WO1995023506A1

WO1995023506A1 - Microencapsulated compositon of chlorpyrifos or endosulfan

Info

Publication number: WO1995023506A1
Application number: PCT/US1995/002736
Authority: WO
Inventors: Arie Marcus
Original assignee: Ben Gurion University Of The Negev Research And Development Authority; Cohen, A., David
Priority date: 1994-03-03
Filing date: 1995-03-03
Publication date: 1995-09-08
Also published as: JPH09509945A; IL108835A0; IL108835A; JP3816098B2; PT748158E; EP0748158A1; ATE241266T1; PL186227B1; ZA951786B; EP0748158B1; EP0748158A4; DE69530913D1; ES2197197T3; AU684627B2; DK0748158T3; NZ282973A; BR9507127A; DE69530913T2; AU2094995A; US5549903A

Abstract

The present invention relates to a microencapsulated chlorpyrifos or endosulfan composition comprising a polyurea shell and one or more photostable ultraviolet and visible light absorbent compound having a log molar extinction coefficient of from about 2 to 5 with respect to radiation having wave lengths in the range of about 310 to 450 nanometers, wherein said photostable ultraviolet and visible light absorbent compound does not react with the monomer used in building the polyurea shell. The result is a microencapsulated composition having unexpected long, extended insecticidal activity with high toxicity to target species and very low toxicity to non-target animals.

Description

MICROENCAPSULATED COMPOSITION OF CHLORPYRIFOS OR ENDOSULFAN BACKGROUND OF THE INVENTION

The present invention relates to microencapsulated insecticide compositions which are stabilized against

environmental degradation. The present invention more

specifically relates to microencapsulated chlorpyrifos or endosulfan stabilized against degradation by visible and ultra-violet light having unexpected extended insecticidal activity while having unexpected low toxicity to non-target species.

Chlorpyrifos, which is the common name for 0, 0-diethyl-0-(3,5,6-trichloro-2-pyridyl)-phosphorathioate, is a well-known insecticide. Two major problems of this

insecticide is on the one hand its ease of decomposition when exposed to the environment and the concomitant high toxicity to non-target animals. Thus, technical

chlorpyrifos has a toxicity to rats (acute oral) of an LD₅₀ of 168 mg/kg and a toxicity to trout (acute) of an LC₅₀ of 0.007mg/kg.

Endosulfan, which is the common name for

6,7,8,9,10 hexachloro- 1,5-5a,9a tetryhydro-6,9-methano-2 ,4,3-benzodioxathipia-3-oxide, is also a well-known

insecticide, with stability and toxicity problems. Its toxicity problem is most acute to non-target species such as fish and bees as the technical material has an LD₅₀ to non-target species such as mice of 30 mg/kg. For an EC

formulation to be classified as "only harmful" its LD₅₀ to mice must be at least 200 mg/kg. However, to reach such a toxicity, the concentration of endosulfan must be dropped to 3%, resulting in a non-economical mixture of very low

activity.

The microencapsulation of pesticides and

insecticides has been proposed in the prior art as a way of extending the insecticidal life of pesticides while

supposedly decreasing their toxicity to non-target animals. Examples are: United States Patent Numbers 2,800,458;

3,069.370, 3,116,216, 3,137,631, 3,270,100; 3,418,250;

3,429,827; 3,577,515; 3.959,464; 4,417,916; and 4,563,212.

British Patent Number 1,371,179; European Patent Publication Numbers 148,169 and 165,227; and Israel Patent Numbers

79,575 and 84,910.

Microencapsulated chlorpyrifos has been reported in European Patent Application No. 140,548. Microencapsulated endosulfan has been reported in US 4,230,809. In neither case is there any report of the use of

ultraviolet absorbers in these micro- encapsulated

formulations.

The use of an ultraviolet absorber to protect insecticides, especially pyrethroids, has been reported in United States Patent Numbers 2,168,064; 3,063,893;

3,098,000; 3,130,121; 3,264,176; 3,541,203; 3,560,613; and

3,839,561.

United States Patent Numbers 4,056,610 and

4,497,793 describe the use of specific UV absorbers in microencapsulated pyrethrins. However, these require in the case of US 4,056,610 - the use of a UV absorber in both the outer casing and in the liquid fill.

Regardless of the disclosure in the prior art, there has not yet been offered for sale microencapsulated chlorpyrifos or endosulfan, which has both extended

insecticidal activity and extremely low toxicity to nontarget animals.

