AU504792B2 - Insecticide dispenser - Google Patents

Description

&COMM4ONWEALTH OF AU STRAL-I A PATENTS ACT 1952-1969. "I

CONVENTION APPLICATION fW APATENT ~ (This form mnay be signed by the applicant or by the Australian Patent Attorney)

nd xxx fl ox~amt(s) We H-ERCULITE PROTECTIVE FABRICS COIRPORATION of NfArt 110-7 Bro-adway, New York, New York,

792 United States of America

hereby apply for the grant of a Patent for an invention entitled

SDISPENSER FOR COCKROACH CONTROL

460*

which is described in the accompanying complete specification. The application is a o Convention application and is based on the application(s) for patent or similar protec- sea Wert namne of country, tionniadein The United States of America

Oil Z5th September 1973 under No: 400,584

Inetdate and number 4"'f eac application on which priority is based.

000

address for service is care of DAVIES COLLISON, Patent Attorneys, Our 0000. of Cromwell Building, 374 Bourke Street, Melbourne, in the State of Victoria Commonwealth of Australia.

Dated this 17th day of September 1974

Signature(s) of applicant(s). if a Company, form to b~e executed in a manner (a member of the firm of DAVIES COLTLISON) binding on thu Company for and on behalf of according to its Articles of Association or the HERCULI TE PROTECTIVYE Z~O AIQ laws of the country. Scal of Company (if any). tied. i3 Note: Initial all Alterations. To: THE COMMISSIONER OF PATENTS DAVIES COLLISON, Pat 'nt Attorneys, Melbourne and Canberia.

50470 Zopresent invention relates to dispensers for, the evC conri of xnzectg, es~pecially cockroaches, over extended pe- riodr; ofT tima, in a manmer which allows a reduction in the

COMM NEEAM ZS' V T PATEN~TS ACT 195,',4966

DECLARATION IN SUPPORT OF C05NVENTION. APPLICATION- FOR A PATENT OR PATEN~T OF ADDITION

Me/i declaration shall bet made by she,,applkaa., or, if the applicant is a body corpor. ate. by a person authorized by ltew body corporale to make the declaration on its behsalf.)

7 391./14 Insupport of the Convention Application made for a for an invention entitled DISPENSER FOR MXCK1R)ACH COTROL Seymour Insert full nameWs I S1/Hyman, President of Herculite Protective Fabrics and addresa%"st of AM Corporation, 1107 Broadway, New York, New York, deciamnt U*S.A.

do solemnly and sincerely declare as follows- D~elete the words which ftO P ptn~oa Iio avo not applicable. Insert full namne of or Mb I ami authorized by applicant Company. 5 5* HERCULTE PROTECTIIVE FABRICS CORPORATION

9) .J the applican. for tbe6W' bb to make this declaration on its behalf. U U 5@ .5 2. The basic application...as defined by Section 141 of the Act Was made .as* a Insert country and date of filing of each ap- plication on which priority as S a. is based. tnA~5-raX-~ae~ 4 h Insert full name of appli 0O cant In each loasic in on a application.

in on by

a Delete the wards which S. are not applicable. 3. (a) a

V Insert lull name(s) nod 59-. address(cst of or Agis Frank Kydonieus, 17 Sava~ e 2 J k actual inntor(s). New Jersey, U.S.A. CO' S

is tlue actual inventor...~.... of the invention and the facts 'qvuiicM ap4 licant,. U S 1,9 55 I. 5 is entitled to make the application are as folw ,pAT~p~t C~yi,.C A State manner in whirl a applicant(s) derive title Ayan Assignment betveen the parties dated Septenbez 20, 1973. 912

fran actual iventor(s). whereby t~he actuial inventor assaigned the invention to the sa~id applicant.

was 4. The basic application referred to in paragraph 2 of this Declaraton ~ft

the first applicatio, made in a Convention country in respect of the invention the subject of the application. U.S.A. Signature(s) of declarant(s), Declared at NTew York, N.Y.A(is 3 0 day Of Sept~mber, 1974. (No attestation or other HERCULITEPPYIECIW F BRICS CORPORATITON..... signature is required.)

Nose. Initial all Alterations. t~tnPresident TO-

and insoct attractitng composition. An intermediate layer may

be rovided between the insecticidal composition and the sub- str-ate laoier, such as cellulose fibers, matted, felted or r l (11) AU-B1-73491/74

(12) PATENT SPECIFICATION ABRIDGEMENT (19) AU

(21) 73491/74 504,792 (22) 19.9.74 (23" 19.9.74 (24) 25.9.73 400,584 (32) 25.9.73 (33) US (43) 25.3.76 (44) 1.11.79 (51) A01N 9/36 A01N 9/28 A01N 9/30 A01N 17/12. (54) INSECTICIDE DISPENSER. (71) HERCULITE PROTECTIVE FABRICS CORPORATION. (72) KYDONIEUS, A.F. (74) DM (56) 61087/73 491714 87.16 38193/72 439987 87.18 2475il'7 422274 87.16 (57) CLAIM 1. A dispenser for insecticidal agents effective against cockroaches and other insects comprising: a laminated polymeric article comprising a first outer layer, at least one core layer, and a second outer layer, said core layer comprising a solid, non-porous layer of polymeric material selected from polyethylene, polypropylene and polyvinylchloride, and containing an anticockroach agent selected from chlorpyrifos, diazinon, chlordane, carbaryl, mal- athion, bioresmethrin, propoxur and fenchlorphos, and mixtures thereof, said first outer layer being a polymer selected from polyethylene, polypropylene and polyvinylchloride, through which said agent is capable of migrating from said core layer to provide an effective level of said agent on the exposed surface of said outer- layer, and said agent being present in an amount of at least 10% by weight of the total weight of the laminate.

