AP1387A - Composition for impregnation of fabrics and nettings. - Google Patents
Composition for impregnation of fabrics and nettings. Download PDFInfo
- Publication number
- AP1387A AP1387A APAP/P/2002/002515A AP2002002515A AP1387A AP 1387 A AP1387 A AP 1387A AP 2002002515 A AP2002002515 A AP 2002002515A AP 1387 A AP1387 A AP 1387A
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- Prior art keywords
- cis
- insecticide
- dimethyl
- fabric
- phenoxybenzyl
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
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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
- A01N25/24—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 ingredients to enhance the sticking of the active ingredients
-
- 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
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
There is provided an impregnated netting or fabric for insect or tick killing and repellence which comprises an insecticide and/or repellant, and a film forming component which reduces wash off and degradation of the insecticide component from the netting or fabric. This is achieved by forming a water resistant and optionally an oil resistant film which is a molecular shield around the fibres incorporating the insecticide or the repellant, either by integration of the insecticide or the repellant in the film, or by forming a substantial continuous film surrounding the insecticide/repellant together with the fibre.
Description
The invention relates to a pesticidal composition containing pesticidal components preferably for use against biting and nuisance insects and impregnated to fabric or netting. The composition comprises a pesticidal component from the groups of pyrethroids and other insecticides with a fast kill effect and preferably also a repellent effect, awash protective agent, a fixating agent, a solvent for the pesticide and optionally one or more detergents. The invention also relates to a process for the preparation of the pesticidal impregnation composition and curing to the fabric or netting.
Background for the invention
A number of different insects cause substantial problems as vectors and transmitters of infectious diseases affecting humans, and tremendous efforts are invested in controlling these insects. Efforts have been concentrated on controlling insects belonging to the order Diptera (covering mosquitoes, gnats, black flies, tsetse flies and other biting flies), Hemiptera (covering bed bugs) and Siphonaptera (covering fleas). Methods to control these insects include treating inner and outer surfaces of walls, air spraying, and recently also impregnation of curtains and bednets. The impregnation of curtains and bednets has the advantage that the surface area io be treated Is much reduced compared to a surface spraying of a house. The impregnation of the bednet reduces nuisance during sleeping and has been shown to be effective even if the net is slightly tom due to use. Several studies have shown that mosquitoes belonging to the genera Anopheles and Culex preferably bite during night time and that oviparous mosquitoes (i.e. mosquitoes that have passed at least one egg laying cycle and thus have bitten at least once, therefore potentially infected with a disease) bite closer to midnight than nulliparous (first time biting) females. Accordingly, bednets protect even better against disease transmitting mosquitoes than against nuisance caused by the same species since first time biters cannot be infected. Contrary to that, they do not protect against mosquitoes of the genus Aedes, black flies and species of biting flies that bite during daytime and for seme species, only out door. Cloth impregnated with an insecticide and/or a repellant can provide protection against these insects and also reduce bites from night active insects when the person is not under the protection of the bednet.
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The effect of 2 netting or fabric impregnated with a pyrethroid is partly based on tne fafo insecticidal property co these insecticides, but aiso on the repellent effect inherent in most of these insecticides. Tests have shown (Vincent et al.) that an impregnated fcednet reduce the number of mosquitoes entering the room with up till 75 %. Thereby, tris net aiso provides some protection for other persons sleeping in the same room even -hey are not covered by the net.
Large scale fieid experiment with netting have shown that they may reduce rmriana infection rate as measured directly or indirectly as gross children mortality. Accordingly, netting has been selected as a priority area for the campaign against malaria and other mosquito born diseases by WHO, the World Health Organization.
'η .in some areas mosquitoes are resistant to pyrethroids. One of these resistu, .teysc- i.ro called knock down resistance or kdr, also provides resistance to the repellent effect a «•β’-» (Chandre et al., Hodjati and Curtis, 1999). This allows the mosquitoes to rest for a longer )j time on the net and thus to accumulate a lethal dosage of the insecticide, but it also gives · the mosquitoes the possibility to bite before dying (Skovmand, unpublished information).
In areas where these mosquitoes are dominating, a repellant can be added to the net with · great advantage. '
-The advanfaaes of the impregnated nets, curtains and fabric disappear at v.~ , '«7 s.uce ‘Ts riff these oils are washed off with reduced enect as a consequence. The fabric co netting must then be re-impregnated according to washing rate (Lines, 1996), but this have in . w practice shown *0 he very difficult to organise, especially in remote African or r ·. vs therefore, an impregnation method that provides wash resistance will prolor ..- we of protection of the net and promote their use.
m some areas, pecpis sleep outdoor cfonng the hot season of the year and risk to exposed io UV light. Some pyrethroids degrade slower than others n <„'·
3U ot UV light Put none cithern are veiv ·:-o;rant. The addition of UV protector; can thus < 3 u. .: V * , < <e net.
The generally
Nets of pome:
vd world wide preferred material for bedneis are cotton and r nas oeen chosen by WHO as the favourite material for L· their better strength, their cotton like feeling and reduced flammability. Opposite to that, nets of nylon and polyethylene are stiff and nylon is flammable.
Among the current formulations of pesticides for the impregnation of netting, only one 5 method provides a long termed protection (Sumitomo, Olyset). This product is based on a monomer polyethylene fibre that is impregnated during formation of the fibre. The method cannot be used for the impregnation of a polyester fibre that is produced at temperatures destructive for the pyrethroids. Further, the resulting nets are sold at prices that are too high for people in poor countries.
Several methods can be used for the impregnation of fabric. In general, these methods take advantage of the tight structure of fabric and cannot be used on the smooth, open structure of a polyester net.
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US Patent No. 4,056,610 (Barber, et al.), the invention provides for a microcapsular 'CS.' insecticidal composition comprising a pyrethroid and a biological synergist capable of ___ controlling insects for up to four (4) days. This cannot be named residual activity, since a s:mple solution of a pyrethroid on polyester provides longer, residual activity.
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US Patent No. 4,765,982 (Ronning) relates to compositions, devices and methods for controlling insect activity wherein an insect control agent is self-adhered to a rough- $*>.
surfaced fibre and provides extended control of insect activity. The microencapsulated insect control agents disclosed in US Pat 4,056,610 are mentioned as the preferred insecticide for use in the invention. The invention relates to the production of a device made of rough cellulosic fibres.
US 5.089.2S8 (McNally and Samson) teaches that the addition of amylopectine to garment with permethrin offers some wash off protection. However, this binder is water soluble and will only give a poor protection in a polyester netting.
US 5,198,287 (Samson) relates to a tent fabric coated on the inside with a composition which renders it water repellent, flame retardant and insect repellant using permethrin as the insect repellant. Permethrin is incorporated in the inside impregnation of the tent thus protected against sun and atmospheric breakdown. The polymer used for the outside of the tent is coated with a composition, which renders it water repellent and flame retardant.
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The insect-i.m .nt composition on the inner side of the tent nas an effective · .At,;
than six (δ) months. The invention basically relates to tents and the use of permethrin as a combined insect repeilant and insecticide and the protection against UV break · uvn of the permethrin by applying it to the inside of a tent The examples given show the .· a polymers used are acrylic copolymers with zirconium wax for mobilising the permethrin in the polymer.
EP-A 0 731 208 (Samson) teaches that the dosage of 1.25g Permethrin/m2 in fabric is strong enough to repel insects and that the addition of a polyvinyl acetate binac preserves the Insecticidal effect of permethrin through several wash cycles. Tms process As claimed to be more effective than that covered by US Pat 5,089.298, a patent oi the same author. Polymerisation of polyvinyl acetate result in a rather stiff film as * wa from A.) “plastic paintings (that are normally based on this chemical). The net has no longer a “cotton feeling”. The patent discloses the use of polyvinyl acetate as a wash-resistance 15 agent to protect, an impregnation with permethrin.
WO 95/17091 (Tucci) teaches on the slow release from starch encapsulated slow release formulations of DEET. Adhesion of the starch capsules may bs improved by cross-linking to the fabric anc their wash resistance can be improved by adding a silicone polymer. Tne patent covers formulations where the principle is based on starch encapsulation A DEET.
EP 0 787 851 Ai (Samson, corresponds to US pat 5.631.072) teach on the wash resistant impregnation of fabric with a polymer binder and/or a cross-linking agent where foe insecticide is added in an emulsion with a thickening agent. The patent discin'·· .· '—AS permethrin as the insecticide, polyvinyl acetate as the polymer and urethane ί . .: s a cross-im:. a . ’ . > iu jr and the insecticide is tank mixed and added simultaneously, still using 1.25 g Per > , An2 as dosage to obtain that the . .'.j!
Insecticidal by contact after several washes. The invention aiso relates to ussolutions on one side of.the fabric only.. The examples disclose an acrylic binds' and the polymers given as examples are ail rw . The patent does not relate to to resistance ·'. -* · mingse»'·* nolecular shields or the u=-j rr
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US 5,630.841 (Kraft) relates to a metrics for the producing of an insect-active : trial can be t * j meet. The patent follows the same principle as cis
- A: Ά . ,.. ; : o improves · ·· ? c.d for production to avoid hiah ten ssrnpry snbed m
ΑΡ ε β 13 8 z during the production process, since these makes the DEET to evaporate or deteriorate. The patent refers to a US Pat 4,752,477 of the same author. The patent regards the production of a device and not impregnation of fabric or garment.
US 5,733,550 (Davister et al.) teaches the use of a chemical linker to link a range of organic compounds to a surface. The range includes insect repeliants. The chemical linker is an ethoxylated glycerol compound, optionally a carbolic acid having 4-6 carbon atoms, a polyvinyl pyrroiidone and a polyethylene glycol having a molecular weight of 600 to 10,000. Our invention does not contain suck chemical linkers.
US 5,884,418 (Me Naily) relates to a process and system for impregnating garments with i' ‘ y bb insect repellant by placing the garment in tumbling machines with nozzles that spray a water emulsion containing permethrin onto the garment. This process is close to a dry cleaning process, and different from a process where the garment, fabric or netting is impregnated in a liquid (water with emulsion or solvent with solution) containing an insecticide composition or an insect repellant or a combination hereof. The process A relates to garments and not to fabrics or nettings. θ
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US 5,916,580 (Shober et al.) (equivalent to British Patent 9505653) relates to a method of θ controlling dust mites involving impregnating pre-formed netting with a liquid composition including a pyrethroid insecticide. The netting is applied around an article, such as a' teSiK pillow, mattress, duvet, cushion, beanbag or domestic pet bed. The impregnation sfiS* insecticide is a pyrethroid such as permethrin or deltamethrin. The claimed method consists of dipping a netting in a commercially available water emulsion of the pyrethroid and air-drying, i.e. the standard method for dipping beanets. This method does not provide fabric or’netting able to resist many wash cycles, and the new perspective is only that it is used against dust mites.
US 5,930,909 (Me Nally) is a continuation of US 5,884,418, but now several garments are 30 impregnated at the same time and the process is controlled by use of a microprocessor.
Summary of the invention
Biting insects and mites are paralysed even after a short contact with a surface treated with some kinds of insecticides like pyrethroids and may even be repelled before the
contact. This combined ability can aiso bo obtained by using the combination insecticide and a repeiiant. Fabric or netting impregnated with these active ingredients can therefore prevent the insects in biting or kill them after short contact. Several biting insects ars vectors of diseases where the disease-causing agent has a ripen: -hose or a development within the Insect before it becomes infective at a bite of the next host.
Whan the garment is carried by a person or a net suspended around a bed or sn a window or door, the attractive stimuli of the target is counteracted by the evaporated r. _w_.:es of the insecticide or repeiiant and on contact with the garment or netting, excitak , : witact repulsion effects are involved. For the netting and especially the garment, the choice of insecticide ot repeiiant should not be irritating or intoxicating by contact or re-. - ..-srirritation effect (coughing, headache) is often reported when using traditionally methods for impregnation with insecticides. In accordance with the present invention n - .n-.-cm ft. J can be counteracted by a surface coating that also provides wash resistance. Further, art • -¾
UV inhibitor, reflector or absorber can be added to protect against deterioration of the ’ insecticide and/or repeiiant. , -.
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Insects have been able to develop an inherited tolerance to insecticides: resm.. : -.
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Resistance against pyrethroids has been found for several mosquito species, Inducing Anopheles species. To avoid further build up of such resistance and to overc-c: tne ack o of efficacy when pyrethroid impregnated nets are used in areas with pyrethroid resistant (T or avoiding insects, other insecticides can c»e used either alone or in combine:.. · -.- iih a Tv pyrethroid. For toxicological and registration reasons, the two insecticides sh - -*.· r... * · ·.( applied on various parts of the net or fabric and not mixed and used horrogs- , A choice of alternative or supplementing insecticides can be taken from carb&r. ·.· .
C J '-WS organophosphorous or sterilising insecticides or other insecticides. Preferably.
insecticides witn low mammalian tocT· ft s. high insect toxicity, low skin or u xa.i rn ability, low vapour pressure and low water solubility are applied.
Any surface impregnation will in the long run be washed off and it is thereic .· inters rt-g ‘ . = m :, g educing > - -treatmentthatwilireducetherintensive washing of the garment or . The combination of a wash reslm treatment and a soring resistant tm -: on therefore further prolong m.
The present appiication relates to such a pesticidal or pesticidal-repellant composition that provides wash resistance, reduce irritability of the insecticide, reduce soiling, do not increase flammability and still ieaves the fabric or netting with the same sensation of cloth and not stiffened. An UV agent can be added when relevant. The invention is not based on a polymer of polyvinyl acetate. The invention relates to the addition of a thin layer of a wash resistant agent that protects a layer of insecticide or insecticide-repellant or the protection is obtained by incorporation of the insecticide composition in the wash resistant agent The composition may aiso be partly absorbed in an absorptive fabric. The added layer is so fine that it does not stiffen the fabric or netting.
The invention aiso relates to the process for preparation of the impregnation. This process may be of industrial scale using machines of the textile industry normally used for colouring or impregnation and this will give the most stable and homogenous results. One of the two types of compositions presented may also be used for simple hand dipping of tn c\s garment or netting and will after horizontal drying result in an impregnation with reduced ς irritation and increased wash resistance as compared to traditional insecticide emulsions · used for impregnation of netting. The method will not give the same homogenous distribution of impregnation as in the machine impregnation described in this invention.
Detailed description of the invention lib ο**
The pesticidal composition according to the invention relates to a composition consisting · of a pesticide or a pesticide and a repellant. The protective composition according to the invention relates to a single component or a mixture of components giving water or water and oil resistance. One or several detergents may be added to increase wettability of the agent to the fabric, to stabilise emulsions used, or to increase fixation. A cross-linking agent or a catalyser may be used to increase fixation. The pesticidal composition and the protective composition may be added successively (process 1) or in one process (process 2). An improved finish and curing may be obtained by finally passing a heated surface such as an iron or a heated roller or heating with hot air. An UV agent may be added during the process when needed in the final product.
In the present context, the term “pesticidal component” means any component having a pesticidal effect and being active in controlling or combating insects such as biting insects.
According to the present invention, the ·.. .ucsdai component is preferably a .- Λ;. a fast paralysing or killing effect of the insect and very iow mammalian toxicity, Preferred, insecticides are insecticides belonging to ine group of pyrethroid compounds. ., ·. a-, ethoienprox: 2-(4-ethoxyphenyi)-2-rr.:-'. :: opyi-3-phenoxybe.nzyl ether,
Fenvalerate: (RS)-alpba-cyano-3-phenoxybenzyl (RS)-2-(4-chiorophenyl)-3 rnethylbutyra-e
Esfenvaleratc . -alpha-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-r.t , Fenpropathrin: (RS)-aipha-cyano-3-phenoxybenzyl 2,2,3,3ietramethylcyciopropanecarboxyiate,
Cypermethrin: (RS).....alpha-cyano-3-phenoxybenzyi (1RS)-cis, irans-3-(2,2-dschnvavmyi)2,2-dimeim * ' rboxylate,
Permethnn: 3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2r dimethylcyclopropanecarboxylate,
Cyhalothrin: (RS)-aipha-cyano-3-phenoxybenzyl (2)-(1 RS)-cis-3- (2-chloro-3R .
trifiuoroprop-1-enyl)-2,2-dimethylcycsOprO panecarboxyiate,
Dettamethrin: (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl) -2.2dlmethylcydopropanecarboxylate,
Cycloprothrin: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2,2-dichloro -1-(4ethoxyphenyi)cyclopropanecarboxyiate,
Fiuvalinate (alpha-cyano-3-phenoxybenzyl N-(2-chloro-alpha.aipha,alpha-trifluoro-p-tolyl)-D-valinate),
Bifenthrin: (2-methylbiphenyl-3-yimethyi)0(Z')-(1RS)-cis-3-(2-chloro-3,3,3-triti'. . tat ’ aa ,-L propenyl)-2,2-d?methylcydopropan-'· < ,-iate,
2-methyl-2-(4-bromodifluoromethoxyphenyi)propyl ^25 (3-phenoxybenzyi) ether.
Tralomethrin aipna-cyano-3-pheno benzyl (1Β<ί5)3((1Έ8)(1',2·,2’,2'tetrabromoethyf)) -2,2-dirnetfiy!cyd· r ι-carboxyiate,
SBafluofen: 4-efhoxyphenyi (3-(4-fluorp-3-ohenoxyphenyl)propyl}dimethyisiiche
D-fenothrin: '· myi (IR)-cls,
Cyphenot „ ' ano-3-phe.
,r' τη.? rs C . mRmC ,
Acnnathrin: (8(-mpha-cyano-3-phenoxy (1,1,1.5.3 5- se- .,,ryloxylproDe· .: ι. ir , - ’ .o-d-fluoro- j· ; ’ net. y ?v c .-'viate, ,-cnrysanthemats, no.xybenzyl (1R-cis, transj-chr/sanihem as Iransf-chrysanthemate, cyl (1 R-cis(Z) )-(2,2-dimethyF3- (cxq y -. a/clopropanecarboxyiate,
-phenoxybenzyl 3-(2,2-daNorovmyA,2 uAP-01387
Tefluthrin: 2,3,5,S-tetrafluoro-4-methy!benzyl (1RS-cis (Z))-3-(2-chloro-3,3,3-trifluoroprop1-enyl)-2,2-dimethylcyclopropanecarbo xyiate,
Transfluthrin: 2,3,5,6-tetrafluorobenzyl (1R-trans)-3-(2,2-dichlorovinyl) -2,2dimethylcyclopropanecarboxylate,
Tetramethrin: 3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis, trans-chrysanthemate, Aiiethrin: (RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1 RS)-cis, trans-chrysanthemate, Prallethrin: (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyi (1R)-cis, transcnrysanthemate,
Empenthrin: (RS)-1-ethynyl-2-methyi-2-pentenyl (1R)-cis, trans-chrysanthemate,
Imiprothrin: 2,5-dioxo-3-(prop-2-ynyl)imidazofidin-1-y!methyl (1R)-cis, trans-2,2-dimethyl-3-(2-methy!-1-propenyl)-cyclopropanecarboxyiate,
D-flamethrin: 5-(2-propynyl)-furfuryl (1 R)-cis, trans-chrysanthemate, and 5-(2propynyl)furfuryl 2,2,3,3-tetramethylcyciopropanecarboxylate.
Insects are capable of developing resistance, and mosquitoes and other biting insects have already been observed to develop resistance to pyrethroids. In such cases, it may be advantageous to replace the pyrethroid with another insecticide with a low mammalian toxicity or to impregnate a part of the mosquito net with a pyrethroid and a part of it with another insecticide. Such a combination may also be used in general as a strategy to delay resistance development. Care should be taken to combine insecticides that have little or no chance to develop cross resistance, e.g. where the development of resistance to one of them also confer resistance to the other even the two insecticides are of different type. Such alternative or supplemental insecticides may be compounds such as organophosphorous compounds including
Fenitrothion: Ο,Ο-dimethyl 0-(4-nitro-m-tolyl) phosphorothioate,
Diazinon: 0,0-diethyl-0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate,
Pyridaphenthion: 0-(1,6-dihydro-6-oxo-1-phenylpyrazidin-3-yl) 0,0-diethyl phosphorothioate,
Pirimiphos-Etyl: 0,0-diethyl 0-(2-(diethylamino) 6-methyl-pyrimidinyl) phosphorothioate, Pirimiphos-Methyl: 0-[2-(diethylamino)-6-methyl-4pyrimidinyl] 0,0-cimethyl phosphorothioate, iu“>
o zv· o
Etrimphos: 0-5-ethoxy-2-ethyl-pyrimidin-4-yl-0,0-dimethyl-phosphorothioate, Fenthion:
0,0-dimethyl-0-[-3-methyl-4-(methyithio) phenyl phosphorothioate, Phoxim: 2(diethoxyphosphinothoyloxyimino)-2-phenylacetonitrile.
Ar
Chiorpynkc: r r-0-(3,5,6-%. . - 5/rinyi) phosphorothioate,.i > - methy!: 0,0-dimeihyi 0-(3,5.6-trichloro-2~pyridinyl) phosphorothioate, Cyano-.. dimethyl Q-(4cyariophenyl) phosphoroiruoate,
Pyracioms’,< )-- ..-phenyi;-;· · '-yi]-O-ethyl-S-n-propyl phospho’.
Acephate: O.S-dsmethyi acetylphosphoroamidothioate,
Azsmethiphosi S-(6-chioro-2,3’dihydro-oxo-1,3-oxazolo [4,5-b] pyridin-3-yir .· phosphorothioate,
Malathion: O.iAdimethyi phosphorodlihioaie ester of diethyl msrcaptosuccinate,
Temephos; (0,G’(thiodi-4-1-phenylene) 0,0,0,0-tetramethyS phosphorodithioate,
Dimethoate: ((0,0-dimet'nyl S-(n-methyicarbamoylmethyl) phosphorodithioate, Formothion; S[2-formy!methyiam!no]-2-oxoethyi]-010-dimethyl phosphorodithioate, Phe·- : a _ dimethyl S-ialpiia-ethoxycarbonylbenzvit-Dhosphorodithioate;
V
Furthermore, carbamate compounds may be applied including compounds $ : ac
Alanycarh: Sinethyi-Ni[N-methyl-N-iNteen2yl-N(2-efhoxy-carbonyie{hyi) amsnothiojcarbarnoyfjthioacetirnidate,
Bendiocarb: CM-dimeihyM.S-benzodioxoMyl- methy lcarbamate),
Carbaryl (1-naphthyi N-rnethylcarbamale, isoprocarb: 2-(1-methylethyl) phenyl methy lcarbamate,
Carbosulfan: 2,3 dihydro-2,2-dimethyl-7-benzofuranyl i(dibutyiaminonh!O]methyicarbamate,
Fenoxycarb: Bhyl[2-(4-phenoxyphertoxy)eihyl] carbamate,
Indoxacarb: Meihyi-7-chloro-2,3,43,5»ietrahydro-2~imethoxycarbonyl (-4triiluoromeihoxvDhenyOj j
Propoxur: 2-isopropyioxypheno! me «. mate,
Pirimicarb; 2-dimethylamino-5,6-^ir; . pyrimidinyl-dimethylcarhamate.
Dimethyl N.N’iihiobtsfbmethyliminoJcaroonoyioxy^isethanimidiothioaie),
Methomvi: G-mstny! N-(fmethy!carbamoyl)oxy)thio3cetamidate,
Ethiofenco - ,.- methyl.ip·-··---·-. oMnylcarbamate, :' : enter,.,;. -. *- ,·- - /ουη··-'’: · :’nyl thiocarbamats, .teriao . - -· ,io'ter - ·- ic.s (thiocarbamate)hydrochlorid-:;,
-•an.-.\ - :·. . c,?'./'·:>te . mate,
-.M 2 ° 7 - ’ ·, -et y! :.
.v :a - - , ί/t i_-fr Js
APi 0 138 7
Where nets are used in mass campaigns the alternative or supplemental insecticide may also be an insecticide with a sterilising effect thus to sterilise the mosquitoes and avoid the next generation of mosquitoes. Such insecticides can be of the benzoyl urea group such as 1-(a!fa-4-(chloro-aIpha-cyc!opropyibenzyiidenamino-oxy}-p-tolyI)-3-(2,65 diflourobenzoyl)urea, Diflubenzuron: N-(((3,5-dichioro-4-(1,1,2,2tetraflouroethoxy)phenylamino) carbonyl)2,6 diflouro benzamid, Triflumuron: 2-Chloro-N(((4-(triflouromethoxy) phenyl)-amino-)carbony!) benzamide, or a triazin such as Ncyclopropyl-1,3,5 -triazine-2,4,6-triamin or other insecticides with a sterilizing effect on adult mosquitoes.
In process 1, the insecticide is dissolved in a proper solvent (acetone, hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichioroethane, chlorobenzene and dichlorobenzene; ether solvents such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene giycol dimethyl ether; ester solvents such as ethyl acetate and butyl acetate; nitro compounds such as nitroethane and Nitrobenzene; dimethylformamide; and mixtures thereof).
G
The insecticide can be a pyrethroid such as listed above or any other insecticide repellant „ or a mixture of an insecticide and a repellant such as dimethyl-toluamid. in addition, a ov repellant can be used alone. ‘ ,
The solution is transferred to alcohol or glycol (ethyl-alcohol, propyienglycoi, etc.) and the fabric or netting passes through this bath. To reduce the amount of solvents used in the process, the fabric or netting passes two rollers or a roller against a fixed surface to squeeze off as much as possible of the fluid. The concentration of the pyrethroid in the solution is calculated on the amount of solution remaining in the fabric or on the netting after this process. The fabric or netting is then dried, e.g. by a passing air stream or in an oven. The fabric and especially the netting may be kept fixed under this process not to change shape. The temperature used in the drying process must be beiow 220cC, preferably below 100°C.
After drying, the fabric or netting passes a second bath where a solution or emulsion of the wash resistant agent is added. A cross binding cr a catalysing agent may be added.
This emulsion can be based on hydrocarbon such as mineral wax or oil, or based on a sisicone such as a silicon wax or oil, or based on a polynuorocarbon oii or aic-o <mineral or silicone emulsion will form a continuous film on the evaporation of the water. The fluorocarbon molecules form a physical barrier in a process called telomcn, '· ..·όπ --> unification of larger molecules of fluorocarbons directed by additives that form · r.e structure with the fluorocarbon units. The protective agent added must bs of n - .allows the pyreihrord to migrate through the agent to the surface of the film to ; .mow against the insects on contact and by stow evaporation. Flour carbon protection rs normally oil repellent, and the migration of the pyrethroid is only possible in a ;; - n lattice structure.
In process 2, the insecticide or insecticide-repellant mixture is dissolved as r co mixture is then mixed under stirring into a water emulsion of the wash protective agent eventually with the addition of catalytic or cross binding agent or into organic solution of the protective agent. For reasons of workers safety, a water emulsion is prefer. ί »reprocess is not totally contained. One or several detergents may be added to stabilise the organic solution cf the pesticide in the water emulsion and to ease wetting. An optimal concentration that allows for emulsion stability without reducing wash resistance has to be found. The level and type of detergent used to stabilise the insecticide in the wafer emulsion is dependent on the insecticide and the protective agent and the emuAifiers used in that mixture. After completely wetting, the fabric or netting may pass a press, e.g. comprising two rollers io reduce the amount of composition absorbed, or surpi- .composition is removed by centrifuging. Ihe fabric or netting is finally dried as described above or dried by passing a warm saw - a warm roller. Alternatively, the : : may be partly or iciaiiy air dried, e.g. under vacuum, and then passed between one or two heated rollers or a roller and a heated surface. For the netting, the temperate.. · no to? drying process must not exceed 2?b , preferably be beiow 120° during ' · : i and below 20CFC during tne passage between the heated rollers. For the fair·. -re temperatures might be higher since the fabric absorbs more water and thus have a lower temperature aurreg the evaporation t refined by the air temperature r temperature of triaccelerate the co homogenoLA wer neated surface. Th Asnon of the molec repo lien! film. This fins! drying at elevated process aiso • toe wash protective agent io to: re is often named as the ‘curing’' j '..nom-ci'.....may · in a modified colouring or
Whereas u re 1 ro above fits mostly to netting before cutting and oereno into mosquito bednets, curtains, garments etc., the foiiowing process may be used after such finishing. The cloth, curtain, net or whatever finished made textile that are to be impregnated is put into a wash machine, modified wash machine or colouring machine, and the emulsion is added. The textile is completely wetted during the process, but fluid content may be reduced in a vacuum process or by centrifugation. The surplus fluid is recycled for further use. Since some fibres may retain the insecticide or protective agent and thus leave the recycled process water with a lower percentage of these agents, the concentration in the textile or the fluid must be measured and the fluid for recycling must be upgraded.
A typical amount of pesticide is between 0.001 and 5% (dry weight) of the (dry) weight of the fabric or netting dependent on the insecticidal efficacy of the insecticide. A preferred amount is between 0.05 and 1 % of the fabric or netting dependent on the insecticide. For a pyrethroid like deltamethrin or alphacypermethrin, the preferred amounts are between 0.05 and 0.3 % of the weight of fabric or netting. For a pyrethroid like permethrin or etofenprox, the preferred amount is between 0.1 and 6 %.
A typical amount of protective agent is between 0.001 and 10 % (dry weight) of the (dry) weight of the fabric or netting, depending on the chemical type of the protective agent. As a rule, the higher the amount of insecticide of a specific type to be added, the higher the concentration of the protective agent so that the ratio between insecticide and protective agent is approximately constant with a value depending on the insecticidal and migratory ability of the insecticide. For a silicone protection, the typical amount is between 0.01% and 2%, preferably between 0.05% and 0.5%. For a fluorocarbon protection, the typical amount is between 0.1% and 10 %, preferably between 0.5% and 3%. For a mineral oil (wax) protection, the typical amount is between 0.01% and 10 %, preferably between 0.2 and 5 %. Cross binding and linking agents and catalysers are typically added in a ratio of less than 1:1 based on the amount of protective agent. A polyurethane or polyacryl fixative may be added at a low concentration to increase the fixing of the insecticide. The fixative is added in the water emulsion with the flour carbon, mineral oil or silicon oil emulsion (or resin derivatives of flour carbons, mineral oils and silicon oils).
O
• }
A typical amount of repeilant used in combination with an insecticide or alone is 0.1% to
10% of the solvent or water emulsion, resulting in 0.001% to 1% of the impregnated netting or fabric on a dry weight basis.