SUMMARY OF THE INVENTION

According to the present invention there is provided a microencapsulated chlorpyrifos or endosulfan composition comprising a polyurea shell and one or more photostable ultraviolet and visible light absorbent

compounds having a log molar extinction coefficient of from about 2 to 5 with respect to radiation having wave lengths in the range of about 310 to 450 nanometers wherein said photostable ultraviolet and visible light absorbent compound does not react with the monomer used in building the polyurea shell. The result is a microencapsulted

composition having unexpected long, extended insecticidal activity with high toxicity to target species and very low toxicity to non- target animals.

DETAILED DESCRIPTION OF THE INVENTION

The microencapsulted insecticidal composition of the present inventions are prepared using standard

processes. Details for chlorpyrifos appear in Example 1. Details for endosulfan appear in Example 10. The percentage of the envelope - excluding the water and the polyvinylalcohol varies from 3% to 50%, preferably up to 30%.

Similarly, the fill contains from 0.5% to 5% preferably 1% to 3%, of the photostable ultraviolet and visible light absorbent compound.

Details of the stability of chlorpyrifos are listed in Example 2. For endosulfan, it was found that it decomposed after irradiation for 100 hours at 310±5

nanometers and 475± nanometers.

The photostable ultraviolet and visible light absorbent compounds are selected from the group consisting of sterically hindered amines and dyes. The sterically hindered amines are in turn selected from the Ciba-Geigy products known by the general trade name "TINUVIN" where the preferred ones are "TINUVIN -770" and "TINUVIN -780" having the following structures and Chemical Abstract Numbers as follows:

Designation: Butanedioic acid, bis-(2,2,6,6-tetramethyl-4- piperidinyl) ester

These ultraviolet and visible light absorbent compound were chosen among other reasons because they did not react with the monomers that build the envelope.

The microencapsulated compositions of the

invention may also optionally contain in addition to one of the "TINUVINS" dyes selected from the group consisting of Thermoplast green, Blue paste, Fluorescein, Sudan blue, Macrolex blue and Sudan III.

The microencapsulated compositions containing chlorpyrifos are listed in Table 1. Several of these compositions were studied to determine which had the longest activity against target species, such as beetles and cockroaches, even after exposure to sunlight, (Examples 4, 5 and 8) while having the lowest toxicity to non-target species, represented by mice, fish and bees (Examples 3, 6 and 9). The result was that Composition Numbers 14 and 15 containing chlorpyrifos were the preferred compositions, with Number 14 most preferred.

Almost all of the microencapsulated compositions of the present invention containing endosulfan gave poor toxicological results on mice. That is, in order to obtain a formulation with an LD₅₀ of 200 for mice the formulation would have to be very diluted; making it commercially unacceptable. However, compositions numbers 59 and 61 showed appreciably lower toxicity to non-target species at a commercially viable concentration of endosulfan, with number 61 the best. Examples 11 and 12 show the toxicity of these two formulations against the non-target species represented by mice and fish, respectively.

Thus, the present invention affords a novel microencapsulated composition containing chlorpyrifos or endosulfan, which not only can withstand relatively long exposure to sunlight, has a low toxicity to non-target species such as mice, bees and fish, while retaining commercially acceptable toxicity levels to target species such as beetles and cockroaches.

While the invention will now be described in connection with certain preferred embodiments in the following examples, it will be understood that it is not intended to limit the invention to these particular

embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention, as defined by the appended claims. Thus, the following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrate discussions of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of procedures as well as of the principles and conceptual aspects of the invention.

EXAMPLE 1

Representative Preparation of the Microencapsulation of

Chlorpyrifos

Four separate solutions: A, B, C and D were prepared as follows:

Solution A: 1520 ml water

15.2 g polyvinylalcohol ("MOWIOL-G-4) Solution B: 720 g melted chlorpyrifos

140 g Voranate M-580

4 g "TINUVIN - 770"

Solution C; 360 ml water

20 g ethylene diamine

18.3 g diethylenetriamine

Solution D: 14 g propylene glycol

58.4 Nonylphenol 6 mole ethoxylated (NP-6) 10g xanthan gum

A good emulsion of Solution B in A was made by mixing for 5 minutes in a high sheer mixer, keeping the mixture at 40°C. To this emulsion was slowly added Solution C, keeping the temperature at 40°C. The reaction mixture was cooled to 25°C to 35°C and the stirring was continued for 4 additional hours. Solution D was added and the mixture stirred for 15 minutes. Representative

microencapsulated compositions of chlorpyrifos are listed in Table 1.