41.2

Co.MMONWEALTH of AU ST RA L I A PATENTS ACT 1952-1969

COMPLETE SPECIFICATION (Original) FOR OFFICE USE:

c lass tnt. Class Appi cotton Nomber: Lodged: Section 49.

1Complete Spec ificat ion Lodg,&d: Smdis cm pliitng Accepte~d: Publi!shed:

A~elated Art,.

Name of Applicant: MXLTCULITE ?ROMCT IVE FA1BR ICS CORP ORAT ION 4. 9941 4.* i i.e *4

Addressof Applicant; 1107 Br~oadway, New York, New York, United States of America

1;,AcdtuoI Inventor(s): AGIS FRANK KYDONIFUS

Address for 'arvice; DAVIES COLLISON, Patent Attorneys, IL-Jffi(e- &S00r'tS

Complete Specification for the inventior entitled: f Street, Meib~urne, 3000

AU514AA J

11DISENSER FOR COCKROACH CONTROL"

The following statement is a full description of this invention, including the Sest method of' performing it known to us

I: To: THE COMMISSIONER OF PATENTS DAVIES &COLLISON, Patpnt Attorneys, Melbourne and Canben c

04p 1Tile prosztit inivention relates to dispensers for the

cntx~l of insectsi, especially cockroaches, over extended pe- ridof timnein a manner which allowvs a reduction in the

cncentration of toxicants in the atmosphere and also protects C;Ie toxionto from premature degradation due to exposure to atmpberi conditiLons.

Various 4pecies of insects, and especially 'cock-

roaches, have bean a target for eradication by iqan for centu- ries. Lately, pesticides have been developed which have high toxi 2'ty for cockroaches, but present environmental hazards when used in effective concentrations. Repeated low concen-

tration application of available chemical toxicants reduces the danger to the environment but is also le'ss effective and relatively more expensive,. Accordingly, attempts have been made to develop systems, methods and products for the control- led release of cockroach -Lo-ricants over extended periods of time in a manner which is relatively less dangerous to man's

environment and also is effective to protect the toxicants r:from premature degradation. 2 CrAccording to the prior arts, insect repellent tapes

*0 or strips have been provided, comprising laminated materials at 0* least one laver of which comprises an insecticide, alone or in combination with insect bait or attractants. Representative

of T.his prior art are U. S. Patent 2,911,756 Geary and U. S.

*lot Patent 3,295,246 Landsman et al, although the foregoing re- Sferences are by no means exhaustive of the prior disclosures concerned with toxicant carriers for pest control. In the

Geary patent a flexible sheet or strip is provided with a 00 pressure-sensitive ad~~esive on one side for mounting -the strip Is"ace. The ol;her side is providEd with an insecticidal

(No attestation or other HERCULITE PROTECTIVE BRICS CORPORATION signature is reqlired.)

Note: Initir all Alterations. B f President TO:

and insect attracting composition. An intermediate layer may

be provided between the insecticidal composition and the sub-

strate layer, such as cellulose fibers, matted, felted or

otherwise joined and bonded to the flexible sheet. When the

insecticidal, insect attracting composition is applied over

such an intermediate layer it is said that the composition is

absorbed and'kept in close contact therewith, Such devices,

of which the Geary structure is typical, have been generally

objectionable for a number of reasons, including the availabil- ity on the exposed surface of the main concentration of toxi-

cant, lack of protection of the toxicant from atmospheric con-

ditions which may result in rapid loss of efficiency, rela-

tively low control over the rate at which the toxicant be-

comes available to the environment, and lack of structural

protection of the toxicant layer from abrasion or other mechan-

ical attrition.

The structure disclosed in the Landsman et al patent

remedies some of the foregoing deficiencies of Geary, by pro-

viding a protective surface coating on the laminated insect

repellent tape. The essential feature of the Landsman et al

o* o structure is said to be the provision of absorbent paper

saturated with a residual insecticide. The tape is then coated s" with a light resinous solution of vinyl or polyethylene or

S nylon merely to form a surfacing without forming a substantial

g.o coating layer on the top face of the tape and absorbent mate-

rial. Such structures, with their fragile outer facings, are

subject to rupture with resultant rapid evaporation, valatil-

ization and loss of the insecticide which is merely absorbed

in the absorbent core layer of paper or other porous'material. 3 0 *^itO^'4 a aloz ateare that the asoign c-ef the przcont

3 I- I; ,I ,i.

i dition, WO b~e pioeered a new~ technology for imnpart- iri 'aciv'e pzripaties to the surfaces of solid, non-porous Polymeric substrate materials by a techniquie which comprteeg applying to tipeated solid, nont-porous polymeric substrate materials a solid, non-poroxs layer of a polymeric compositic'n containing salected activating agents capable of migrating, from the layer into and throughouiC the substrate. The Migring agent is incorporated in the layer in an amount sufflicient to produce an effectivo level of activity on the extorior surf~ace of the substrate. The application of the fercutite. technology, known in he industry as the HERCON process, to the production of pesticidally active polyraeric 'materials is generally described in U.S. Patent 3,705,938,

:~and in U.S. Patents No. 3,857,934 and 3,864,468, which is resulted from divisional applications related to the first- mentioned issued patent, also in our British Patent 2,169, 288I and its Patents of Addition Nos. 1,376,223 and 1,376, 274. Additionally, our British Patent No. 1,391,248 relates to pesticide dispensers also based upon the HERCON technology. The present invention relates to specific systems for controlling insects, and especially crawling insects such as the cockroach target species, in a particularly effective manner, especially in terms of prolonged effect

with minimum hazard to the human environment.

