyl phthalate: 19.8%

PVA polymer (a "'): 9.9%

(a '") Polyvinyl acetate hydrolyzed to 88% 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 so that they are cube-shaped Grains with an edge length of 4 mm received.

The grains are near the foot of in a pebble clay soil in the Vienne department, France, Bury planted rose bushes of the Red Favorite variety.

Three dosages are used: 30, 45 and 67 grams per rose bush. The rose bushes are three times Poured weekly with 6 liters of water. After 15 days, the rose petals are a grind and Subjected to extraction to determine their insecticidal content. The following contents can be found determine:

30 gram dose. = 35 ppm

45 gram dose = 60 ppm

67 gram dose = 75 ppm

It also shows that these levels are sufficient to allow aphids to multiply on the plants to prevent.

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

030087/0776

Table XXXIV

2OA , 3 2OB 5 2OC 7th 2OD 2OE 2OF Butocarboxim, technical 35 ,8th 23, 9 14, 2 35.3 23.5 14.7 Polyvinyl chloride 38 , 9 45, 6th 51, 1 35.0 35.0 35.0 Dioctyl phthalate 25th 30, 34, 19.8 27.7 33.5 Solubilized _ - - 9.9 13.8 16.8 Corn starch (i)

(i) Starch modified by carboxymethylation and pasting.

These compositions are formed into 4 mm thick sheets, which are cut so that one can do so cube-shaped grains with an edge length of 4 mm are obtained.

The grains from the compositions are sprinkled on the surface of the earth in each case in pots of 11 cm Diameter, each of a plant of the species Hibiscus rosasinensis contain; after spreading, cover the grains thinly with earth and then pour one liter each Water per pot; the amount of composition is calculated on the basis that it contains 50 mg butocarboxim per pot is equivalent to:

2OA and 2OD: 167 mg 2OB and 2OE: 250 mg 2OC and 2OF: 400 mg

The plants are infected with aphids of the species Myzus persicae, and the insecticidal activity is measured from time to time over 35 days. Use 5 plants per composition.

The results recorded are summarized in the table below and expressed as a percentage dead insects expressed in relation to the number recorded on the first day; the values given represent the for each composition over the 5 plants in total obtained average:

030067/0776

Table XXXV

Measured by 2OA 2OB 2OC 2OD 2OE i 2OF 3 days ^ 59 49 57 86 f 69 7 days 71 76 69 79 95! 89 12 days 76 75 62 82 91 I 90 16 days 93 84 79 90 96 94 20 days 90 79 77 89 95 j 90 24 days 93 80. 85 85 93 j 95 28 days 87 79 74 77 82 · 74 35 days 79 74 72 69 79 67

G30067 / 0776

Claims (19)