TABLE 1

REPRESENTATIVE MICROENCAPSULATED COMPOSITIONS OF CHLORPYRIFOS

isocyanates E.D.A. DETA PDA Tinuvin TEPA Tinuvin TiO2 Escalol Water PVA

Formulation 770 P

no. types amount (g) (g) (g) (g) (g) (g) (g) (g) (ml.) (g)

1. ISONATE 35 6.2 5.7 - 0.9 - - - - 360 4

M-309

2. ISONATE 35 6.2 5.7 - - 1 360 4

M-302

3. ISONATE 35 - 5.7 - - 9.6 - - 1 360 4

M-302

4. ISONATE 35 - 5.7 - 0.9 9.6 - - - 360 4

M-302

5. ISONATE 35 6.2 5.7 - 0.9 - - - - 380 3.8

M-302

6. Voranate 35 - 5.7 7.7 0.9 - - - - 380 3.8

M-580

7. Voranate 35 6.2 5.7 - 0.9 - - - - 380 3.8 m-220

8. HMDI 2. 61 6.1 5.7 - - - 1 - - 360 3.6

9. HMDI 2.61 6.2 5.7 - - - - - 1 360 3.6 10. TDI 27 6.2 5.7 - - - 1 - - 360 3.6 11. TDI 27 6.2 5.7 - 1 - - - - 360 3.6 12. TDI 27 - 5.7 - - 9.6 1 - - 360 3.6 13. Voranate 35 6.2 5.7 - - - 1 - - 360 3.6

M-580

14. Vorante 35 6.2 5.7 - 0.9 - - - - 400 4

M-580

15. Voranate 280 39.7 36.8 - 8 - - - - 3040 30.4

M-580

TABLE 1 (continued)

isocyanates E.D.A. DETA PDA Tinuvin TEPA Tinuvin TiO2 Escalol Water PVA Formulation 770 P

no. types amount (g) (g) (g) (g) (g) (g) (g ) (g) ml. (g)

16. Voranate 280 39.7 36.8 - 8 - - - - 3040 30.4

M-580

17. Voranate 280 39.7 36.8 - 8 - - - - 3500 35

M-580

18. Voranate 280 34.7 31.9 - 9 - - - - 3040 30.4

M-580

19. Voranate 4.4 0.62 0.58 - 1 - - - - 380 3.8

M-580

20. Voranate 35 4.3 4 - 1 - - - - 380 3.8

M-580

21. Voranate 140 20 18.3 - 4 - - - - 1520 15.2

M-580

22. Voranate 35 5.6 5.3 - 1 - - - - 380 3.8

M-580

23. Voranate 35 5.6 5.3 - 1 - - - - 380 3.8

M-580

24. Voranate 11.7 1.86 1.71 - 1 - - - - 380 3.8

M-580

25. Voranate 35 5 4.6 - 1 - - - - 380 3.8

M-580

26. Voranate 35 6.2 5.7 - - - 1 - - 360 3.8

M-580

EDA - Elhytene diamine

DETA - Diethylene triamine

PDA - Propylene diamine

TEPA - Tetra ethylene penta amine

EXAMPLE 2

STABILITY OF UNPROTECTED CHLORPYRIFOS TO UV/Visible LIGHT

Unprotected chlorpyrifos was irradiated by an ultraviolet/visible light lamp for 68 hours. The stability versus the wavelength of the light is summarized as

follows:

Wave Lengths Extent of Degradation

313± 5 Total degradation

365+ 5 Low degradation

404± 5 Low degradation

436± 5 Medium degradation

^a In nanometers

EXAMPLE 3

METHOD FOR DETERMINING ACUTE ORAL TOXICITY WITH MICE

It is preferable to use Adult males (2-2.5 months) weighing 25-30 g. A solution of the formulation was obtained by using a "Vortex" mixer for 5 min. The quantity of the solution depended on the weight of mouse. Thus, 1 ml. solution was administered for 20 g of mouse weight. The solution was introduced by using a syringe (2 ml) through the mouth into the stomach of mouse. The test was performed in 5 replications and mortality was checked after 0,5,24,72,96,120,144,168 hours. Standardized mouse food was given during the experiment. The results for three

composition of the present invention are listed in Table 2 together with the data for a standard Emulsifiable