According to the present invention, there is

provided a dispenser for insecticidal agents effective

against cockroaches and other insects comprising:

a laminated polymeric article comprising a

5 first outer layer, at least one core layer, and a

second outer layer, said core layer comprising a solid, non-porous

layer of polymeric material selected from polyethylene,

polypropylene and polyvinylchloride, and containing an 0** 10 anticockroach agent selected from chlorpyrifos, diazinon,

chlordane, carbaryl, malathion, bioresmethrin, propoxur

and fenchlorphos, and mixtures thereof,

S*0"

said first outer layer being a polymer selected

from polyethylene, polypropylene and polyvinylchloride,

15 through which said agent is capable of migrating from

said core layer to provide an effective level of said

agent on the exposed surface of said outer layer, and

said agent being present in an amount of at

least 10% by weight of the total weight of the laminate.

In order to achieve the desired level of

structural integrity, satisfactory migration, and still

retain flexibility, the outer layer of the polymer

through which the active agent migrates preferably

has a thickness on the order of from 0.001 to 0.010

inches, the polymeric-core layer containing the active agent preferably has a thickness on the order of from

P, I PM

.002 to .O0e20inches and the f Overall Xlaminate preferably bog a total thickness of up to, 0430 inches. it should

be uanderstood that the polynmers and thicknesses may be selected so that a relatively stiff strip is obtained which is capable of being foi'ced iznto cracks and crevices to reach areas in which insec-ts would ordinarily be protected.

4 -4 AM b "g j V. P94

may br composed of polymers containing blocking plasticizers

or relatively migration resistant polymers, such as polya'mides

and polyesters, for example, nylon and polyethylene tereph-

thalate. The latter materials are not resistant to migration 0 of ill active materials as has been disclosed in the issued

0 Herculite patent describing the basic HERCON technology, but

a they are sufficiently resistant to the present active agents

largely to control and direct migration of the cockroach 0 5

toxicants through the desired surface layer. *0 a The resulting dispensers are tough, flexible laminates

of integrally bonded layers and are highly resistant to mech-

anical destruction which could result in accidental and S 9

0 rapid loss of the active agent to the environment. The lami-

nate may be used in any configuration or as part of any

9. a structural assembly suited to maximize efficacy against

cockroaches. Forms such as adhesive backed sheet of strips, S and confetti are rseful. The laminate may also be incorporated 0

into loops, shelters or traps. A particularly preferred embodi-

ment of the invention comprises a strip of the laminated mate-

rial provided with a pressure-sensitive adhesive coating on

all or part of one surface to facilitate locating the dis-

penser in a manner to allow maximum effect against roaches.

6

V- L.:4~p

The strips may also be formed of dark, light absorbing, non- reflective materials, particularly attractive to roaches and

other insects when deployed as arborages..

More specific aspects of the invention will be appre-

ciated in view of the following specific Examples, which

include comparisons, indicated by "(COMP)" with materials

prepared by the basic technique of the present invention but

using less than 10 wt %of insecticide, and also untreated

materials and insecticide alone.

Example 1

A sheet of polyvinylchloride film having a thickness

of .004 inch was coated with a plastisol coating prepared by

dispersing 100 parts of polyvinylchloride resin in about

parts of dioctylphthalate and then dispersing 120 parts of

chlorpyrifos into the 125 parts of plastisol. The plastisol o thus prepared was mixed until uniform and the coating was

applied to the base sheet of polyvinylchloride in a thickness

of about 0.02 inches. The coated polyvinylchloride film was 2 then overlaid with a second sheet of polyvinylchloride also

i: having a thickness of 0.004 inches. The assembled layers

were then laminated under suitable conditions of heat and 1 i a pressure.until an integral firmly bonded product was obtained. 8o40

The laminated structure thus produced contained approximately *1 30.8% chlorpyrifos insecticide based on the total weight

of the laminate.

Exampltes 2 8

Additional dispensers were prepared in accordance

with the procedure described in Example 1 but replacing the

active agent as follows:

IL

Example 2 M~Ia1lat1Uion 5% (COMP) Example 3 -Malathion 33.7% .4. 'Example 4 -Chlorpyrifos 5% (COMP) Example 5 -Chlor~1ane (COMP)

Example 6 -Chlor~1ane -20.7%

9e*

0 0 a 0

0 00

0 0 S

S..

Pea 2*

a,

T7 a

I

1

I! S

Example 7 Diazinon 21.2%

Example 8 Carbaryl 22.7%

The testing was performed by the methods developed

by J. M. Grayson and H. G. Townsend and described in Pest

Control, 30(6), page 14 (1962) and by J. M. Grayson in Pest

Control, February (1970). Two tempered masonite panels,

held apart by staples, were placed in the bottom of a one

gallon glass jar to provide a hiding place for the insects.