DR.BESQ D I PL.-1 NQ. ST APF D> PL.-ING. SCHWABE DR.DR. SANDMAIR F-ATENTANWÄLTE Attorney files: 31 0598MONCHENeO-MAUEnKIRCHEASTR-O patent claims 1. Systemic insecticide compositions consisting of a solid, homogeneous, hard or soft mass and A - an insecticidal substance, B - a polyvinyl chloride with a molecular weight over 10,000, C - one selected from hydrophobic diluents Regulating agents and D - optionally contain an additional regulating agent selected from hydrophilic diluents and powdery fillers, characterized in that the insecticidal substance A consists of an oxime carbamate of the formula R ₁ -C = NO-CO-NH-CH, (I) ¹ I ³ R ₂ where R _{1 is} a monovalent group R ¹ X- and R'-XC (R ") (R"') -, in which X is a sulfur atom or a sulfonyl radical, R' is a methyl or ethyl radical and R "and R" ¹ independently represent a hydrogen atom or a methyl or ethyl radical, and Rp are selected from methyl, ethyl, isopropyl and tert-butyl radicals. 2.. Compositions according to claim 1, characterized in that that they contain the insecticidal substance A to a composition between 5 and 50 parts per 100 parts Contained by weight. 3. Compositions according to claim 2, characterized in that they the insecticidal substance A to an intermediate 10 and 40 parts by weight per 100 parts of composition contain. 4. Compositions according to one of claims 1 to 3, characterized in that they contain the polyvinyl chloride B. in a proportion by weight of 20 to 70 parts per 100 parts of composition. 0300Β7 / 077Θ ORIGINAL INSPECTED --89- 5. Compositions according to claim 4, characterized in that they contain the polyvinyl chloride B in a proportion by weight Contains from 30 to 50 parts per 100 parts of composition. 6. Compositions according to any one of claims 1 to 5, characterized in that they contain the regulating agent C in a proportion by weight of 15 to 70 parts per 100 parts of composition. 7. Compositions according to claim 6, characterized in that they contain the regulating agent C in a weight proportion of 20 to 55 parts per 100 parts of the composition contain. 8. Compositions according to one of claims 1 to 7, characterized in that the insecticidal substance A under 2-N-methylcarbamoyloxyimino-2-methylthio-ethane, 2-N-methylcarbamoyloxyimino-3-methylthio-butane, 2-N-methylcarbamoyloxyimino-3-methylsulfonyl-butane and 2-N-methylcarbamoyloxyimino-3,3-dimethyl-1-methylthio-butane is selected. 9. Compositions according to claim 8, characterized in that the insecticidal substance is 2-N-methylcarbamoyloxyimino-3-methylthio-butane is present. 10. Compositions according to any one of claims 1 to 9, characterized in that the regulating agent C among low molecular weight polymers, chlorinated paraffins and .higher esters is selected. 11. Compositions according to any one of claims 1 to 10, characterized in that it acts as an additional regulating means one of water-miscible, soluble or dispersible polymers, polyols and esters and polyoxyalkylated Contain selected hydrophilic diluent from products. 12. Compositions according to any one of claims 1 to 11, characterized in that it is in the form of a solid, homogeneous, compact, hard or soft mass of any desired Present shape. 13. Process for the preparation of compositions according to one of claims 1 to 12, characterized in that 0300S7 / 0778 that the powdery polyvinyl chloride B "at room temperature mechanically with components A and C of the composition to form a dry powder or a flowable one Paste mixed, which or which then by pressing, spraying or pouring or by heating is transferred to the gelation temperature of the mixture in a solid homogeneous mass. 14. Process for the preparation of compositions according to one of claims 1 to 12, characterized in that that you dissolve the components A, B and C in a volatile solvent and this then with more or less evaporated at elevated temperature or reduced pressure. 15. A method for the preparation of compositions according to any one of claims 1 to 12, characterized in that that the polyvinyl chloride is dispersed in the sol state in the previously heated, liquid mixture of components A and C. and that the mixture is allowed to cool after a homogeneous dispersion has been obtained. 16. A method for the preparation of compositions according to any one of claims 1 to 12, characterized in that that one introduces the components A and C in vinyl chloride or a prepolymer of this compound and that one then, after adding a catalyst, the mixture is polymerized. 17. Process for the preparation of compositions according to one of claims 1 to 12, characterized in that a solid mass of polyvinyl chloride for the finished composition desired shape in the liquid component A? which may contain component C, if this is not already contained in the polyvinyl chloride, bring in all liquids can penetrate into the polyvinyl chloride composition for a period of time that is inversely proportional to the temperature. 18. The method according to claim 17 »characterized in that that you put the components A + C into one impermeable to them Introduces packaging container, the internal volume of which is adapted to the liquid mixture with the largest 030087/0771 possible surface of the solid polyvinyl chloride mass in contact, and then the packaging is closed and then stored until it no longer contains any free liquid at the end of the storage period. 19. Use of compositions according to any one of claims 1 to 12 as systemic insecticide compositions, which allow a controlled diffusion of the active ingredient in the water or in the soil. 0300Β7 / 077Θ