Concentrate formulation of chlorpyrifos after a time of 168 hours. TABLE 2

LD₅₀ ON MICE OF SEVERAL FORMULATIONS OF CHLORPYRIFOS

LD₅₀

Formulation³ Technical Material^b Formulation of Number 250 g/l

6 2250 9,000

13 2250 9,000

14 >2700 >10,800

E.C. formulation 120 480 ^a From Table 1

b mg/kg

EXAMPLE 4

METHOD FOR DETERMINING THE SUSCEPTIBILITY OF BEETLES

(TRIBOLIUM CASTANEUM AND MALADERA MATRIDA TO INSECTICIDES)

This method was used to measure the levels of susceptibility of population of beetles to a given

insecticide. The method was carried out in a room free from insecticide contamination. The beetles were treated and held at a temperature of 30°C for Tribolium castaneum and 25°C for Maladera matrida and a relative humidity above 25%. Beetles were obtained, as far as possible, from the same area, and kept in a suitable container until required; and they were given adequate and standardized food before the experiment. Adult beetles of either sex were used.

Tribolium castaneum were grown on flour enriched with 1% of beer yeast. Maladera matrida were obtained from the land of the farm "Sufa" and held in the laboratory in a suitable container on the ground which was used for food. A solution of each of the different formulations and the commercial material was obtained by using a high-shear mixer for 5 min. For each formulation Whatman paper No. 41 (d = 9 cm.) was dipped into the solution during mixing and put into a petri dish (d = 9 cm). The filter paper for exposure time 0 was dried in the hood, and the others were taken to the roof of the laboratory and exposed to sunlight. Approximately every 5 days, 3 petri dishes were removed from the roof and 5 beetles were placed inside each dish by using an aspirator for Trillium castaneum. The experiment was performed in 3 replications and mortality was checked each replication. The results for Maladera matrida treated with various chlorpyrifos compositions are shown in Table 3.

TABLE 3

Maladera matrida TREATED WITH VARIOUS CHLORPYRIFOS

MICROENCAPSULATED FORMULATIONS

Per Cent Killed

Exposure^a Concentration^c Formulation Type^b

to sun ppm 14 13 6 EC₄₅ Blank

0 500 100 100 100 100 0

6 86.7 100 100 53.3

10 80 93.3 93.3 53.3

17 6.7 0 33.3 0 ^a In days

b From Table 1

c Of chlorpyrifos

EXAMPLE 5 METHOD FOR DETERMINING THE EFFICACY OF COCKROACHES

(GERMANICA BLATELLA) TO INSECTICIDES

This method measured the levels of susceptibility of a population of cockroaches to Chlorpyrifos. Cockroaches were exposed to standard chlorpyrifos residues in petri dish and mortality was determined. From the results, the times necessary for 50% and 95% knockdown (LT₅₀ and LT₉₅) can be determined. Adult males were used. If it was not feasible to obtain enough males, information on susceptibility can be obtained by using females. The test was carried out in a room free of insecticidal contamination. The cockroaches were exposed to the chlorpyrifos and held at a temperature between 25°C and 30°C and at a relative humidity above 25%. Cockroaches were given adequate and standardized food before the experiment. Cockroaches, Germmanica blatella were grown in the laboratory in containers with ready-to-serve meaty dog food.

A solution of each of the different formulations and the commercial material was obtained by using a highshear mixer for 5 min. A solution of different

concentrations was prepared. For each formulation Whatman paper N41 (d = 9) was dipped into the solution during mixing and put in a petri dish (d = 9). The filter paper for exposure time was dried in a hood and the others were taken to the roof of the laboratory and exposed to sunlight.

Approximately every 5 days a petri dish was removed from the roof, and 5 Germanica blatella cockroaches were placed inside. To introduce 5 cockroaches into each petri dish, the cockroaches was first anaesthetized with carbon dioxide. The test was performed in 3 replications and mortality was checked. The exposure times examined were 0,5,10,15 and 20 days, approximately. Control dishes - untreated Whatman paper with 5 cockroaches after 24 h. A cockroach was considered knocked down if it fails to move on being

returned to a normal posture. The results for various microencapsulated formulations of chlorpyrifos are shown in Tables 4 and 5.

The tests were carried out according to the World

Health Organization Technical Report Series No. 443 Geneva 1970, pp 130-133.

TABLE 4

Germanicia blatella TREATED WITH VARIOUS CHLORPYRIFOS

MICROENCAPSULATED FORMULATIONS

Per Cent Killed

Exposure Formulation Concentration (ppm)

to Sun^a Type^b 100 200 300 400 500 Blank

0 14 100 100 100 100 100 0

0 13 26.7 80 100 100 100

0 6 0 93.3 93.3 93.3 100

0 EMPIRE^c 73.3 100 100 100 100

0 EW-20^d 100 100 100 100 100

0 EC-45^e 93.3 100 100 100 100

a Hours

b From Table 1

c Dow Chemical Company microencapsulated chlorpyrifos, 200g/l ^d Water based formulation of Makhteshim Chemical Works.

e Standarized Emulsified Concentrate

(non-microencapsulated) formulation of chlorpyrifos.

TABLE 5

Germanicia blatella TREATED WITH VARIOUS CHLORPYRIFOS

MICROENCAPSULATED FORMULATIONS

Per Cent Killed

Exposure Formulation Concentration (ppm) to Sun^a Type^b 25 50 100 150 200 Blank

0 14 100 100 100 100 100 0 0 EMPIRE^c 26.7 33.3 53.3 80 100

0 EC-45^d 60 60 73.3 100 100 ^a Hours

b From Table 1

c Dow Chemicals Company microencapsulated chlorpyrifos, 200g/l ^d Standarized Emulsified Concentrate

(non-microencapsulated) formulation of chlorpyrifos.

EXAMPLE 6

METHOD FOR DETERMINING TOXICITY OF FISH (GUPPIES)

All guppies require about the same basic care: water quality as close as possible to pH = 7.0 (neutral); water temperature about 24-25°C, and good strong light for least 12 hours a day (more light makes them grow faster). The test method was carried out in a room free of

insecticidal contamination. Adult fish of either sex were used.

Guppies were obtained from a fish shop and kept in a suitable 16-liter aquarium (water temperature 23-25°C), 10 fish/aquarium. The guppies were given adequate and standardized food (Europet Basic Food) before and after the experiment. Food was withheld for 2 days before the experiment.

Solutions of formulation and commercial material were obtained by using a high-shear mixer for 5 min.

Solutions 250, 500, 100, 2000, 4000, 5000, μg/liter of the formulations were prepared. Mortality was checked after 3, 6, 24, 48, 72 and 96 hours. From the results, the times necessary for 50% and 95% mortality (LT₅₀ and LT₉₅) can be determined for each formulation. Tests were carried out also on with golden orfe fish. The results are listed for golden orfe fish in Table 6.

TABLE 6

TOXICITY OF A CHLORPYRIFOS MICROENCAPSULATED FORMULATION TO GOLDEN ORFE FISH

Concentration (μg/l)of Formulation 14 EC(μg/l)^b

5000 2000 1000 250 50 250

Time^a Per Cent Killed

0 0 0 0 0 0 0

3 100 0 0 0 0 0

6 100 0 0 0 0 10

2244 110000 3300 10 0 0 10

48 100 40 20 0 10 30

72 100 40 20 10 10 30

96 100 40 20 10 20 30

a Hours

b Standarized Emulsified Concentrate

(non-microencapsulated) formulation of chlorpyrifos. EXAMPLE 7

Microencapsulated chlorpyrifos using variations of formulation 14 and containing various concentrations of dyes.

Following the method of Example 1, one of the preferred microencapsulated formulation, Type 14 was prepared containing various different dyes. The

microencapsulated formulations prepared are shown in Table 7.

TABLE 7

VARIATIONS OF FORMULATION TYPE 14 CONTAINING VARIOUS DYES

Formulation Isocyanate EDA DETA Tinuvin Colour

Number Type Amount (g) (g) 770 type amount (g)

(g)

14-G Voranate 35 5.0 4.6 1 Thermoplast 1

M-580 green

14-H Voranate 35 5.0 4.6 1 Blue paste 1

M-580

14-I Voranate 35 5.0 4.6 1 Fluorescein 1

M-580

14-J Voranate 35 5.0 4.6 1 Sudan Blue 1

M-580

14-K Voranate 35 5.0 4.6 1 Macrolex 0 . 25

M-580 Blue

14-L Voranate 35 5.0 4.6 1 Sudan III 1

M-580

14-M Voranate 35 5.0 4.6 1 Sudan III 1

M-580

14-N Voranate 157.5 22.3 20.7 4.5 Macrolex 1 . 5

M-580 Blue

14-O Voranate 360 36.7 34 7.7 Macrolex 3 . 0

M-580 Blue

14-P Voranate 140 19.8 18.4 4 Macrolex 1 . 6

M-580 Blue

14-Q Voranate 385 54.5 50.6 11 Sudan Blue 4 . 4

M-580

14-R Voranate 420 59.5 55.2 12 - - - -

M-580

14-S Voranate 385 54.5 50.6 11 Sudan Blue 4 . 4

M-580

14-T Voranate 525 74.4 69 15 Sudan Blue 6

EXAMPLE 8

Following the method of Example 4, several microencapsulated formulations of chlorpyrifos were compared as to their effect against Tribolium Castaneum in petri dishes after exposure to sunlight. Results are shown in Table 8.

EXPERIMENT 9

TOXICITY (Acute Contact and Oral LD₅₀ ) OF MICROENCAPSULATED

CHLORPYRIFOS TO HONEY BEES (Apir mellifera L.)

A. General

The study was performed with worker honey bees of about the same age, bred in a normal beekeeper's manner. For the tests, the bees were caught from the entrance hole of the hives in groups of ten with glass capture tubes, without anesthetics. During the tests, the bees were provided ad libritum with commercial ready to use syrup for honey bees as food. Stainless steel chambers (width 10 cm, height 8.5 cm, and depth 5.5 cm) served as test cages. The inner sides of the cages (except the front side) were covered with filter paper. The test cages were exposed in incubators at about 28°C, at 40 to 60% relative humidity in darkness, while being ventilated to avoid possible

accumulations of pesticides vapor. The tests were performed in five dosages of microencapsulated chlorpyrifos and one solvent control with three replicates per dosage or control.

B. Contact Toxicity Test

First the test cages with the bees in it were exposed to CO₂ in an incubator to anaesthetize the test animals with CO₂ dosage chosen so that the anaesthetization was shorter than five minutes. The test substance was then applied to the anaesthetized bees; and the treated bees were then returned to the test cages and kept under test conditions for 48 hours. Five dosages of the test

substances were tested in order to provide a rational base for a proper assessment of the control LD₅₀ of

microencapsulated chlorpyrifos to honey bees. The

anaesthetized bees are laid, ventral surface up, on filter paper in petri dishes. One μl drop per bee of

microencapsulated chlorpyrifos in solvent was placed in the ventral thorax using a GC-syringe. The result was an LD₅₀ contact of 22.1 μ/bee compared to a toxicity of 0.059 μ/bee for technical chlorpyrifos. C. Oral Toxicity Test

Five dosages of microencapsulated chlorpyrifos in acetone were tested in order to provide a rational base for a proper assessment of the oral LD₅₀ to honey bees. Ten cages containing 10 bees each were prepared without food, letting the bees starve for 1 to 2 hours. Following this, 250 μl of the prepared solutions in type of Eppendorf-pipettes were hung in each cage through one of the top openings. The bees were observed as long as uptake of the solution takes place. Each bee that vomited the solution was excluded from the test. The bees were provided with normal food after the uptake of the tested solution, but at the latest after 3 hours.

The result was an LD₅₀ oral of 118.5 μ/bee compared to a toxicity of 0.25 μg/bee for technical chlorpyrifos.

EXAMPLE 10

Representative Preparation of the Microencapsulation

of Endosulfan

Following the general method of Example 1 four solutions, A-D were prepared. Solution A: 380 ml water

3.8 g polyvinyl alcohol (MOWIOL-G4)

Solution B: 180 g melted endosulfan

42 g Voranate M-580

1 g "TINUVIN- 770"

1 g Irganox 1076 Solution C : 9 g water

9 . 3 g tetraethylinepentamine

5 . 6 g Diethylene triamine

Solution D: 3.5 g propylene glycol

14.6 g Nonylphenol 6 moles ethoxylated

(NP-6)

2.5 g xanthan gum Solution A is heated to 80°C and Solution B is added and an emulsion is made using a high sheer mixer for 1-2 minutes. Solution C is then added and the reaction mixture is stirred for an additional 4 hours keeping the temperature of the mixture at 50°C. The pH of the solution is then reduced to 7.6 by adding H₃PO₄, Solution D is added, and the reaction mixture stirred for 15 minutes. Representative microencapsulated composition of endosulfan are listed in Table 9 and 10.

TABLE 9

Nonylphenol6-mole

ethoxy¬

Sample Isocyanates Ethylene Diethylene U.V. Propylene TetraPropylene lated Xanthan Other Conc. Number Type Quantity diamine triamine absorbdiamine ethylene glycol: g (NP-6) gum additives a.i.%

(g) (g) (g) er: (g) (g) pent% (g)

amine: (g)

31 Voranate 11.7 2.0 1.9 Tinuvin - - 1.2 14.6 2.7 - 25.8

M-580 770

32 Voranate 11.7 - 1.9 Active C 2.6 - 1.5 14.6 2.7 - -

M-580

33 Voranate 11.7 2.06 1.9 Active C - - 1.5 14.6 2.7 - -

M-580

34 Voranate 11.7 - 1.9 Active C 2.6 - 1.5 14.6 2.7 - -

M-580

35 Isonate 11.7 2.0 1.9 Tinuvin - - 1.5 14.6 2.7 - -

M-301 770

36 Isonate 11.7 - 1.9 Tinuvin 2.6 - 1.5 14.6 2.7 - -

M-301 770

37 Voranate 11.7 1.86 1.71 Tinuvin - - 1.2 14.6 2.7 - 24

M-580 770

38 Voranate 11.7 1.86 1.71 Tinuvin - - 1.2 14.6 2.5 - 25

M-580 770

39 Voranate 11.7 1.86 1.72 Tinuvin - - 1.2 14.6 2.5 - 25

M-580 770

40 Voranate 35 5.6 5. .3 Tinuvin - - 3.5 14.6 2.5 Ca(No3)2 17

M-580 770

41 Voranate 35 5.6 5. ,2 Tinuvin - - 3.5 14.6 2.5 - - M-580 770

42 Voranate 35 5.6 5. ,3 Tinuvin - - 3.5 14.6 2.5 - - M-580 770

TABLE 9 (continued)

Nonylphenol

6 mole

ethoxySample Isocyanates Ethylene Diethylene U.V. Propylene TetraPropylene lated Xanthan Other Conc. Number Type Quantity diamine triamine absorbdiamine ethylene glycol: g (NP-6) gum additives a.i.%

(g) (g) (g) er(g) (g) pent% (g)

amine (g)

43 Voranate 35 5.6 5.3 Tinuvin - - - 2.5 - - -

M-580 770

44 Voranate 35 - 5.3 Tinuvin - 8.69 - 2.5 - - -

M-580 770

45 Voranate 35 - 5.3 Tinuvin 6.9 - - - 2.5 - -

M-580 770

46 Isonate 35 5.6 5.3 Tinuvin - - 3.5 - 2.5 - -

M-301 770

47 Voranate 35 - - Tinuvin 6.9 8.64 7.0 14.6 2.5 - -

M-580 770

48 Isonate 35 - 5.3 Tinuvin 6.9 - 3.5 - 2.5 - -

M-301 770

49 Voranate

M-580 18 - 5.3 Tinuvin - 8.64 3.5 14.6 2.5 - -

+ TDI 17 770

50 HMDI 26. 1 5.6 5.3 Tinuvin - - - 14.6 - - -

770

51 TDI 26. 1 5.6 5.2 Tinuvin - - - - - - - 770

52 TDI 26. 1 - 5.7 Tinuvin 7.7 - - - 2.5 - - 770

53 HMDI 26. 1 - 5.7 Tinuvin 7.7 - - 14.6 - - -

TABLE 10

Nonylphenol

6 mole

ethoxy¬

Sample Isocyanates Amines Irganox lated Xanthan %

Number Type Quantity Type Quantity 1076 gr. (NP-6) gum a.i .

54 Isonate 38. 5 DETA 5.0 1 Solid - 19.4

M-342 PDA 6.8 additive

55 Voranate 45. 5 DETA 5.98 1 Solid - 21.3

M-580 PDA 8.06 additive

56 Voranate 38. 5 DETA 5.01 1 Solid - 23.8

M-580 PDA 6.8

57 Voranate 42 DETA 5.7 1 Solid 14.8 26.0%

M-580 PDA 7.4 Liquid 2.5

58 Voranate 42 DETA 5.57 1 Solid 14.8 30.7%

M-580 PDA 9.3+ Liquid 2.5

59 Isonate 42 DETA 5.57 1 Solid 14.8 25.1%

M-342 PDA 7.4 Liquid 2.5

60 Isonate 42 DETA 5.57 1 Solid 14.8 25.2%

M-310 TEPA 9.3 Liquid 2.5

61 Isonate 42 TEPA 9.3 1 Solid 2.5 25.6%

M-342 DETA 5.57 Liquid

EXAMPLE 11

Following the method of Example 3, the two best microencapsulated formulations of the present invention containing endosulfan were tested for their toxicity to non-target species, represented by mice. The results are shown in Table 11. This shows the lower toxicity of formulation 61 as against formulation 59.

EXAMPLE 12

Following the method of Example 6, the two best microencapsulated formulations of the present invention containing endosulfan were tested for their toxicity to non-target species, fish, compared with the non-microencapsulated EC-35 formulation. The results are shown in Table 12. This shows the lower toxicity of formulation 61 as against both formulation 59 and against the non-microencapsulated EC-35 formulations of endosulfan.

Claims

1. A microencapsulated composition comprising a polyurea shell, a pesticide selected from the group consisting of chlorpyrifos and endosulfan, and one or more photostable ultraviolet and visible light absorbent compounds having a log molar extinction coefficient of from about 2 to 5 with respect to radiation having wave lengths in the range of about 300 to 500 nanometers wherein said photostable ultraviolet and visible light absorbent compounds does not react with the monomer used in building the polyurea shell.

2. A composition in accordance with Claim 1 wherein the photostable ultraviolet and and visible light absorbent compounds are selected from the group consisting of sterically hindered amines and dyes.

3. A composition in accordance with Claim 2 wherein the sterically hindered amines are selected from the group consisting of "TINUVIN 770" and "TINUVIN 780".

4. A composition in accordance with Claim 3 wherein the sterically hindered amine is "TINUVIN-770".

5. A composition in accordance with Claim 2 wherein the dyes are selected are selected from group consisting of Thermoplast green, Blue paste Fluorescein, Sudan Blue, Macrolex blue and Sudan III.

6. A composition in accordance with any of Claims 1 to 5 wherein the percentage of the envelope excluding the water and polyvinyl alcohol - varies from 3% to 50%.

7. A composition in accordance with Claim 6 wherein the percentage of the envelope - varies from 10% to 30%.

8. A composition in accordance with any of

Claims 1 to 7 wherein the fill contains from 0.5% to 5% of the photostable ultraviolet and visible light absorbent compound.

9. A composition in accordance with Claim 8 wherein the fill contains from 1% to 3% of the photostable ultraviolet and visible light absorbent compound.

10. A composition in accordance with any of Claims 1 to 9 having a high toxicity to target species while having a very low toxicity to non-target species.

11. A microencapsulated composition comprising a polyurea shell, chlorpyrifos and a photostable ultraviolet and visible light absorbent sterically hindered amine selected from the group having the trade names "TINUVIN 770" and "TINUVIN 780".

12. A composition in accordance with Claim 11 wherein the sterically hindered amine is "TINUVIN-770".

13. A composition in accordance with Claims 11 and 12 wherein the composition also contains dyes selected from the group consisting of Thermoplast green, Blue paste Fluorescein, Sudan Blue, Macrolex blue and Sudan III.

14. A composition in accordance with any of Claims 11 to 13 having a high toxicity to target species while having a very low toxicity to non- target species.

15. A microencapsulated composition comprising a polyurea shell, endosulfan, and a photostable ultraviolet and visible light absorbent sterically hindered amine selected from the group having the trade names "TINUVIN-770" and TINUVIN-780".

16. A composition in accordance with Claim 15 wherein the sterically hindered amine is "TINUVIN-770".

17. A composition in accordance with Claims 15 and 16 wherein the composition also contains dyes selected from the group consisting of Thermoplast green, Blue paste Fluorescein, Sudan Blue, Macrolex blue and Sudan III.

18. A composition in accordance with any of Claims 15 to 17 having a high toxicity to target species while having a very low toxicity to non-target species.

19. A microencapsulated composition of chlorpyrifos stable to ultraviolet and visible light which has a high toxicity to target species and a very low toxicity to non-target species substantially as

hereinbefore described in the examples and in accordance with Claims 1 to 11.

20. A microencapsulated composition of endosulfan stable to ultraviolet and visible light which has a high toxicity to target species and a very low toxicity to non-target species substantially as

hereinbefore described in the examples and in accordance with Claims 1 to 10 and 15 to 18.