The polymeric dispenser was placed on the top of the bottom

panel. A sample of 30 female cockroaches was placed in each

jar and observations on mortality were then made. In the

case of the low concentration dispensers, the mortality

(dead and moribund) was observed after six days; in the case

of the high concentration dispensers, mortality was observed

at the end of one day, three days and six days. The test

with the high concentration dispensers was also repeated

after 60 days and 150 days after the date of preparation of

the dispensers. The results of this testing are shown in 5 Table 1.

S. 0

0so500 o *S.

So o SoS 35

0

S S 0

S S.

i i.

5*S. 5 0 0 0 0 0 0* b 0 0 o OS S 0 S S S *t~0 5 0 *e*5 *at0*S S e 0@ 55 a

Table 1

Active Cockroach Mortalities- After Ex. No. Insecticide Ingredient Strain Specified Time of Aging

2 days 60 d ays 150 days 4 kOtA? chlorpyrifos diazinon-r 73 Normal 100

30.8 diazon, .n-r 1-00 100 100 100 100 100 100 10-0 lOG0 Normal 100 100 100 100 100 100 100 100 100

(CM?)chlordane diazonon-r 100 Normal 100

7 diazinon-r 0 67 74 97 97 100 71 97 100 Normal 63 97 97 100 100 100 97 100 100

2 malathion diazinon-r 0 Normal 77

33 .7 diazinon-r 0- 23 53 41 71 90 83 100 100 Normal 77 97 97 100 100 100 100 100, 100

diazinon 21.2 diazinon-r 30 93 100 97 100 100 100 100 100 Normal 97 97 100 100 100 100 100 100 100

carbaryl 22.7 diazinon-r 0 0 0 3 3 17 3 10 53 Normal 3 3 16 77 100 100 81 93 100,

Under each column the first figure is the percentage mortality at the end of a 1-day exposure period, the second figure is the same for a 3-day exposur e period and the third figure is the same for a 6-day period.

S 0* 0 0 a. 0 0 0. a 0 0* 0a00 o 06 0 0 0 a a 0 00 00 *o 00 0

Table 1

Active Cockroach Mortalities After Ex. No. Insecticide Ingredient Strain Specified Time of Aging

2 days 60 days 150 days 4 (CORP) chlorpyrifos diazinon-r 73 Normal 100

30.8 diazonon-r 100 100 100 100 100 100 100 100 100 Normal 100 100 100 100 100 100 100 100 100 COM) chlordane diazonon-r 100 Normal 100

20.7 diazinon-r 0 67 74 97 97 100 71 97 100 Normal 63 97 97 100 100 100 97 100 100 2 (Q0M malathion diazinon-r 0 Normal S 77

33.7 diazinon-r 0. 23 53 41 71 90 83 100 100 Normal 77 97 97 100 100 100 100 100 100 diazinon 21.2 diazinon-r 30 93 100 97 100 100 100 100 100 Normal 97 97 100 100 100 100 100 100 100 carbaryl 22.7 diazinon-r 0 0 0 3 3 17 3 10 53 Normal 3 -13 16 77 100 100 81 93 100 Under each column the first figure is the percentage mortality at the end ofi a 1-day exposure period, the second figure is the same for a 3-day exposure period and the third figure is the same for a 6-day period.

After two days of aging and six days of exposure

to the dispenser, diazinon killed all of the female German

cockroaches in both strains. Malathion also was effective

in killing cockroaches in a normal strain, but not in the

diazinon-resistant strain. Chlorpyrifos was the most effec- tive of the treatments, as it gave complete kill of cock-

roaches in both strains at the end of one day of exposure.

Chlordane was reasonably effective against the normal strain,

but only moderately effective against the diazinon-resistant

strain. Carbaryl exhibited little activity against cock-

roaches in either strain.

The dispensers were then aged and retested. The results, as seen in Table 1, after sixty (60) and one hun-

dred and fifty (150) days of aging are generally better than

those obtained after two days of aging. This may be

explained by the fact that it take. a period of time, some-

times several days or more, depending on the toxicant, and

polymer laminate system for the toxicant to migrate and allow the dispenser to become fully functional. Thus, dia-

zinon, chlorpyrifos and chlordane gave complete kill of nor- 66e0 mal and diazinon-resistant cockroaches after six days of ex- 0 posure to the dispensers which had been aged for 60 days. *0 Malathion gave complete kill of normal strain and better kill

Sof diazinon-resistant cockroaches than was the case in the

0 first test. Carbaiyl gave the poorest results on the dia- O, zinon-resistant strain, but produced complete kill of the

normal cockroaches after six days of exposure. The results

S after 150 days of aging do not show any signs of diminishing

effectiveness.

Grayson, in his continuous study (Pest Control,

February, 1972) to find chemicals that will be effective as

residual applications against resistant and susceptible

strains of German roaches used chlorpyrifos, diazinon, chlor-

dane and malathion oil sprays as controls in his experiments.

The test method used was the same as described above and the

deposit of insecticide on the masonite panels was approxi-

mately 150 mg/ft. 2 The results obtained by Grayson are shown

in Table 2. A comparison of the data in Tables 1 and 2 shows

that present dispensers give superior results, especially

after two months of aging.

Table 2

Percentage Mortalities at the end of one, three

and six days! following exposure of female German cockroaches

to panels which had been treated with differe2t insecticides

and the deposits allowed to age for various periods of time.

(Testing done at Blacksburg, Virginia, 1971)

2/ Cockroach Age of Insecticide Deposits(Days) Insecticide- Strain3/ 2 Days 60 Days

S malathion 3.0% diazinon-R 48 92 100 4 18 56 2P' oil-base Normal 97 99 100 44 90 99

chlorpyrifos 0.5% diazinon-R 56 100 100 0 8 46 oil-base Normal 99 100 100 59 97 99

chlordane 3.0% diazinon-R 52 74 92 14 56 82 oil-base Normal 100 100 100 29 100 100

diazinon 1.0% diazinon-R 82 100 100 4 16 34 oil-base Normal 100 100 100 82 100 100

Under each column the first figure is the percentage mortality at the end of a 1-day exposure period, the second is for a 3-day exposure period, and the third figure is for a 6-day exposure period.

2/ All materials were applied on a weight/volume basis. The deposit of insecticide was approximately 150 mg/sq.ft. from 1.0% formulations. a e I gI

S

Tests with normal strain were replicated 4 times. Dupli- cate tests were made with strains resistant to diazinon or malathion, making a total of 4 replicates with resistant strains.

Example 9

A synthetic pyrethroid (d-trans resmethrin, also

known as bioresmethrin) was incorporated into a dispenser

constructed in accordance with Example 1 at a concentration

of 12.5% of the total weight and the dispenser was evaluated

in sheet as well as 1/8" confetti form in tests against adult,

male German cockroaches. Squares of active sheet dispenser

were sealed to the upper surfaces of 3" x 3" glass plates,

with opaque plates mounted 3/16" above these surfaces to

give the insects a hiding place. These assemblies were then

placed in containers with 20-100 adult, male German cock-

roaches and knockdown and kill counts were made as shown in

Table 3. The insects and the opaque covers were removed

after 48 hours so the active dispenser was fully exposed to

ambient -aboratory lights (65 fc), temperature and humidity (50% RH) until the next test pe-riod. The dispenser

was compared with the untreated PVC contxul and with filter

paper surfaces treated with bioresmethrin (12.5% of total S The "confetti" form dispenser (2542 mg) was com ared

with an equal weight of No. 1 Whatman filter paper/containing

12.5% pyrethroid by continuous exposure of adult, German

cockroaches to the treated materials in large crystallizing

dishes.

The sheet dispenser containing synthetic pyrethroid

continued to show good knockdown and kill of the insects 0

after 34 days in the laboratory, while the treated filter

S* paper rapidly decreased in activity to a complete loss of

,^1A

,ffectiveness at the 15 day test. Similarly, the confetti gave high activity through the 15 day period, with loss of effectiveness at the 29 day reading, but the treated filter paper was active only on the first test day (Table 3). The sheet axnd confetti forms of the dispensers of this invention containing the bioresmethrin dramatically extended the residual activity of this light degradable

compound.

0

0 o 0 o 0. C C

'aeC 11e0 *0 B *0

8.S .5

410*e V**

*0 41

l0•

1 0

S

1 1 C C

THE CLAIMS DEFINING THE INVENTION ARE AS FOILLOWS:

A dispenser for insecticidal agents effective

~I

a 0 09 9 *0 0 Soso

0 a 0 *000 *0 0

0 a 0

00 *0 0 00

0 S 0 so

s 00 o 0

0

Table 3

Tests Against AduLt, Male German Cockroaches (Hazard Strain) with M Dispensers Containing Bioresmiethrin*

Total Knockdown Dead and No. 15 30 45 60 90 120 Moribund 0 Material Davs Roaches gin. Min. Min. Min. Min. Mlin. 24Hr. T4 Hr. :3 M a Sheet Form (Averages of 5 Replicates) o 00 r 98 24 24 28 352 79 Dispenser with 100 29 32 33 57 74 ci ID 98 58 59 59 86 91 1 12.5% P,~P 37 97 100 bioresmethrin 100 35 37 100 48 62 70 94 98 fl~ 0o P- Pr 0 0 0 1 1 PVC Control 100 Dispenser 100 0 0 0 0 1 O a 100 0 0 0 0 0 (Untreated) Lch 100 0 0 S0 0 14 H I-ic 0 100 0 0 0 0 0 C)~

i-iti Filter Paer 99 73 75 74 86 91 wi.h 12.5% 98 2 13 19 26 37 i lra 0r i-C bioresmethrin 100 0 0 0 0 0

o Confetti Form (Continuous Exposure) 'r Hbc 95 95 100* .100 100 0 Dispenser with 95 100 100* 100 100 12.5% 95 95 95 100* 100 pi ti 0 0 0 4 13 bioresmethrin&coM 0 0 0 0 2

i-I Filter Paer 100 100 100 100 100* 100 100 with 12.5% 0 0 0 0 0 0 bioresmeuhrin(0M? 0 0 0 0 0 0 0

ii

C C S a CC *9S 0 C C S *0

Table 3

Tests Against Adult, Male German Cockroaches (Hazard Strain) with Dispensers Containing Bioresmethrin*

Total Knockdown Dead and No. 15 10 4' 60 90 120 Moribund Material Days Roaches Min. V Min. Min. Min. Min. 24Hr. 48Hr.