Depending on the use of the final product, an UV filter may be added to prevent or reduce the inactivation of the sunlight of the insecticide and/or repeliant. Such UV filters or reflectors may oe para-aminobenzoic acid (RASA), Octyl Methoxycinnamate.. .Rcer5 brighteners, styryl or coumarin derivates, pyrazolin derivates, oxasol derivatives, bsnzaxo derivatives, l.l'-BspherjyMA'bis 2-(methoxypheny)ethenyl or other fluorescer.t . wearing agents.
it is apparent from the foregoing brief description that the invented insect and tick wash 10 resistant composition can be applied to fabric and nets in diverse ways. How a ..n. -,j the most useful products produced with these composition are impregnated ' -. , ,V curtains, especially of polyester, and fabnc of polyester, cotton, and silk us;' . ml ) garments such as socks, trousers, shirts, rs. garments used in body areas -·' . w H mosquito bites.
Accordingly, in one embodiment, the present invention relates to an impregnated netting or fabric for insect or tick killing and/or repefence of an insect or tick compn .·
a) an insecticide and/or a repeliant
(a) a film forming component reducing wash off and degradation of the inse.-.u. .component from the netting or fabric by forming a water and optionally an oil resistant film, the film being a molecular shield around the fibres incorporating the insecticide and or repeliant either by integration of the insecticide/repellant in the film or by for. ‘ · substantial continuous film surrounding trie insecticide/repellant together wrr , , .p--The film forming component whir n ..- , able of forming a film resistant to ,i .
include parafsnic oil or wax derivatives, silicon derivatives, silicon oils or wa m·', and polyfiourocarbon derivatives. These components will allow a miaravon .
ingredients in form of Insecticides a . ..pellants to migrate from the ecu.
surface of ine film with s sustained · -fi fhe active ingredient. The wafer resistance of the film WT at the same time mai - auric or netting more resistant t ·· · .mo*.
a .·’ - ι. '’.tor tie i. -my further reduce soiling a'' 'he · nettings ano tnorefcy cocrease the need 'ior washing.
APC 0 1387
In a preferred embodiment, the impregnated netting or fabric comprises a silicon oii or wax which is a polysiloxan.
In a further embodiment, the impregnated netting or fabric is one wherein the fiim forming 5 component comprises a polymeric backbone selected from a resin, a polyurethane or a polyacryl. Preferable, the parafinic oil or wax derivatives, silicon derivatives, silicon oils or wax derivatives, or polyflourocarbon derivatives is attached to such polymeric backbone.
Accordingly, the migration and wash resistance may in one embodiment be obtained by 10 mixing the parafinic oil derivatives and polyflourocarbon derivatives or by combining silicone oii or parafinic oil side chains with polyflourocarbon side chains on the same polymer backbone.
In a further embodiment, the impregnated netting or fabric according to the present invention also comprise one of more components selected from water, solvents, preservatives, detergents, stabilisers, agents having UV protecting properties, spreading agents, anti-migration agents, preservatives, foam forming agents, and soiling reducing
Mr—·* agents. The soiling reducing agent is preferable selected from flourcarbons which is aiso ___* a film forming agent according to the present invention. Accordingly, flourcabons may be ‘ cm added in case other film forming agents are used in order to reduce soiling of the impregnated product and to decrease wash off. The agents having UV protecting * properties are preferably selected from UV filters or reflectors such as para-aminobenzoic·Λ4?!* acid (PABA), Octyl Methoxycinnamate, stillbene brighteners, styryl or coumarin derivates, *··'·> pyrazolin derivates, oxasoi derivatives, benzaxo derivatives, 1,1’-Biphenyl-4,4'bis 225 (methoxypheny)ethenyl or other fluorescent whitening agents.
In another useful embodiment more than one insecticide is applied in accordance with the invention. Accordingly, one part ofthe netting may e.g. be impregnated with one insecticide and another part with another insecticide thus to prevent insecticide resistance or obtain control when insecticide resistance is already present to one of them. The two insecticides should preferably belong to groups where cross resistance is not likely to play a major role.
In a further embodiment, the protecting film is further fixed by the addition of a fixating 35 agent. An emulsion of the fixating agent is mixed with the emulsion of polyflorucarbon and
emulsions are compatible. The fixating agent may be a polyurethane or polya, ' ?e fixating agent used alone will not contain and slow release the insecticide in 3 manner suitable for bsdnets.
It is generally preferred that the insect anti tick killing and/or repelling comp: ;
used for impregnation of fabric and no* - · : also contains a component to pre··, ·: / degradation of the said active ingredients, 'When the impregnation composition is a wafer emuision of the active ingrec.
preferred to stabilise the emulsion witn suitable detergents and preservatives to avoid physical or biological deterioration during long termed storage. Preservatives src ) especially important when the product according to the invention is a kit for impregnation or re-impreyns ,-. .
The impregnated netting or fabric according to the present invention may come· we the active ingredient In an amount from about 0.001% w/w to 95 %,w/w by weight, cf the snsecticide/repehant In general the inseciicide/repellant is used in an amount of 0.01% w/w to 10% w/w (weight of insecticide/weight of fabric).
The present invention relates to but are not limited to the following active inc. - ,. ss selected from the group comprising pyrethroid compounds such as ethofenprox: 2-(4ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether,
Fenvalerate: (R8)-aipha-cyano-3~phenoxybenzyl (RS)-2-(4-chiorophenyl)-3 ♦ % r* xb methyibutyrate,
Esfenvalera.. - vpr- · yano-3~phe;>. nzyl (S)-2-(4-chlorophenyi)-3-n ·
Fenpropaihrift: {RS}-alpha-oyano-3-phenoxybenzyl 2.2,3,3tetrarnethyicyciopropanecarboxyiaie,
Cypermethrin: (RS)-aipha-cyano-3-p, · , enzyl (1RS)-cis, trans-3- L-ou
2,2-dimethyicycicpropanecarboxylate
dimethylcyciopcrnanecaricoxyiate,
Cyhaiothrin: 72-aiphsmyano-o-po., - yi (Z)-(1RS)-css-3- (2-cnioro-3,3 tnfluoroprop- 7mpv.O7n'netnyiC\c: . -.-carboxylate.
ΑΡίΟ 1 3 8 7
VDeltamethrin: (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl) -2,2dimethylcyclopropanecarboxylate,
Cycloprothrin: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2,2-dichloro -1-(4ethoxyphenyl)cyclopropanecarboxy!ate,
Fluvalinate (aipha-cyano-3-phenoxybenzyl N-(2-chloro-alpha,alpha,alpha-trifluoro-p-toiyl) -D-valinate),
Bifenthrin: (2-methyibiphenyl-3-ylmethyl)0(Z}-(1 RS)-cis-3-(2-chloro-3,3,3-trifluoro-1 propenyl) -2,2-dimethylcyclopropanecarboxylate, 2-methyl-2-(4-bromodifIuoromethoxyphenyl)propyl (3-phenoxybenzyl) ether,
Tralomethrin: (S)-alpha-cyano-3-phenoxybenzyl (1 R-cis)3((1'RS)(15252^2tetrabromoethyl)) -2,2-dimethylcycIopropanecarboxylate,
Silafluofen: 4-ethoxyphenyl (3-(4-fluoro-3-phenoxyphenyl)propyl}dimethylsilane,
D-fenothrin: 3-phenoxybenzyl (1R)-cis, trans)-chrysanthemate,
Cyphenothrin: (RS)-alpha-cyano-3-phenoxybenzyl (1R-cis, trans)-chrysanthemate, D- vc resmethrin: 5-benzyl-3-furylmethyl (1 R-cis, trans)-chrysanthemate, ~~~
Acrinathrin: (S)-alpha-cyano-3-phenoxybenzyl (1 R-cis(Z))-(2,2-dimethyI-3- (oxo-3- .
(1,1,1,3,3,3-hexafluoropropyloxy)propenyl(cyclopropanecarboxylate, ο»
Cyfluthrin: (RS)-alpha-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichIorovinyl)-2,2CO dimethylcyclopropanecarboxylate,
Tefluthrin: 2,3,5,6-tetrafluoro-4~methylbenzyl (1RS-cis (Z))-3-(2-chloro-3,3,3-trifluoropropt · \
1-enyl)-2,2-dimethylcyclopropanecarbo xylate, 'fog
Transfluthrin: 2,3,5,6-tetrafluorobenzyl (1R-trans)-3-(2,2-dichlorovinyl) -2,2- ‘7 7 dimethylcyclopropanecarboxyiate,
Tetramethrin: 3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis, trans-chrysanthemate,
Allethrin: (RS)-3-allyl-2-methyI-4-oxocyclopent-2-enyl (1RS)-cis, trans-chrysanthemate, Prallethrin: (S)-2-methyl-4-oxo-3-(2-propynyI)cyclopent-2-enyl (IR)-cis, transchrysanthemate,
Empenthrin: (RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis,trans-chrysanthemate,
Imiprotnrin: 2,5-dioxo-3-(prop-2-ynyl)imidazoiidin-1-ylmethyl (1R)-cis, trans-2,2-dimethyi-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate,
D-flamethrin: 5-(2-propynyl)-furfuryl (IR)-cis, trans-chrysanthemate, and 5-(2propynyl)furfuryl 2,2.3,3-tetramethylcyclopropanecarboxyIate;
Tne presently preferred pyrethroid me oeuamethrin, etofenprox, siisc,. . - h, ·; iambdacyhaiothrin and cyfluthrin.
Other active insecticides that may bs used alone or in combination, but prei- · ’ mixed with pyretrhoids, are e.g. carbamate compounds such as aianycarb: S-rn=thyl-Ni[Nmeihyl-N-[N-benzy!-N(2-ethoxy-carbonytethyi) aminothio]carbamoyl]thioace;· -. --te, Bendiocarb: 2.2-dimethy!~1,3-benzodioxoMyl· methylcarbamate),
Carbaryl (1- naphthyl N-methylcarbamste.
isoprocarb: 2-(1-methylathy!) phenyl methylcarbamate,
Carbosuifan: 2,3 d!hydro-2,2-dimethylte'“herizofuranyl [(dfbutylaminojihiojmethyicarbamate,
Fenoxycarb; Ethy![2-(4-phenoxyphenoxy)ethyl] carbamate,
I Indoxacarb: Meihyl-7-chioro-2,3,4a,5-tetrahydro-2-[methoxycarbonyl RIrifiUoromethoxyphenyl)!
Propoxur. 2-isopropyioxyphenoI methylcarbamate,
Ptrimicarb: 2-dimethylamino-5,6-dimethyl-4-pyrimidinyl- dimethyIcarbamate, I .wcarc·· Dimethyl N,N‘(thiobis((methylimino)carborioyioxy)bisethanimidiothioate),
Methomyl: S-methyl N-((methylcarbamoyi)oxy)thioacetamidate,
Ethiofencarb: 2 ((eihylthio)methyl)pheny! methylcarbamate,
Fenothiocarb: S-(4-phenoxybutyl)-N,N«dimethyl thiocarbamate,
Cartap: S,S’-(2-5dtmethyiamino)trimethyiene)bis (thiocarbamate)hydrochloride, Fenobucarb: 2-sec-butylphenylmethyi carbamate,
XMC: 3,5-dimethylphenyl-methyl carbamate,
Xylyicarb: 3,4-dimethylphenylmethylcarbsrnate, is
Additionally, active insecticides such as organophosphorous compounds may be applied in accordance with the invention including compounds such as .
Femtrothion: Ο,Ο-dirnethyl 0-{4-nnrc-i· -0+5) phosphorothioate,
Diazinon: . ..-isopropyl .· : .. 5-4-pyrimidiny!) phosphorothioate,
Pyridaphenthion; 0-(1.6-a!hydro-6-oxo-1~phenyipyrazidin-3-yl) 0,0-diethvl cnosphar+.a -· . .
nm ο -ϊ - . ' 0-(2-01=.2-, .-Ί«ηο) 6-methyl-pyrlrnidinyl) phosphor-tebiosie,
Pirimspnos-Me+iyl: 0-r2-(digthy!amino}~Rrnethyl-4pyrimidinyi] 0,0-dimeihyl s' ί
,ξ
Etrimphos: 0-6-ethoxy-2-ethyl-pyrimidin-4-yl-0,0-aimethyl-phosphorothioate, Fenthion: 0,0-dimethyl-0-[-3-methyl-4-(methylthio) phenyl phosphorothioate, Phoxim: 2(diethoxyphosphinothoyloxyimino)-2-phenylacetonitrile,
Chlorpyrifos: 0,0-diethyl-0-(3,5,6-trichloro-2-pyrinyl) phosphorothioate, Chiorpyriphos5 methyl: 0,0-dimethyl 0-(3,5,5-trichloro-2-pyridinyl) phosphorothioate, Cyanophos: 0,0dimethyi 0-(4cyanophenyl) phosphorothioate,
Pyraclofos: (R,S)[4-chlorophenyl)-pyrazol-4-yl] -O-ethyl-S-n-propyl phosphorothioate, Acephate: 0,S-dimethyl acetylphosphoroamidothioate,
Azamethiphos: S-(5-chloro-2,3-aihydro-oxo-1,3-oxazoio [4,5-b] pyridin-3-ylmethyl 10 phosphorothioate,
Malathion: 0,0-dimethyi phosphorodithioate ester of diethyl mercaptosuccinate,
Temephos: (0,0’(thiodi-4-1-phenylene) 0,0,0,0-tetramethyl phosphorodithioate,
Dimethoate: ((0,0-dimethyl S-(n-methylcarbamoylmethyl) phosphorodithioate, Formothion: S[2-formylmethyiamino]-2-oxoethyl]-0,0-dimethyl phosphorodithioate, Phenthoate: 0,015 dimethyl S-(aipha-etnoxycarbonylbenzyl)-phosphorodithioate.
Furthermore, active insecticides with a sterilising effect on adult mosquitoes may applied such as: 1 -(alfa-4-(chloro-a!pha-cycIopropylbenzylidenamino-oxy)-p-tolyi)-3-(2,6diflourobenzoyi)urea, Diflubenzuron: N-(((3,5-dichloro-4-(1,1,2,220 tetraflouroethoxy)pheny!amino) carbonyl)2,6 diflouro benzamid, Triflumuron: 2-Chloro-N(((4-(trifiouromethoxy) phenyi)-amino-)carbonyl) benzamide, or a triazin such as Ncyclopropyl-1,3,5 -triazine-2,4,6-triamin; and
Additionally, the present invention also relates to a composition for impregnation of fabrics or nettings comprising
CVi o
(ft
-
a) an insecticide and/or a repellant selected from the group comprising pyrethroid compounds such as ethofenprox: 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether,
Fenvalerate: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2-(4-ch!orophenyl)-3 methylbutyrate,
Esfenvalerate:(S)-alpha-cyano-3-phencxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate, Fenpropathrin: (RS)-alpha-cyano-3-phenoxybenzyl 2,2,3.3tetramethylcyciopropanecarboxylate,
Cypsnrisihnrr. iRSHiDha~cyarso-3-pnenoxybenzyi (IRS)-cis, trans-3-:2.2-a· . ,0/:-,,
2,2-dsmethyicyciopropanecarboxylate,
Permethrin; 3-phenoxyhsnzyl (1RS)-C:S,trans-3-(2,2-dichlorovinyl)-2,2dimeihyScycSopropanecarboxyfate,
Cyhaioihrin; (RS)-alpha-cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3- (2-chlorc-J trifluoroprop-1 -enyl>-2.2-dimsthylcyclopn> panecarboxylate,
Deltamethrin: yS}-3ipha-cyano-3-phsnoxybenzyl (1R}-C!S-3-(2,2-dibrorooviny2 -2,2dimethyicyciopropanecarboxyiate,
Cycioprothrin: (RS)-a!pha~cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1»(410 ethoxypheny!)cyciopropanecarboxyiate,
Riuvaiinats (aipha-cyano-S-pbenoxybenxyi N-(2-chioro-alpha,alpha,aipha-trr : ,;.-r.ddyh
-D-valinaie), '2 Bifenihrin; (2-msthyibIphenyl-3-ylmethyl)0(Z)-(1RS)-C!S-3-(2-chloro-3,3,3-tnfluoro-1propenyi) -2,2-dimethyScyclopropanecarboxylate,
2-metriyi-2”(4-bron')odifIuorometbox';'[> yl)propyl (3-phenoxybenzyi) ether,
Traiomethrin: (S)-alpha-cyano-3-phenoxybenzyI (1R-cis)3((TRS)(r,2',2',2‘tetrabromoeihyn) -2,2~dimethylcyclopropanecarboxylate,
Silaftuofen: 4-ethoxyphenyl (3-(4-ftuoro-3-phenoxyphenyl)propyl}dimethylsiiars«,
D-fenothrin: 3-phenoxybenzyl (1R)-cis, trans)-chrysanthemate,
Cyphenothrin; (RS)-alpha-cyano-3-pher!Oxybenzyl (1R-cis, trans)-chrysanihern«ie, Dresmethrin:'5-benzyl-3-furylmethyi (1 E~as, trans)-chrysanthemate, •iff
Acrinathrin; (S)-alpha-cyano-3-phenoxybenzyl (1R-cis(Z))-(2,2-dimethyl-3(1,1,1,3,3,3-hexafiuoropropy!oxy)propenyi(cyclopropanecarboxyiate,
-fefa Cyfiuthnn; (R5)-alpha~cyano-4-fiuoro-3-phenoxybenzyl 3-(2,2-dicbiorovinyl}-2,2dimethyicyciopiOpanecarDoxySate,
Tefluthrin: 2,3,5,6~ietrafiuoro-4-moi, _ /1 (IRS-cis (Z))-3-(2-chloro-3,23 ; ....
1-eny0-2.2-diniethylcydopropanecarbo xyiate,
TransfliPhrin: 2,3,5,6-tetrafluorobenzyi (1 R-trans)-3-(2,2-dichiorovinyh -2.230 dimeihyicydor ,·> 3 'f”1 , jpanecarboxyiats, idddeirahyarophthadxxdorrsethyi (iRSCcts, irans-chrysantrr
-••-t <'! ' oxocycic.pertt-2-enyl (1RS)-c.:s, trans-crirvs.
i: I
Rraliethii fe. -..-2- 2 , · J)-yciopsni-2-eny1 (IR)-cis, irar . ip> >2' ’ .
3o tmpu' c - . r, . Ά-ΓΓίειη. c.tenyl (1R)-c:s,trans-cnrysanihemmr.,
APS 0 13 8 7
Imiprothrin: 2,5-dioxo-3-(prop-2-yny!)imidazoiidin-1-yimethyl (1 R)-cis, trans-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxyIate, D-flamethrin: 5-(2-propynyl)-furfuryl (1R)-cis, trans-chrysanthemate, and 5-(2propynyl)furfunyl 2,2,3,3-tetramethylcycIopropanecarboxylate;
carbamate compounds such as alanycarb: S-methyl-N[[N-meihyl-N-[N-benzyl-N(2-ethoxycarbonylethyl) aminothio]carbamoyl]thioacetimidate,
Bendiocarb: 2,2-dimethyi-1,3-benzodioxol-4yl- methyicarbamate),
Carbaryl (1-naphthyl N-methylcarbamate,
Isoprocarb: 2-(1-methylethyl) phenyl methyicarbamate,
Carbosulfan: 2,3 dihydro-2,2-dimethyl-7-benzofuranyl [(dibutylamino)thio]methylcarbamate,
Fenoxycarb: Ethylf2-(4-phenoxyphenoxy)ethyl] carbamate,
Indoxacarb: Methyl-7-chloro-2,3,4a,5-tetrahydro-2-[methoxycarbonyi (-4trifluoromethoxyphenyl)] ~*J'
Propoxur 2-isopropyloxyphenol methyicarbamate,
Pirimicarb: 2-dimethylamino-5,6-dimethyl-4-pyrirnidinyl- dimethyicarbamate, Thidiocarb: ov
Dimethyl N,N’(thiobis((methylimino)carbonoyloxy)bisethanimidiothioate), :s>
Methomyf: S-methyl N-((methylcarbamoyl)oxy)thioacetamidate, fX
Ethiofencarb: 2-((ethylthio)methyl)phenyl methyicarbamate, ;'χ
Fenothiocarb: S-(4-phenoxybutyl)-N,N-dimethyl thiocarbamate, ·
Cartap: S,S’-(2-5dimethylamino)trimethyiene)bis (thiocarbamate)hydrochloride,
Fenobucarb: 2-sec-butylphenyImeth'yl carbamate,
XMC: 3,5-dimethylphenyl-methyl carbamate,
Xylylcarb: 3,4-dimethyIphenylmethylcarbamate, organophosphorous compounds such as
Fenitrothion: Ο,Ο-dimethyl 0-(4-nitro-m-to!yl) phosphorothioate,
Diazinon: 0,0-diethyl-0-(2-isopropyl-5-methyl-4-pyrimidinyl) phosphorothioate,
Pyridaphenthion: 0-(1,6-dihydro-5-oxo-1-phenylpyrazidin-3-yl) 0,0-diethyl phosphorothioate,
Pirimiphos-Etyl: 0,0-diethyl 0-(2-(diethylamino) 6-methyl-pyrimidinyl) phosphorothioate,
Pirimiphos-Methyl: 0-[2-(diethylamino)-o-methyl-4pyrimidinyl] 0,0-dimethyl phosohorothioate,
Etnmphos: 0-5~ethox'y-2-ethyl-pyrimidin-4-yl-0,0-dimethyl-phosphorothioate, · . ·:
O.O-dimethyi’O-l-S-methyM-fmethyithioj phenyi phosphorothioate, Phoxim: 2(diefhoxyphosphiriothoyloxyimino)-2-phenylacetonitrile,
Chloro,.ns_ *. v fe,5.o-trichforO’2-pyrinyl) phosphorothioate, Chiorp·' methyl: 0.0-dimethyi 0-(3.5,6-trichioro-2-pyridinyl) phosphorothioate, Cyanopm 0 Cdimethyl 0-(4cyanopheny0 phosphor. · · -;,
Pyracioios: (R.S)[4-chsorophenyi)-pyra2oM-yl] -O-ethyl-S-n-propyl phosphor·:.· -./c Acephate: O.S-dimeihyi acetylphosphoroamidothioate,
Azamsthiphos: S-(6-ch,toro-2,3-dihydro-oxo~1,3-oxazolo [4,5-b] pyridin-3-ylr phosphors. _· Malathion: 0,0-dimethyi phosphoroalthicate ester of diethyl mercaptosuccinate, Temepnos: (O.COhiodi-A-i-phenylene: 0,0,0,0-tetramethyl phosphorodithioate.
j Dimethoate: ((0,0-dimethyl S-(n-methylcarbamoylmethyl) phosphorodithioate, Formothion S[2-formylmethyiamino]-2-oxoethyl]-O,O-dimethyl phosphorodithioate, Phenthoate; 0,015. dimethyl S-ialpha-eihoxycarbonylbenzyiAphosphorodithioate;
insecticides with a sterilizing effect on aduit mosquitoes such as: 1-(aifa-4-(«· r · alotm cyc!opropyibenzylidenamincH>xy)-p-tolyi>-3-(2,6-diflourobenzoyl)urea, Diflubenzuron; N(((3,5-dichioro-4-(1,1,2,2-tetraflouroethcxy)phenyIarnino) carbonyl)2,6 diflourc benzsmid,
Triflumuron: 2-ChSoro~N-(((4-(trifiourornethoxy) phenyl)-amino-)carbonyl) benzamide, ora triazin such as N-cyciopropy!-1,3,5 -tnazine-2,4,6-triamin; and the repellant is selected from N,N-Diethyi-meta-toluamide(DEET), N.Ndiethyiphenylscstamidf; (DEPA), · ,exen-1-yl~carbonyl)-2-meihylpbc 025 hydroxymethyteyciohexyi) acetic ac a, (2-ethyl-1,3-hexandiol), indaion-x
Methylneooecanarnide (MNDA), a ,.yr, . r ,d not used for insect control sue - -> -
Eucemalol (12 (-)-1 -epi-eucamaio! or crude plant extracts from plants like 5 ’ ~
ΑΡ ν-01387 the filmforming agent being capable of forming a continuous layer substantially enclosing the fibres of a fabric or of a netting.
Polysiloxanes have, as described above, shown excellent properties as a film forming 5 polymer. The derivatives referred to as parafinic oii or wax derivatives, silicon derivatives, silicon oils or wax derivatives, and polyflourocarbon derivatives represent the addition of functional groups to the backbone of the molecule. Accordingly, the derivative in the present context relates to groups capable of attaching the polymer to the fabric inter alia by a chemical attachment. In another embodiment the derivative increases the film forming properties of the polymer. The filmforming agent may advantageously be amplified with a fixative agent for improved attachment. The fixative agent may be a
'.polymer in the form of polyurethane or poiyacryl.
Fabrics and nettings to be impregnated according to the present invention and by use of a composition as described herein, may be impregnated locally when the composition is delivered in the form of a kit comprising the relevant ingredients in a handy form. Any of the ingredients may be in the form of a premix comprising the insecticide and/or repellant together with the polymer or the two may be separated, in a preferred embodiment the kit is adapted for preparing a emulsion by adding water. The ingredients of the kit may accordingly be in the form of a dry composition such as a powder, a capsule, a tablet, or an effervescent tablet. In a further embodiment, the kit comprises an emulsion wherein water is added by the end-user. The emulsion may be a micro-emulsion which is generally very stable. The emulsion may be embodied in a capsule.
r>j ;;λ,
In a further embodiment, the invention relates to a process for impregnation of a fabric or a netting comprising (a) forming a solution or a water emulsion of an insecticide and/or repellant and a polymer and passing the fabric or netting through the solution or emulsion or spraying the solution or emulsion onto the fabric or netting at a temperature within a range of 10-120°C, or applying an insecticide and/or repellant on the fabric or netting and passing the fabric through a polymer solution or emulsion to fixate and wash protect the insecticide b) optionally removing surplus composition by pressing of the fabric or netting
c) drying the fabric passively or actively at a temperature within 20-150°C.
The surplus composition may alternative!/ be removed by centrifuging or ·,·= pressure. 5 it wilt be appreciated, that in accordance with the invention, the fabric or net!·. , may either be passed through the solution or emulsion, or the solution or emulsion may be passed through the net.
fo·
The emulsion may also be in the form of a foam which is applied to the fabric or netting. A 10 foam comprises less water/solvent and the drying process may be very short. !r should be noted that the drying process may be a passive drying as the process rnay bo earned out in rather hot climates. An active drying process will normally be performed during nigh scaleprocj bid
The net or fabric may also pass a roller mat is partly dipped into the solution or emulsion and draw the solution or emulsion to the side of the net or fabric in contact wim a roller.
As described in detail above, the solution or emulsion may further comprise c . ·. · r more ingredients selected from detergents, stabilisers, agents having UV protecting properties, solvents, spreading agents, anti-migration agents, preservatives, foam forming agents, and anti-soiling agents.
Further agents to be used are anti-static, anti-calcareous agents, and anti-'< . mm · Furthermore, the composition according fo the invention may also be incorporated into detergent mixtures used for washing doth or in rinse fabric conditioner (fat u i··
It should be considered that most fabric softeners are based on cationic ce··· ' :, anu that these may degrade insecticides. Special formulation considerations sit’ · _-►·>' m this ; am ·
The process may aiso involve use of ih impregnating mocess may be carried c kit as describe herein. acccr‘ i g , , cy the eno user in 3 icw-sra t
Impregnation vein the insecticide is ejt at temperatures beiow „0 beiow ??! · , η· ~ .ο ,m,ui with the lowest boiling point io reduce e,m durina trim cm cess
AP ;J 1 3 8 7
In the succeeding drying process, temperatures are below 200°C. The temperature choice is a funciion of the evaporation temperature and mobility of the insecticide in the formulation. The mobility of the insecticide is a function of the molecular formula and structure. With a formulation wherein the diffusion ability in the specific formulation is high and wherein the vapour pressure of the insecticide is high, a lower drying temperature is sufficient or required.
After drying, the netting or fabric further passes an impregnation process with a composition that reduce wash off, and eventually soiling and UV degradation. These ingredients may be dissolved in organic solvents, but are preferably in water emulsions. After transfer of the protecting agents, pressure or centrifugation removes surplus liquid. The fabric or netting is subsequently dried. This drying process may be prolonged continuously into a curing process during which the temperature may be more elevated. The drying process is below 200°C, preferably below 120°C for netting. The curing process is below 220°C, though a fast curing may take place at higher degrees. When the fabric is dense and thick, the ambient temperatures in the process may be higher than c fed above as long as the temperature in the fabric does not exceed these limits. The curing process may also include or consist of passing the fabric or netting by a heated surface under pressure such as an iron or a heated roller. During drying processes and curing, the fabric or netting is mechanically fixated in a way to prevent change of the form.
/37
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CM
The impregnation process consist of dissolving the insecticide composition in a solvent and mixing this solvent into the part of the composition that provides water repelience, reduced soiling and eventually reduced UV degradation. This part may be as mentioned be dissolved in a solvent or be a water emulsion. Detergents may be added to either of the phases to be mixed to ease and stabilise the final emulsion. The fabric or netting passes through the emulsion or solution and pressure or centrifugation removes surplus liquid. Subsequently, the fabric or netting is dried at temperatures below 200°C, preferably below 120°C for netting, and eventually finally cured and/or fixated. A part of the drying process may be under vacuum.
The curing process is below 220°C, though a fast curing may take place at higher degrees. When the fabric is dense and thick, the ambient temperatures in the process may be higher than cited about as long as the temperature in the fabric does not exceed i'i 5·1 these limits. The curing process may ateo include or consist of passing the . .:
netting by a heated surface under pressure such as an iron or a heated rohet ·, .-,r, drying processes and curing, the fabric or netting may be mechanically fixated In a way to prevent change of form.
. .
Tne application of the insecticide and/or impregnation liquid may also be co. om a foam of the emulsion with the composition and applying the foam on the netting or fabric. This process reduce the amount of liquid applied, and thus reduce ti, . m consumption during the succeeding drying process.
I
According io the present invention, the impregnation process may aiso be u, mm very simple equipment. The fabric or net is dipped into the water emulsion or solution .13) containing the claimed insecticide/repeitant and the protective agent(s), suitable detergents to ease wetting and to stabiiisc the emulsion/soiution with the concentrations ; ,.r>
needed. The superfluous water is pressed out either by hands or by a simp· fabric, garment or net is laid horizontally and dried, preferably in the shadow. The curing ,,., may be improved by ironing at temperatures below 200’C. o
The impregnation may be carried out by applying the emulsion with a simple speayer as 20 used in agriculture or for house spraying In mosquito control campaigns. This reef-hod is an aftemative method and is very likely io be used to re-impregnate nettings cr fabric previously impregnated with less effective impregnations or not impregnated Taring spray application, precautions must bs taken to avoid inhalation as with other mixtures containing insecticides, in addition, solvent removed by evaporation, e.g. in . . ν,
JS process 'ε r :-· mied.
in a further embodiment ot the invention, ihe impregnation process as described herein rnay aiso take place before the fibres are spun, woven or knitted. