WO1990000005A1 - Microencapsulated pesticides with a lure - Google Patents
Microencapsulated pesticides with a lure Download PDFInfo
- Publication number
- WO1990000005A1 WO1990000005A1 PCT/US1989/002903 US8902903W WO9000005A1 WO 1990000005 A1 WO1990000005 A1 WO 1990000005A1 US 8902903 W US8902903 W US 8902903W WO 9000005 A1 WO9000005 A1 WO 9000005A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- poison
- acetate
- encapsulated
- capsule
- lure
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/002—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits
- A01N25/006—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits insecticidal
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
Definitions
- This invention relates to microencapsulated poisons and to encapsulated poisons using a lure or baiting technique.
- This invention may help destroy such plant and animal pests as fungi, bacteria, insects, rodents, birds, worms, and the like.
- the odor in most such pesticides is intended to repel pests from a certain area.
- the repulsion odor is generally shortlived and is, therefore, an
- Microencapsulation provides a time-release function, isolating the pesticide until it is triggered. Microencapsulation increases the efficiency of use, reduces handling and environmental hazards, improves compatibility with other chemicals, extends shelf life, and masks poison odors and tastes.
- Such a product would bait or lure a pest to a capsule and release a poison only when the pest digests or attacks the capsule. Until that time, the odor of the poison would not be allowed to escape the capsule. Only the odor of the bait would be able to escape.
- This bait-and- kill approach is used in larger pest traps, where an odor emanates from a box containing an adhesive. As the pest enters, pursuing the bait odor, it becomes trapped by the adhesive and eventually dies.
- a microencapsulated pesticide with a similar bait-and-kill technique would be more
- This invention uses a capsule within a capsule to bait and kill pests.
- the inner, smaller capsule contains a pesticide core surrounded by a polymeric shell.
- the outer capsule contains a substance that will both attract a pest and mask the odor of the poison. All that escapes the outer capsule is the lure odor, which attracts the pest to the capsule. The pest then breaks or ingests the capsule, which releases the poison that exterminates the pest.
- Another approach would be to construct the poison capsule with materials known to attract a given pest.
- An additional approach is to coat a poison capsule with a lure substance.
- the present invention encompasses encapsulation of substances in liquid, solid or slurry form.
- Encapsulating walls may or may not be permeable to core material or other materials to which the completed capsules may later be added.
- Capsules provided by the present invention may be capable of slow-release mechanisms (commonly referred to as "time-release") or may be released during ingestion by the pest.
- Capsule walls may be made of various polymeric and elastomeric materials.
- a first object of this invention is to provide a product that attracts a pest to a capsule containing a poison, where the size of the capsule may be termed as either a microcapsule or a large capsule,
- a second object of the invention is to enable capsules to attract, bait or lure pests to a poison, where the bait also masks, hides or disguises the presence of the poison.
- a third object of the invention is to provide bait-and-kill encapsulated poisons that will be effective against various forms of "pests", including, but not limited to, farm insects, household insects, mosquitoes, flying insects, ants, bacteria, fungi, rodents, worms, birds and barnacles.
- a fourth object of this invention is to provide means of luring or baiting a pest to a poison capsule within a larger bait capsule.
- a fifth object of the invention is to provide a pesticide capsule that is coated with a lure or bait
- a sixth object of the invention is to provide a pesticide that is contained in a capsule made of lure or bait substance.
- a seventh object of the invention is to provide methods of making such capsules.
- Figure 1 shows a preferred embodiment of the invention, in which a capsule exists within another capsule.
- the inner capsule contains a poison; the outer capsule, a bait substance.
- Figure 2 is a cross-section of a capsule in an alternative embodiment, in which a lure substance is coated onto a poison-containing capsule.
- Figure 3 shows a variation of the embodiment in Figure 2 in which a lure substance is imbedded between multiple capsule shell layers.
- Figure 4 illustrates a method of forming the capsules.
- Figure 1 shows a preferred embodiment of the invention, in which a larger capsule 8 contains a microcapsule 6 within its confines.
- the inner shell 2 surrounds poisonous core 1, isolating it from the rest of capsule unit 8.
- Lure outer core 3 lies between inner shell 2 and outer shell 4 of capsule unit 8.
- each capsule unit 8 contains several microcapsules 6. As above, pests are attracted by a lure outer core and exterminated when they open or ingest microcapsules 6.
- FIG. 2 shows a Reservoir-type microcapsule 14 having a single shell layer 12.
- the capsule contains a single poisonous inner core 1 trapped by a single shell layer 12.
- Bait substance 13 has been coated onto the outer surface of the shell 12. The bait coating 13 retards diffusion of pesticide odors across shell layer 12 and provides an attracting odor 5 to lure the pest to capsule 14.
- capsule 9 has multiple shell layers 10 and a single poisonous core 1.
- Bait substance 11 is either coated on the outer surface of capsule 9, embedded within the shell layers, or is itself the shell material of the outermost shell layer. Multiple shell layers 10 retard diffusion of the poison better than a single shell layer. This approach may be useful for extremely volatile cores.
- a pest may be attracted with a food source lure, a sex attractant or any such similar effective means of chemically attracting the pest.
- Examples of potential baits or lures are listed in Tables 1 and 2.
- Examples of potential shell mater ials for inner shell 2 or outer shell 4 are indicated in Table 4 .
- FIG 4 illustrates a popular method of capsule manufacture called coacervation.
- high speed agitation produces small capsules.
- the small capsules are then filtered from the liquid media and dispersed in a bait substance.
- This mixture goes through a second coacervation run to form a capsule unit.
- the agitation level is reduced in the second run, which tends to make larger capsules.
- the resulting capsule unit 8 contains the inner microcapsule 6 (see Figure 1).
- the bait substance 3 which becomes the outer core.
- This experiment produced a bait-and-kill microcapsule with the food source lure as the shell of the capsule itself.
- Type A, 300 bloom gelatin was combined with 40 grams of gum arabic and 20 grams of ethylcellulose in 3.7 liters of tap water. This solution was mixed at room temperature under mild agitation with a "lightening mixer" operating at 100 r.p.m. After 60 minutes of agitation, a partially dissolved, pre-condensate colloid wall material was formed.
- the wall material was composed of gelatin, gum arabic and ethylcellulose.
- the cockroaches which are known to use cellulosic starches and wallpaper pastes as foodstuffs, were attracted to the cellulosic shell
- the capsules were then dispersed in a beaker containing water and peanut oil. Under mild agitation for 30 minutes, the capsules became coated with the peanut oil.
- the capsules were then filter-dried and exposed to cockroaches.
- the peanut oil coating lured the roaches directly to the capsules.
- the roaches were readily
- Gelatin-based wall materials have low resistance to Dursban-R permeation, resulting in a short shelf life.
- the Dursban-R was encapsulated first in a resin-based shell and then in a layer of gelatin.
- Stage 1 Preparation of Small Capsules
- Precondensate urea-formaldehyde resin was formed first. 120 grams of urea was mixed at room temperature with 325 grams of a 37% aqueous formaldehyde solution containing 15% Methyl Alcohol. Drops of triethanolamine were added to adjust the pH 8. The mixture was then warmed to 70° (C), keeping the pH below 8.5. After one hour of agitation, 600 ml. of distilled water was added at room temperature. 130.5 grams of the precondensate solution was further diluted with 200 ml. of distilled water, producing a final resin-based, polymeric, urea-formaldehyde wall solution.
- This mixture was kept under rapid agitation for 60 minutes. This stage, which is generally referred to as an Interfacial Polymerization Process, produced capsules 25 to 65 microns large.
- Type A, 300 bloom gelatin was mixed at room temperature with 40 grams of gum arabic and 20 grams of ethylcellulose in 3.7 liters of tap water. This mixture was kept under mild agitation for 60 minutes to form a "bloomed" wall material solution.
- the capsules manufactured in Stage 1 were immersed in the new wall solution, under mild agitation, with heating to 65o (C). After 60 minutes, the mixture was allowed to cool to room temperature while the agitation continued. The capsules were then filter-dried by Buchner funnel
- This procedure layered the gelatin-based shell material onto the resin-based wall of the capsule, creating a capsule with distinct wall layers.
- capsules may have unusual strength, slowed release
- Stage 2 of this experiment the capsules from Stage 1 were filter-dried and mixed with a second core material and a second shell mixture.
- the dried capsules from Stage 1 were then added to the first mixture, and the resulting second mixture was agitated for another 60 minutes with heating to 65o (C). At the end of the 60-minute time period, the second mixture was allowed to cool naturally to room temperature while
- the resultant large capsules ranged from 30 to 50 microns in size and had several small capsules encased within each large capsule.
- the peanut oil deposit lay between the inner urea-formaldehyde layer and the outer gelatin-based layer.
- the pesticide core material lay in the core of the small capsules.
- this capsule-within-a-capsule unit worked best.
- the cockroaches were attracted by peanut oil odors from the outer capsules and began to eat the capsule units.
- the Dursban-R poison thereby escaped from the small capsules and killed the cockroaches.
Abstract
The invention is a microencapsulated poison containing an attractant (3), in which the poison is detectable only when the pest ingests or opens the capsule (7) and releases the poison. The preferred embodiment of the invention is a capsule (7) containing one or more smaller capsules (6) within. The inner capsule (6) contains a pesticide core material (1) surrounded by a thin polymer membrane (2). The outer capsule (4) contains a pest attractant (8) such as a pheromone or food source, that partially diffuses through the final outer shell of the capsule unit (4). The inner capsule (6) virtually seals in the poison core (1). The attractant masks any escaping poison core odors and exhibits a lure odor (5). Pests, attracted by the lure odor, open or ingest the capsules (7), thus releasing the poison.
Description
MICROENCAPSULATED PESTICIDES WITH A LURE
Field of the Invention
This invention relates to microencapsulated poisons and to encapsulated poisons using a lure or baiting technique. This invention may help destroy such plant and animal pests as fungi, bacteria, insects, rodents, birds, worms, and the like.
There are several microencapsulated pesticides presently available. All suffer one simple defect: the odor of the poison core permeates the capsule shell and is easily detected by pests. When a pest detects the poison odors, it merely avoids the capsule. Accordingly, such pesticides rarely kill pests.
The odor in most such pesticides is intended to repel pests from a certain area. However, the repulsion odor is generally shortlived and is, therefore, an
inefficient pest control agent. Since a pest constantly searches for food and a mate, a poison incorporating a food source or sex-attractant would be a more effective pest control agent.
One way to incorporate such a lure is by microencapsulation. Microencapsulation provides a time-release function, isolating the pesticide until it is triggered. Microencapsulation increases the efficiency of use, reduces handling and environmental hazards, improves compatibility with other chemicals, extends shelf life, and masks poison odors and tastes.
There exists several distinct problems with microencapsulation of pesticides:
(1) Repulsion without Elimination. Most such encapsulated pesticides contain a volatile poison with a high vapor pressure. The volatility enables poison vapors to seep through the capsule shell, giving the pest notice of the poison. The pest is therefore able to avoid the
encapsulated poison completely, with no extermination.
As noted above, the diffusion of the poison vapors is sometimes intended to repel pests and keep them from
returning. While this approach has merit in many
applications, its effectiveness is minimal. The escaping odors quickly evaporate, and pests soon return.
(2) Failure to Release Poison. In some products, encapsulation is so effective that it inhibits release of the poison core. This usually occurs when the shell of the capsule is too thick. These products have no time-release function and nothing to attract pests resulting in an ineffectual product.
(3) Population Control without Elimination.
Several approaches have been attempted to attract a pest to a capsule. These approaches use Pheromones (sex-attracting chemical compounds) to draw the male of the species to the capsules, where it mates with a capsule instead of a female. The result is population control by improper mating without actual extermination. This approach works well with certain insects but is ineffective with many critical pests.
For these reasons, most encapsulated pesticides are not as effective as the raw poison itself.
Disclosure of Invention
The effectiveness of microencapsulated pesticides would be improved by a capsule that would:
1. Attract a pest rather than repel it.
2. Exterminate the pest when it breaks the capsule.
3. Mask the odor of a poison contained in the microcapsule, making the odor undetectable until the pest reaches the capsule.
4. Protect the environment and workmen by insulating poisons.
Such a product would bait or lure a pest to a capsule and release a poison only when the pest digests or attacks the capsule. Until that time, the odor of the poison would not be allowed to escape the capsule. Only the odor of the bait would be able to escape. This bait-and- kill approach is used in larger pest traps, where an odor
emanates from a box containing an adhesive. As the pest enters, pursuing the bait odor, it becomes trapped by the adhesive and eventually dies. A microencapsulated pesticide with a similar bait-and-kill technique would be more
effective than conventionally encapsulated poisons.
This invention uses a capsule within a capsule to bait and kill pests. The inner, smaller capsule contains a pesticide core surrounded by a polymeric shell. The outer capsule contains a substance that will both attract a pest and mask the odor of the poison. All that escapes the outer capsule is the lure odor, which attracts the pest to the capsule. The pest then breaks or ingests the capsule, which releases the poison that exterminates the pest.
Another approach would be to construct the poison capsule with materials known to attract a given pest. An additional approach is to coat a poison capsule with a lure substance.
The present invention encompasses encapsulation of substances in liquid, solid or slurry form. These
substances may be pesticidal, fungicidal or bactericidal chemicals. Encapsulating walls may or may not be permeable to core material or other materials to which the completed capsules may later be added. Capsules provided by the present invention may be capable of slow-release mechanisms (commonly referred to as "time-release") or may be released during ingestion by the pest. Capsule walls may be made of various polymeric and elastomeric materials.
Accordingly, a first object of this invention is to provide a product that attracts a pest to a capsule containing a poison, where the size of the capsule may be termed as either a microcapsule or a large capsule,
whichever is sufficient for the desired use.
A second object of the invention is to enable capsules to attract, bait or lure pests to a poison, where the bait also masks, hides or disguises the presence of the poison.
A third object of the invention is to provide bait-and-kill encapsulated poisons that will be effective against various forms of "pests", including, but not limited to, farm insects, household insects, mosquitoes, flying insects, ants, bacteria, fungi, rodents, worms, birds and barnacles.
A fourth object of this invention is to provide means of luring or baiting a pest to a poison capsule within a larger bait capsule.
A fifth object of the invention is to provide a pesticide capsule that is coated with a lure or bait
substance, so that the lure masks the odor of the pesticide.
A sixth object of the invention is to provide a pesticide that is contained in a capsule made of lure or bait substance.
A seventh object of the invention is to provide methods of making such capsules.
Other objects and advantages of the present invention will be obvious from the following drawings, descriptions, and experiments.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a preferred embodiment of the invention, in which a capsule exists within another capsule. The inner capsule contains a poison; the outer capsule, a bait substance.
Figure 2 is a cross-section of a capsule in an alternative embodiment, in which a lure substance is coated onto a poison-containing capsule.
Figure 3 shows a variation of the embodiment in Figure 2 in which a lure substance is imbedded between multiple capsule shell layers.
Figure 4 illustrates a method of forming the capsules.
Detailed Descripton of Invention
Figure 1 shows a preferred embodiment of the invention, in which a larger capsule 8 contains a
microcapsule 6 within its confines. The inner shell 2 surrounds poisonous core 1, isolating it from the rest of capsule unit 8. Lure outer core 3 lies between inner shell 2 and outer shell 4 of capsule unit 8.
Odors emanating from the poisonous inner core 1 should be blocked by the inner shell 2. If any poison diffuses through inner shell 2, its odor will be absorbed and masked by the lure outer core 3. Since such diffusion will be minimal, the odor of poisonous inner core 1
generally does not detract from the potency of odors 5 from lure outer core 3.
Odors 5 emanating from the outer core 3 permeate and diffuse through the outer shell 4. These escaping lure odors 5 attract pests to capsule unit 8. Once it ingests or breaks the capsule, the pest is exterminated by poisonous inner core 1.
In an alternative embodiment (not shown), each capsule unit 8 contains several microcapsules 6. As above, pests are attracted by a lure outer core and exterminated when they open or ingest microcapsules 6.
In a further extension of the invention, it is possible to bait and kill pests by coating poison capsules with a bait substance. Figure 2 shows a Reservoir-type microcapsule 14 having a single shell layer 12. In this embodiment, the capsule contains a single poisonous inner core 1 trapped by a single shell layer 12. Bait substance 13 has been coated onto the outer surface of the shell 12. The bait coating 13 retards diffusion of pesticide odors across shell layer 12 and provides an attracting odor 5 to lure the pest to capsule 14.
A variation of the embodiment described in Figure 2 is illustrated in Figure 3. In this embodiment, capsule 9 has multiple shell layers 10 and a single poisonous core 1. Bait substance 11 is either coated on the outer surface of capsule 9, embedded within the shell layers, or is itself the shell material of the outermost shell layer. Multiple
shell layers 10 retard diffusion of the poison better than a single shell layer. This approach may be useful for extremely volatile cores.
A pest may be attracted with a food source lure, a sex attractant or any such similar effective means of chemically attracting the pest. Examples of potential baits or lures are listed in Tables 1 and 2.
TABLE 1
PHEROMONES
(SEX ATTRACTANTS FOR INSECTS) endo-Breviccmin 14-Methyl-Z-8-hexadecenal
E,E,8,10-Dodecadien-1-ol 14-Methyl-E-8-hexadecenal
Z-7-Dodecen-1-ol Acetate 2-Methyl-Z-7-octadecene
Z-8-Dodecen-1-ol Acetate Multistriatin
E-8-Dodecen-1-ol Acetate Z ,Z-Octadecadienol
Z-9-Dodecen-1-ol Acetate Z ,Z-3,13-Octadecadien-1-ol Acetate
E-10-Dodecen-1-ol Acetate E,Z-3,13-OctadierHL-ol Acetate
Frontalin Z-13-Octadecenal
Z-6-Heneicosen-11-one Z-9-Octadecen-1-ol
Z,Z-7,11-Hexadecadienal Z ,E-9,12-Tetradecadien-1-ol
Z ,Z-3, 13 Hexadecadienal Tetradecenal
Z,Z-11,13 Hexadecadienal Z-9-Tetradecenal
E,Z-7,11 Hexadecadienal-1-ol Acetate Z-11-Tetradecenal
Z,E-7,11-Hexadecadienyl Acetate Z ,E-11-Tetradecenal
Z-9-Hexadecenal Z-9-Tetradecen-1-ol Acetate
Z-11-Hexadecen-1-ol Z-11-Tetradecen-1-ol
Z-11-Hexadecen-1-ol Acetate Z-8-Tetradecen-1-ol Acetate
Ipsdienol Z-11-Tetradecen-1-ol Acetate
Ipsenol Z-9-Tetradecen-1-ol Formate
2-Methyl-2-cyclohexen-1-one cis-Verbernol
3-Methyl-2-cyclohexen-1-one trans-Verbenol
Verbenone
EXAMPLES OF PBEROMONES AND ATTSACTANTS
AND THEIR APPLICATION PRCDDCT NAME USE
Codlure Codling Moth
Cuelure Melon Fly, Queensland Fruit Fly
Disparlure (Racemic) Gypsy Moth
Dorsalure Oriental Fruit Fly
Grandlure Boll Weevil
Muscalure House Fly
3-Methyl-2-cyclohexene-1-one Douglas Fir Beetle
E-4-Tridecen-1-ol Acetate Tomato Pinworm
Trimedlure Mediterranean Fruit Fly
cis-Verbenol Bark Beetle
Alphar-Cubene Elm Bark Beetle
Z-9-Dodecenyl Acetate Western Pine Shoot Moth
Gossyplure European Grape Berry Moth
E,E-10,12-Hexadecadienal Pink Bollworm
Z-11-Hexadecenal Spiny Bollworm
E-11-Tetradecenal Heliothis
Spruce Budwoπti
TABLE 2
FOOD SOURCE LURES FOR INSECTS AND RODENTS Carboxymethylcellulose Zein
Cellulose acetate phthalate Nitrocellulose
Ethylcellulose Cheese
Gelatin Bacon Grease
Gum arabic Succinylated Gelatin
Starch Peanut Oil
Bark Proteins
Methylcellulose Kraft lignin
Butter Peanut Butter
Examples of potential poisons are listed in Table 3 , along with the pests each poison can exterminate .
TABLE 3
COMMONLY USED PESTICIDES
PESTICIDES PESTS
Alpha-Cubene Elm Bark Beetle Z-S-Dodecenyl Acetate Moths
Gossyplure Bollworm chemical name: (Z)-7-(Z,E)-11- Hexadecadien-1-ol, acetate
Z-11-Hexadecenal Heliothis
E,E-10,12-Hexadecadienal Spiny Bollworm
E-11-Tetradecenal Budworm
Rabon (stirofos) Larval House Fly chemical name: 2-chloro-1- (2,4,5-trichlorophenyl)
vinyl dimethyl phosphate
Purathion (Pennacol) (parathion)
chemical name: 0,0-diethyl
0-(p-nitrophenyl) phosphorothioate
Malathion
chemical name: 0,0-dimethyl
phosphorodithioate of diethyl
mercaptosuccinate
Dursban (DOW) (chlorpyrifos)
chemical name: 0,0-diethyl 0- (3,5,6-trichloro-2-pyridyl)
phosphorothioate
X-Clude
Pyrethrins (include pyrethrin I)
chemical name: 2-methyl-4-oxo-3-(2,4-pentedienyl)-2-cyclopenten-1-yl
2,2-dimethyl-3-(2-methyl-1-propenyl)
cyclcpropanecarboxylate (9CI) ,
and pyrethrin II, chemical name:
2-methyl-4-oxo-3- (2,4-pentedienyl)-2-cyclopenten-1-yl 2,2-dimethylcyclopropanecarboxylate (9CI)
Ficam W (bendiocarb)
chemical name: 2,2-dimethyl-1,3- benzodioxol-4-yl methylcarbamate
Diazinon (Knox-out, Pennwalt)
chemical name: 0,0-diethyl
0- (2-isopropyl-6-methyl-4-pyrimidinyl)
phosphorothioate
Demon -EC (cypermethrin) Roaches
-WP (cypermethrin)
-TC (cypermethrin) Termites
chemical name: (t,-) a-Cyano- ( 3-phenoxypheny 1) methyl- (t,-) - cis, trans-3- (2,2-dichloroethenyl) - 2,2-dimethylcyclopropanecarboxylate
Pryfon-6 (isophenphos) Termites
chemical name: 1-methylethyl 2- { {ethoxi't (1-methylethyl) amino]
phosphinothioyl}oxy} benzoate
Tempo (pyrethroid)
Gencor Roaches
Safrotin (Sandoz) (propetamphos)
chemical name: (E)-1-methylethyl
3- [ [ethylamino methoxyphosphinothioyl]
oxy]-2-butenoate
Examples of potential shell mater ials for inner shell 2 or outer shell 4 are indicated in Table 4 .
TABLE 4
SHELL FORMULATIONS ARE FLUID FILM FORMERS
INCLUDING
• SOLDTIONS
• MELTS
• LATEXES
AND MAY BE HARDENED BY
• CHEMICAL REACTION
• SOLVENT EXTRACTION
• SOLVENT EVAPORATION
• COO LING
OR • COMBINATIONS
SOME MICROENCAPSULATION MATRIX AND WALL CHEMICALS
Natural Polymers
Carboxymethylcellulose Zein
Cellulose Acetate Phthalate Nitrocellulose
Ethylcellulose Propylhydroxycellulose
Gelatin Shellac
Gum arabic Succinylated gelatin
Starch Waxes, paraffin
Bark Proteins
Methylcellulose Kraft lignin
Arabinogalactan Natural Rubber
Synthetic Polymers
Polyvinyl Alcohol Polyvinylidene chloride
Polyethylene Polyvinyl chloride
Polypropylene Polyacrylate
Polystyrene Polyacrylonitrile
Polyacrylamide Chlorinated polyethylene
Polyether Acetal copolymer
Polyester Polyurethane
Polyamide Polyvinylpyrrolidone
Polyurea Poly(p-xylylene)
Epoxy Polymethyl methacrylate
Ethylene-vinyl acetate copolymer Polyhydroxyethyl methacrylate Polyvinyl acetate
Synthetic Elastomers
Polybutadiene Acrylonitrile
Polyisoprene Nitrile
Neoprene Butyl rubber
Chloroprene Polysiloxane
Styrene-butadiene rubber Hydrin rubber
Silicone rubber Ethylene-propylene-diene terpolymer
Several methods may be employed to produce the capsule units described in Figure 1. Most methods require manufacture of microcapsule 6 first, which is then used as core material for a second encapsulation process.
Figure 4 illustrates a popular method of capsule manufacture called coacervation. With this technique, high speed agitation produces small capsules. The small capsules are then filtered from the liquid media and dispersed in a bait substance. This mixture goes through a second
coacervation run to form a capsule unit. The agitation level is reduced in the second run, which tends to make larger capsules. The resulting capsule unit 8 contains the inner microcapsule 6 (see Figure 1). Between the inner shell 2 and the outer shell 4 is the bait substance 3, which becomes the outer core.
This technique is further explained in the
following reports of experiments. Experiment 1: Encapsulated Poison in a Single Shell
Capsule With a Bait Substance as the Shell Layer.
This experiment produced a bait-and-kill microcapsule with the food source lure as the shell of the capsule itself.
40 grams of Type A, 300 bloom gelatin was combined with 40 grams of gum arabic and 20 grams of ethylcellulose in 3.7 liters of tap water. This solution was mixed at room temperature under mild agitation with a "lightening mixer" operating at 100 r.p.m. After 60 minutes of agitation, a partially dissolved, pre-condensate colloid wall material was formed.
300 grams of a pesticide known as Dursban-R, supplied by Dow Chemical Company, was added in liquid form and under vigorous agitation to the vessel containing the wall material. This mixture was heated to 55º (C) and held at that temperature for 60 minutes. While agitation
continued, the mixture was allowed to cool to 28° (C), which required only 10 minutes. Observation at that point
revealed capsules 30 to 75 microns large containing 25% wall material by volume and 75% core material. The wall material was composed of gelatin, gum arabic and ethylcellulose.
The capsules so produced effectively attracted and killed household cockroaches. The cockroaches, which are known to use cellulosic starches and wallpaper pastes as
foodstuffs, were attracted to the cellulosic shell
materials. When the cockroaches ingested the capsules, the Dursban-R poison escaped and exterminated them.
Experiment 2: Single Shell Lure Capsule with a Bait
Substance Coating the Outer Shell
Experiment 1 was repeated fully, producing capsules 30 to 75 microns in size.
The capsules were then dispersed in a beaker containing water and peanut oil. Under mild agitation for 30 minutes, the capsules became coated with the peanut oil.
The capsules were then filter-dried and exposed to cockroaches. The peanut oil coating lured the roaches directly to the capsules. The roaches were readily
attracted to the capsules and exterminated when they opened them.
Experiment 3; A Lure Capsule with Multiple Shell
Layers In this experiment, the chosen poison core was encapsulated in multiple shell layers treated with a lure substance.
Gelatin-based wall materials have low resistance to Dursban-R permeation, resulting in a short shelf life. To solve this problem, the Dursban-R was encapsulated first in a resin-based shell and then in a layer of gelatin.
This Multi-Wall system required two stages.
Stage 1: Preparation of Small Capsules Precondensate urea-formaldehyde resin was formed first. 120 grams of urea was mixed at room temperature with 325 grams of a 37% aqueous formaldehyde solution containing 15% Methyl Alcohol. Drops of triethanolamine were added to adjust the pH 8. The mixture was then warmed to 70° (C), keeping the pH below 8.5. After one hour of agitation, 600 ml. of distilled water was added at room temperature. 130.5 grams of the precondensate solution was further diluted with
200 ml. of distilled water, producing a final resin-based, polymeric, urea-formaldehyde wall solution.
10 grams of this wall solution was then mixed at 25º (C) with 40 grams of Dursban-R in 400 ml. of water.
This mixture was kept under rapid agitation for 60 minutes. This stage, which is generally referred to as an Interfacial Polymerization Process, produced capsules 25 to 65 microns large.
Stage 2: Second Wall Application
40 grams of Type A, 300 bloom gelatin was mixed at room temperature with 40 grams of gum arabic and 20 grams of ethylcellulose in 3.7 liters of tap water. This mixture was kept under mild agitation for 60 minutes to form a "bloomed" wall material solution.
The capsules manufactured in Stage 1 were immersed in the new wall solution, under mild agitation, with heating to 65º (C). After 60 minutes, the mixture was allowed to cool to room temperature while the agitation continued. The capsules were then filter-dried by Buchner funnel
filtration, producing a dry powder of microcapsules.
This procedure layered the gelatin-based shell material onto the resin-based wall of the capsule, creating a capsule with distinct wall layers.
GENERAL RESULTS
Stage 1:
Shell Material,
wall layer #1 Urea-
Formaldehyde
Volume of wall layer #1 in relation to total volume of capsule by weight for wall
layer #1 10% Size of capsules after
Stage 1 25 to 65
microns
Stage 2 :
Shell material mixture . Gelatin
Wall layer #2 Gum Arabic
Ethylcellulose
Volume of wall layer #2
in relation to total volume
of capsule by weight 5 to 10%
Size of final capsule unit 30 to 75 microns
The above table clearly demonstrates that a second wall surrounded the initial polymeric shell, forming a capsule of two distinct wall layers.
The two wall layers masked the Dursban-R odor better than a single wall layer did. This capsule unit was also more attractive to the pest, a household cockroach, which was drawn to the food source materials in the outer layer.
Experiment 4: A Method of Forming Capsules Within
Capsules
The goal of this experiment was first to form small capsules and then to encapsulate those capsules into a larger capsule, forming "Multi-Fill Capsules." Such
capsules may have unusual strength, slowed release
properties, and several unique product applications.
Stage 1; Produce Small Capsules
Experiment 3 above was repeated through Stage 1, except that the capsules were produced in a Waring blender with high shear. This process produced much smaller capsules (averaging 15 microns) than in Experiment 3. As in Experiment 3, these capsules contained a Dursban-R pesticide core in a ureaformaldehyde shell.
Stage 2: Prepare New Capsule Mixture
In Stage 2 of this experiment, the capsules from Stage 1 were filter-dried and mixed with a second core material and a second shell mixture.
100 grams of the shell material from Stage 1 and
400 grams of peanut oil were mixed with the wall solution of Experiment 3, Stage 2 in 4 liters of tap water. This first mixture was stirred under mild agitation for 30 minutes at room temperature.
The dried capsules from Stage 1 were then added to the first mixture, and the resulting second mixture was agitated for another 60 minutes with heating to 65º (C). At the end of the 60-minute time period, the second mixture was allowed to cool naturally to room temperature while
agitation continued for another 60 minutes.
The resulting gelatin-based shell material wrapped around both the peanut oil and the smaller capsules,
eventually encapsulating both. The resultant large capsules ranged from 30 to 50 microns in size and had several small capsules encased within each large capsule. The peanut oil deposit lay between the inner urea-formaldehyde layer and the outer gelatin-based layer. The pesticide core material lay in the core of the small capsules.
In tests against the household cockroach, this capsule-within-a-capsule unit worked best. The cockroaches were attracted by peanut oil odors from the outer capsules and began to eat the capsule units. The Dursban-R poison thereby escaped from the small capsules and killed the cockroaches.
All of the above examples are presented as
experiments to test the concept of an encapsulated pesticide with a lure or bait function. Variations may be possible to anyone skilled in the art.
There are various changes and modifications that may be made to applicant's invention, as would be apparent to those skilled in the art. However, any of those changes
and modifications are included in the teachings of applicant's disclosure, and it is intended that the invention be limited only by the scope of the claims appended hereto.
Claims
1. An encapsulated poison, which comprises:
(a) an outer capsule;
(b) lure material disposed inside said outer
capsule;
(c) at least one inner capsule disposed inside said outer capsule;
(d) poisonous material disposed inside said inner capsules;
so that said lure material attracts pests desired to be eliminated and masks any odors emanating from said poisonous material.
2. The encapsulated poison of claim 1, wherein said poisonous material comprises pesticidal material.
3. The encapsulated poison of claim 2, wherein said poisonous material comprises fungicidal material.
4. The encapsulated poison of claim 1, wherein said poisonous material comprises bactericidal material.
5. The encapsulated poison of claim 2, wherein said pesticidal material is selected from the group consisting of:
Alpha-Cubene Pyrethrins
Z-9-Dodecenyl Acetate Bendiocarb Gossyplure Diazinon
E,E-10, 12-Hexadecadienal Cypermethrin
Z-11-Hexadecenal Isophenphos
E-11-Tetradecenal Pyrethroid
Stirofos Gencor
Parathion Propetamphos
Malathion
Chlorpyrifos
X-Clude
6. The encapsulated poison of claim 1, wherein said lure material comprises at least one food source.
7. The encapsulated poison of claim 6, wherein said food source is selected from the group consisting of:
Carboxymethylcellulose Zein
Cellulose acetate phthalate Nitrocellulose
Ethylcellulose Cheese Gelatin Bacon Grease
Gum Arabic Succinylated Gelatin
Starch Peanut Oil
Bark Proteins
Methylcellulose Kraft Lignin
Butter Peanut Butter
8. The encapsulated poison of claim 1 , wherein said lure material comprises at least one sex attractant.
9. The encapsulated poison of claim 8 , wherein said sex attractant is selected from the group consisting of : endo-Brevicomin 14-Methyl-E-8 hexadecenal
E,E,8,10-Dodecadien-1-ol 14-Methyl-Z-8-hexadecenal
Z-7-Dodecen-1-ol Acetate 2-Methyl-Z-7octadecene
Z-8-Dodecen-1-ol Acetate Multistriatin
E-8-Dodecen-1-ol Acetate Z,Z-Octadecadienol
Z-9-Dodecen-1-ol Acetate Z,Z-3,13-Octadecadien-1-ol Acetate
E-10-Dodecen-1-ol Acetate E,Z-3,13-Octadien-1-ol Acetate
Frontalin Z-13-Octadecenal
Z-6-Heneicosen-11-one Z-9-Octadecen-1-ol
Z,Z-3,13 Hexadecadienal Z,E-9,12-Tetradecadien-1-ol
Z,Z-7,11-Hexadecadienal Tetradecenal
Z,Z—11,13 Hexadecadienal Z-9-Tetradecenal
E,Z-7,11 Hexadecadienal-1-ol Acetate Z-11-Tetradecenal
Z,E-7,11-Hexadecadienyl Acetate Z,E-11-Tetradecenal
Z-9-Hexadecenal Z-9-Tetradecen-1-ol Acetate
Z-11-Hexadecen-1-ol Z-11-Tetradecenr-1-ol
Z-11-Hexadecen-1-ol Acetate Z-8-Tetradecen-1-ol Acetate
Ipsdienol Z-11-Tetradecen-1-ol Acetate
Ipsenol Z-9-Tetradecen-1-ol Formate 2-Msthyl-2-cyclohexen-1-one cis-Verbenol
3-Methyl-2-cyclohexen-1-one trans-Verbenol
Verbenone
10. The encapsulated poison of claim 1, wherein said inner and outer capsules consist essentially of polymeric materials.
11. The encapsulated poison of claim 10, wherein said polymeric materials are selected from the group consisting of:
Natural Polymers
Carboxymethylcellulose Zein
Cellulose acetate phthalate Nitrocellulose
Ethylcellulose Propylhydroxycellulose
Gelatin Shellac
Gum arabic Succinylated gelatin
Starch Waxes, paraffin
Bark Proteins Methylcellulose Kraf t lignin
Arabinogalactan Natural rubber
Synthetic Polymers
Polyvinyl alcohol Polyvinylidene chloride
Polyethylene Polyvinyl chloride
Polypropylene Polyacrylate
Polystyrene Polyacrylonitrile
Polyacrylamide Chlorinated polyethylene
Polyether Acetal copolymer
Polyester Polyurethane
Polyamide Polyvinylpyrrolidone
Polyurea Poly (p-xylylene)
Epoxy Polymethyl methacrylate
Ethylene-vinyl acetate copolymer Polyhydroxyethyl methacrylate
Polyvinyl acetate
12. The encapsulated poison of claim 1 , wherein said inner and outer capsules consist essentially of elastomeric materials.
13. The encapsulated poison of claim 12, wherein said elastomeric materials are selected from the group consisting of:
Polybutadiene Asrylonitrile
Polyisoprene Nitrile
Neoprene Butyl rubber
Chloroprene Polysiloxane
Styrene-butadiene rubber Hydrin rubber
Silicone rubber Ethylene-propylene-diene terpolymer
14. The encapsulated poison of claim 1 , wherein said outer capsule consists essentially of gelatin , gum arabic , and ethylcellulose .
15. The encapsulated poison of claim 1 , wherein said inner capsule consists essentially of a urea-f ormaldehyde resin.
16. An encapsulated poison, which comprises:
(a) a capsule; and
(b) lure material coated on the outside of said capsule; and
(c) poisonous material disposed inside said
capsule; and
(d) further comprising a capsule shell coating surrounding said lure material; wherein said lure material attracts pests desired to be eliminated and masks any odors emanating from said poisonous material.
17. The encapsulated poison of claim 16 , wherein said poisonous material comprises pesticidal material .
18. The encapsulated poison of claim 17 , wherein said poisonous material comprises fungicidal material.
19. The encapsulated poison of claim 17 , wherein said poisonous material comprises bactericidal material.
20 . The encapsulated poison of claim 17 , wherein said pesticidal mater ial is selected from the group consisting of :
Alphar-Cubene Pyrethrins
Z-9-Dodecenyl Acetate Bendiocarb
Gossyplure Diazinon
E,E-10, 12-Hexadecadienal Cypermethrin
Z-11-Hexadecenal Isophenphos
E-11-Tetradecenal Pyrethroid
Stirofos Gencor
Parathion Propetamphos
Malathion
Chlorpyrifos
X-dude
21. The encapsulated poison of claim 16, wherein said lure material comprises at least one food source.
22. The encapsulated poison of claim 21, wherein said food source is selected from the group consisting of:
Carboxymethylcellulose Zein
Cellulose acetate phthalate Nitrocellulose
Ethylcellulose Cheese
Gelatin Bacon Grease
Gum Arabic Succinylated Gelatin
Starch Peanut Oil
Bark Proteins
Methylcellulose Kraft Lignin
Butter Peanut Butter
23. The encapsulated poison of claim 16, wherein said lure material comprises at least one sex attractant.
24. The encapsulated poison of claim 23, wherein said sex attractant is selected from the group consisting of: endo-Brevicomin 14-Methyl-E-8-hexadecenal
E,E,8,10-Dodecadien-1-ol 14-Methyl-Z-8-hexadecenal
Z-7-Dodecen-1-ol Acetate 2-Methyl-Z-7-octadecene
Z-8-Dodecen-1-ol Acetate Multistriatin
E-8-Dodecen-1-ol Acetate Z,Z-Octadecadienol
Z-9-Dodecen-1-ol Acetate Z,Z-3,13-Octadecadien-1-ol Acetate
E-10-Dodecen-1-ol Acetate E,Z-3,13-Octadien-1-ol Acetate
Frontalin Z-13-Octadecenal
Z-6-Heneicosen-11-one Z-9-Cctadecen-1-ol
Z,Z-3,13 Hexadecadienal Z,E-9,12-Tetradecadien-1-ol
Z,Z-7,11-Hexadecadienal Tetradecenal
Z,Z-11,13 Hexadecadienal Z-9-Tetradecenal
E,Z-7,11 Hexadecadienal-1-ol Acetate Z-11-Tetradecenal
Z,E-7,11-Hexadecadienal Acetate Z,E-11-Tetradecenal
Z-9-Hexadecenal Z-9-Tetradecen-1-ol Acetate
Z-11-Hexadecen-1-ol Z-11-Tetradecen-1-ol
Z-11-Hexadecen-1-ol Acetate Z-8-Tetradecen-1-ol Acetate
Ipsdienol Z-11-Tetradecen-1-ol Acetate
Ipsenol Z-9-Tetradecen-1-ol Formate
2-Methyl-2-cyclohexen-1-one cis-Verbenol
3-Methyl-2-cyclohexen-1-one trans-Verbenol
Verbenone
25. The encapsulated poison of claim 16, wherein said capsule is composed of polymeric materials.
26. The encapsulated poison of claim 25, wherein said polymeric materials are selected from the group consisting of:
Natural Polymers
Carboxymethylcellulose Zein
Cellulose acetate phthalate Nitrocellulose
Ethylcellulose Propylhydroxycellulose
Gelatin Shellac
Gum arabic Succinylated gelatin Starch Waxes, paraffin
Bark Proteins
Methylcellulose Kraft lignin
Arabinogalactan Natural rubber
Synthetic Polymers
Polyvinyl alcohol Polyvinylidene chloride
Polyethylene Polyvinyl chloride
Polypropylene Polyacrylate
Polystyrene Polyacrylonitrile
Polyacrylamide Chlorinated polyethylene
Polyether Acetal copolymer
Polyester Polyurethane
Polyamide Polyvinylpyrrolidone
Polyurea Poly(p-xylylene)
Epoxy Polymethyl methacrylate Ethylene-vinyl acetate copolymer Polyhydroxyethyl methacrylate
Polyvinyl acetate
27 . The encapsulated poison of claim 16 , wherein said capsule consists essentially of elastomeric materials.
28. The encapsulated poison of claim 27 , wherein said elastomeric mater ials are selected from the group consisting of :
Polybutadiene Acrylonitrile
Polyisoprene Nitrile
Neoprene Butyl rubber
Chlorqprene Polysiloxane
Styrene-butadiene rubber Hydrin rubber
Silicone rubber Ethylene-propylene-diene terpolymer
29. The encapsulated poison of claim 16 , wherein said capsule consists essentially of gelatin, gum arabic , and ethylcellulose .
30. The encapsulated poison of claim 16 , wherein said lure material comprises peanut oil .
31. A method of encapsulating poisons, comprising the steps of :
(a) mixing poisonous material with material
capable of forming polymers , resulting in a f irst mixture;
(b) heating the first mixture ;
(c) agitating the first mixture until f irst
capsules made of the polymer-forming material enclose the poisonous material ;
(d ) mixing the f irst capsules with lure material and a second set of material capable of forming polymers , resulting in a second mixture;
(e) heating the second mixture; and (f) agitating the second mixture until second capsules made of the second polymer-forming material enclose the first capsules and the lure material ;
so that the lure mater ial exhibits an odor that attracts pests and masks any odors from the poisonous material.
32. A method of encapsulating poisons, comprising the steps of:
(a) mixing lure materials capable of forming a precondensate colloid upon agitation;
(b) agitating the lure materials until a
precondensate colloid is formed;
(c) mixing poisonous material with the precondensate colloid, forming a poison- colloid mixture;
(d) heating the poison-colloid mixture; and
(e) agitating the poison-colloid mixture until capsules made of the lure material enclose the poisonous material;
so that the lure material exhibits an odor that attracts pests and masks any odors from the poisonous material.
33. A method of encapsulating poisons, comprising the steps of:
(a) agitating materials capable of forming
polymers until a precondensate colloid is formed;
(b) mixing poisonous material with the precondensate colloid, forming a poison- colloid mixture;
(c) heating the poison-colloid mixture;
(d) agitating the poison-colloid mixture until capsules made of the polymer-forming material enclose the poisonous material;
(e) immersing the capsules in lure material; and (f) agitating the immersed capsules and lure
material until the lure material coats the capsules.
34. The method of claim 33, further comprising the steps of:
(a) mixing the coated capsules with a second
precondensate colloid of materials capable of forming polymers, forming a second mixture;
(b) heating the second mixture; and
(c) agitating the second mixture until the second set of polymer-forming materials forms shells adhering to the coated capsules.
35. The method of claim 34, wherein the steps listed are repeated.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21377988A | 1988-06-30 | 1988-06-30 | |
US213,779 | 1988-06-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990000005A1 true WO1990000005A1 (en) | 1990-01-11 |
Family
ID=22796479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1989/002903 WO1990000005A1 (en) | 1988-06-30 | 1989-06-30 | Microencapsulated pesticides with a lure |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO1990000005A1 (en) |
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WO1998007315A1 (en) * | 1996-08-21 | 1998-02-26 | The United States Of America, As Represented By The Secretary Of Agriculture | Device for controlling pests |
WO1998010646A1 (en) * | 1996-09-14 | 1998-03-19 | The Minister Of Agriculture Fisheries And Food In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Pesticidal composition and method |
GB2331461A (en) * | 1996-09-14 | 1999-05-26 | Mini Agriculture & Fisheries | Pesticidal composition and method |
FR2772556A1 (en) * | 1997-12-19 | 1999-06-25 | Al Tech | Granules for repelling animals, especially wild boars |
US5925370A (en) * | 1997-12-04 | 1999-07-20 | The United States Of America As Represented By The Secretary Of The Navy | Biorepellent matrix coating |
US6585991B1 (en) * | 1999-04-20 | 2003-07-01 | The United States Of America As Represented By The Secretary Of Agriculture | Termite bait matrix |
US7117631B2 (en) | 2004-06-11 | 2006-10-10 | John Peters | Microencapsulated animal trap bait and method of luring animals to traps with microencapsulated bait |
US7566747B2 (en) | 2004-05-07 | 2009-07-28 | The Board Of Trustees Of The University Of Illinois | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
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WO1998007315A1 (en) * | 1996-08-21 | 1998-02-26 | The United States Of America, As Represented By The Secretary Of Agriculture | Device for controlling pests |
WO1998010646A1 (en) * | 1996-09-14 | 1998-03-19 | The Minister Of Agriculture Fisheries And Food In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Pesticidal composition and method |
GB2331461A (en) * | 1996-09-14 | 1999-05-26 | Mini Agriculture & Fisheries | Pesticidal composition and method |
GB2331461B (en) * | 1996-09-14 | 2000-04-26 | Mini Agriculture & Fisheries | Pesticidal use of halogenated hydrocarbons |
US5925370A (en) * | 1997-12-04 | 1999-07-20 | The United States Of America As Represented By The Secretary Of The Navy | Biorepellent matrix coating |
FR2772556A1 (en) * | 1997-12-19 | 1999-06-25 | Al Tech | Granules for repelling animals, especially wild boars |
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US7117631B2 (en) | 2004-06-11 | 2006-10-10 | John Peters | Microencapsulated animal trap bait and method of luring animals to traps with microencapsulated bait |
US7612152B2 (en) | 2005-05-06 | 2009-11-03 | The Board Of Trustees Of The University Of Illinois | Self-healing polymers |
US7723405B2 (en) | 2006-01-05 | 2010-05-25 | The Board Of Trustees Of The University Of Illinois | Self-healing coating system |
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US7569625B2 (en) | 2006-06-02 | 2009-08-04 | The Board Of Trustees Of The University Of Illinois | Self-healing elastomer system |
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US10980235B2 (en) | 2017-02-13 | 2021-04-20 | Clarke Mosquito Control Products, Inc. | Insecticidal composition |
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US11412732B2 (en) * | 2018-05-17 | 2022-08-16 | International Business Machines Corporation | Light-triggered sustained release of pesticides |
WO2019236669A1 (en) * | 2018-06-08 | 2019-12-12 | The United States Of America, As Represented By The Secretary Of Agriculture | Compositions containing microencapsulated organic compounds |
WO2021013917A1 (en) | 2019-07-23 | 2021-01-28 | Fachhochschule Bielefeld | New formulation based on an oleo gel, in particular for releasing volatile components, and method for the production thereof |
WO2024003267A1 (en) * | 2022-06-30 | 2024-01-04 | Kapsera S.A.S. | Microcapsules controlling the diffusion of an active organic compound |
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