Sheet Form (Averages of 5 Replicates)

98 20 24 24 28 52 79 Dispenser with 100 27 29 32 33 57 74 12.5% 98 52 58 59 59 86 91 bioresmethrin 100 31 35 37 37 97 100 100 43 48 62 70 94 98 PVC Control 100 0 0 0 0 1 1 Dispenser 100 0 0 0 0 0 1 (Untreated) COMO 100 0 0 0 0 0 0 100 0 0 0 0 0 14 100 0 0 0 0 0 0

Filter Paer 1 99 69 73 75 74 86 91 with 12.5% 8 98 1 2 13 19 26 37 bioresmethrin 15 100 0 0 0 0 0 0

Confetti Form (Continuous Exposure) 1 20 =3 90 90 95 95 100* 100 100 Dispenser with 8 20 20 75 95 95 100 100* 100 100 12.5% 15 19 21 74 84 95' 95 95 100* 100 bioresmethrin(coMP 29 20 0 0 0 0 0 0 4 13 34 20 0 0 0 0 0 0 0 2

Filter Paer 1 100 100 100 100 100* 100 100 with 12.5% 8 0 0 0 0 0 bioresmethrino 15 0 0 0 0 0 0 0

Co roaches:i removed to clean containers for remainder of observations.

I xample The polymeric dispensers of this invention have the unique ability to protect active ingredients from degradation,

thus prolonging the effective life of the insecti-ide, with- out increasing its persistence in the environment. This

Example demonstrates the effective life of several dispensers

containing malathion, diazinon, chlorpyrifos, fenchlorophos,

chlordane and carbaryl. All samples contained between 4%

and 11% insecticide based on the total weight of the dispens-

er.

According to the test procedure, Ai.erican cock-

roaches were added monthly to open top jars whose bottoms

were covered with the insecticidal dispensers. The time it

took to kill 100% of the roaches placed in the jars was reg-

istered and shown in Table 4 as a function of time from the

Sday of preparation of the dispensers. Between tests the S dispensers in the open top jars were exposed to the atmo-

spheric conditions of the room (approximately 70°F and

I. 'RH) I !The results shown in Table 4 indicate that all dis-

pensers were capable of killing normal American cockroaches

with undiminished strength after periods of as long as

months. *0 E a*0 a, 04

1 *0 S

a

a- 9

0O

~aarr?-n~~n TI~-

0s 0 r *c 0 e 0 4t0 0 t 00 Fi

Table 4

Persistene of insctcides Applied by the Present Controlled Release Dispensers

Mlonths From Date of Preparation o'f Samnple

'Insecticide

JMalathion Concn.r

lO. 2 1 1Dj 1 2f3 23

4D 3D 45 4__7 1 1 1D fID lD 1D _13

I2D -12 !D,,ilD;B 17H 14 1_ i:s Diazinon 4.7(=AP ID 4H 5H

Chlorpyrifos 4.6&orM ID lD 1 1D 1D 11D 1D 7H

j Fenchlorphos 4. ONtj9 2D 1D 2D_ 2D 4D12D 1j2- j 2D 7D

Carbaryl 10.5 1D iD 4D tH3V5 3121 5H jlHi 84 41

Chlordane 4.3Cwt 3D 2D 6D I 7D 2D 16D I'3D 7D 3D1 J2J

D Days

H Hours

-i I- -i i ii

I~L

0600 *00ob 0 9* 0 @0 9 0 0 9 .6 S 0 0 ro 0 *00 6*: 9 0 0 9 0 *9 0.- 00 00 60.

Table 4

Persistence of Insecticides Applied by the Present Controlled Release Dispensers

Months From Date oi Preparation of Sample I insecticide Concn. *1 VTV 0. I 1 12 13 14 '1 15 161

Malathion 10.2 ID 4D 3D D DI 1DI ID 2D 1D 1D 7_jH I Diazinon 4.7(oi-W) 1D 41H Chiorpyrifos 4.6(coMe) 1D 1D 1D 1D ID 1D LD 1D 7H

Fenchlorphos 4.0LcoM)o 2D 1D 2D 2D 4D 2D 2D 2D 7D

Carbaryl 10.5 1D 1D 4D 611 33/2 15H 8H 4H

Chlordane 4 3 t-i 3D 2D 6D 7D 2D- 6D 3D 7D

D Days

H Hours

I I -V r

Example 11

Three dispensers prepared ;n accordance with Ex-

ample 1 and cuntaining 31.!5% chlorpyrifos, 22.4% carbaryl and

chlordane, respectively, were placed in a weatherometer

to investigate the effect of adverse environmental conditions

on the ability of the dispensers to kill non-resistant Ameri-

can cockroaches. The arc of the weatherometer was operated

at 60 amps and 50 volts and the apparatus was operated in

such a way that the samples were exposed to successive cycles

of 102 minutes of light without water spray and 18 minutes

with spray at 800 F. (Fed. Test Method Std. No. 191 Method

5804). After exposure for 250 hours, the'three samples

were tested for anticockroach activity as set forth in Ex-

ample

The dispensers containing chlorpyrifos and carbaryl

showed 100% kill 'ithin one day and the chlordane sample after

four days. After 500 hours exposure in the weatherometer the

2Q.' three samples were tested again. The chlorpyrifos and car-

1 baryl dispensers again showed 100% kill within one day and

the chlordane sample produced 100% kill after three days. o. Example 12

Proper use of the polymeric dispensers indoors will

require knowledge of the amount of roach toxicant entering the 0O4•

surrounding environment. In Figure 1 the cumulative loss of

toxicant as a function of time has been determined for the

five dispensers of the type described in Examples 1, 3, 6, 7

and 8 and containing the toxicants in the following amounts:

chlorpyrifos 30.8%, chlordane 19.3%, diazinon 21.2%, malathion 33.7$ and carbaryl 22.7%. The weighings were performed against ctntrols, thus minimizing errors due to moisture 'absorption. It is apparent that the loss due to evaporation of toxicant as it becomes available on the sur- face of the dispensers is linear with time. In the case of malathion, however, a parabolic curve was obtained and it is believed that the initial high release rate was caused by volatile impurities in the technical grade malathion. The cumulative loss for any of the insecticides in this graph was Less than 5% per month. Figures 2 and 3 show cumulative diffusion losses, as a function of insecticide concentration, for malathion and chlordane. It is significant that the losses for the insecticides were not related to the vola- tilities of the pure materials, as shown below in Table 7, indicating that the control upon the rate of loss is the rate of migration of the toxicant through the polymeric matrix.

Table

Insecticide Vapor V Pressure mm Hg Temperature OC •00 4 x 10 5 malathion 3 chlorpyrifos 1.2 x 10 OS .8 x 10 4 fenchlorphos

2.8 x 10 4 diazinon 206 4 x 10 4 09 chlordane

<5 x l0 3 26 carbaryl O0

Examples 13 18

Dispensers prepared generally in accordance with

Example 1 were tested by the U3. S. Department of Agriculture

Agricultural Research Service at Gainesville, Florida, with

the results set forth in Table 7.

Procedure For Residue Tests

Compourds that produce 75% to 100% knockdown and

kill within 24 hours as a 2.0% contact spray are tested as

residues on 6 x 6 inch panels of 1/4-inch plywood. Acetone solutions of the insecticides are sprayed on plywood panels

at the rate of 100 mg of active ingredient per square foot.

When warranted, water suspensions and emulsions are substi-

tuted for the acetone solutions. The treated panels are allowed to dry for 2 hours, then 20 adult male cockroaches

(two replicates of 10 each) are exposed to the residues for

minutes. Exposures to the treated surfaces are made under

inverted plastic dishes coated on the inner surface with

pyrophyllite, which prevents the cockroaches from crawling

up the sides. At the conclusion of the exposure period, the

cockroaches are transferred to clean petri dishes. Observa- tions on knockdown and kill are made at this time and after

24 and 48 hours. The treated panels are then allowed to age

and are tested at intervals of 2, 2 and 4 weeks, or longer if

necessary, depending on the effectiveness of the residues.

All tests are conducted in duplicate in comparison to a chlordane standard.

Table 6 V. Soo

0* Results of standard screening tests with insecti-

S cides applied to plywood panels and evaluated for residual effectiveness against German cockroaches. 0

S 0

o *6 o.

Table 6 (cont'd)

Percent mortality on residues aged for indicated period

insecticide 2 hr: 1lwk 2 wk 4 wk: 8 wk

C arb aryl 0

Chlordane 100 60 0

Chlorpyti fos 100 100 100

Di a zion 100 90 0

14a1athion 25

P ropoxur 100 95 100

Check 0 0 0

Table 7

Residuial evaluation of Herculite 'fe4rni dispensers

on plywood against normal Blattella germanica. (Dispensers

stapled on plywood for standard exposure method; 2 tests with

adult males each; 30-mmn exposure; mortality assessed

after 48 hr). Percent mortality on treated 0 fabrics after indicated week 2 of testinga/

Ex. No. Insecticide M% 0!7 1 2 4 8 Residues on Herculite Fabric *0 Dispensers 13 Carbaryl 22 0

14 Chlordane 40 100 100 100, 100 100

15 Chlorpyrifos 27 100 100 100 100 100

16 Diazinon 21 100 100 100 100 100

17 Malathion 25 0 0

-18 Propoxur 23 100 100 100 100 100

eso* No mortality in checks. a/a Aged 2 hr.

A

From the foregoing it is apparent that this inven-

tion will provide efficacy against German and Anmirican cock-

roach s. The dispensers are particularly valuable for the

application of light-sensitive agents or any agent which

degrades upon exposure to atmospheric conditions. Further-

more, insecticide losses are controlled to a predictable rate,

consistent with prolonged effectiveness, without increasing

persistence in the environment.

While the efficacy of the products of the present

invention has been demonstrated in this application primarily by evidence of efficacy against the cockroach species, which

is a particularly hard to kill insect, it will be understood

that the products are also useful against other insects in-

cluding but not limited to ants, earwigs, flies, millipedes,

r-asquitoes, spiders, crickets, clover mites, fleas, scorpions,

sowbugs, ticks, coaterbugs, saw-toothed grain beetles,

silverfish, sod webworm, lawn chinch bugs, sand flies, bill-

bugs, punkies, bollworms, grasshoppers, stink bugs, corn

S erworm, Japanese beetle, fowl mites, lice, tobacco flea

24• beetle, by evdneo and a wide fiay varietygis of other agriculturally okoahseis destruc- hc

isapriual0adt0il net twl "a tive cbeetles, borers, slugs, suckers, aphids, eudrto moths, miners, tha the prdcsaeas sflagis te net n scales worms, cldn bu*o9iie oateawgfis ilpds

.qutos spdrciktcoe mts lasopos

*0

1 iei so*0.

Claims (2)

0* .3 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. A dispenser for insecticidal agents effective

against cockroaches and other insects comprising:

a laminated prlymeric article comprising a

first outer layer, at least one core layer, and a second

outer layer, .0ee

0 said core layer comprising a solid, non-porous

layer of polymeric materi-l selected from polyethylene,

.polypropylene and polyvinylchloride, and containing an 0. anticockroach agent selected from chlorpyrifos, diazinon,

chlordane, carbaryl, malathion, bioresmethrin, propoxur and fenchlorphos, and mixtures thereof,

e said first outer layer being a polymer selected

from polyethylene, polypropylene and polyvinylchloride,

Sthrough which said agent is capable of migrating from

said co. layer to provide an effective level of said

Sagent on the exposed surface of said outer layer, and said agent being present in an amount of at

least 10% by weight of the total weight of the laminate.

2. A dispenser according to claim 1 wherein said second outer layer is a solid, non-porous layer of

polymeric material selected from polyethylene, polypro- pylene and polyvinylchloride.

3. A dispenser according to claim 1 wherein said

second outer layer is a barrier to migration of said

agent.

22

-m

H H *rA H *dl *-H

-14

4. A dispenser according to clai. I. wlherein

said second outer layer is a solid, non-porous layer

of polymeric material selected from nylon and

polyethylene terephthalate.

A dispenser according to claim 1 wherein

said first and second outer layers and said core layer

"are polyvinylchloride.

e*

6. A dispenser according to any one of the *W preceding claims wherein the thickness of said first

outer layer is from 0.001 to 0.010 inches, the thickness

of said core layer is from 0.002 to 0.020 inches, and

the total thickness of said laminated article is up

to 0.030 inches.

7. A dispenser according to any one of the

preceding c3aims further comprising a layer of

S* pressure-sensitive adhesive on at least a portion

of at least one of said outer layers to permit

mounting of said dispenser on a surface compatible

with said adhesive.

8. A dispenser according to claim 1 substantially

as described in any one of the Examples.

Dated this 23rd day of August 1979

HERCULITE PROTECTIVE FABRICS CORPORATION

by its Patent Attorneys

DAVIES COLLISON

7U ENo: -1 2K -N rici 3 8

MAX, MUN 13 37 wl. 6 CARBMRYL' 69 26 *NU Loss OBsERVE3 TOTAL FILM THICKINESS Omi RIPC

30i 4 50 60 70 80 90 t00 Ii~ T1IME DAYS

XRVE No, AUENT CONC %IINITIAL W~EIGHT mq/in2 [ICA' CHLORPYRIFOS 30. 8 86.29 8. 2 CHLORDANE 193 32.49 3 DIAZINON 21 2 69.75 4 MALATHION 33.7 107. 6 7 ICARBARYL' 22 7 69.26 'NO LOSS OBSERVED TOTAL FILM THICKNESS :8 mil PVC to 6.

-44

2.2 xx 3 x

x x x

20 30 409 0 60 i0 80 90 160 11-0 TIME DAYS

CURVE CONC. INITIAL WEIGHT mgIinz F I C3 REL.EASE Of CHILORDARE 1I 4-3 5.8 2 j 19.8 32.49 3 I 409 121.8 TOTAL LM THICKNESS 8mil PVC

7 I'

-f I

20 30 40 50 60 70 80 90 100 110 120 TIME DAYS

ICURVE Nol CONC. IINITIAL WEIGHT mq/in 2 F IC ?RELEASE OF CHLORDANE 4,3 5.8 i9. 8 32.49 40.9 121.8 TOTA L THICKNESS :Bmil PVC

x A

A 1 I

20 30 4'0 50 60 70 80 90 10 110 120 TIME. DAYS

0 ,g*g eeoc Ce 0* 00 C. S I a go C C C 0 0 04 00 0 e @0 S 0 0 04 *0 g g 0003 go. C 04 g g g C e.g egg eg@ 0 gg g go

CURVE No, .4- CONC.% INITIAL WE1G~R mg/in2 r I c. 3 -RELEASE OF MALATHION 6.31 15.7 24.52 24.1 54.06 33.9 107.6 TOTAL FILM THICKNESS 8 mil PVC

3

xx

XX X2

'I

30 40 50 60 70 80 90 100 110 .120 TIME DAYS

C 0 0 POO 0 *00 U 006* 0 00~ *0*e s'~0 00 0 So S 0 0 0 00 .0 0 0 00 0 S 0 00 0 5000 506 a 00 0 06 0 0 0 0 000 000 #40 0 05 S 00

CURVE No.1 CONC INITIAL WEIGHT mg /in 2 IC RELEASE OFMALATH ION I 5 6.31 2 15,7 24.52 3 24.1 54.06 4 33.9 107.6 TOTAL FILM THICKNESS :8 mil PVC

3

x x

2)

x x x xl 3'0 46 5b 60 i0 80 90 100 110 1120 TIME DAYS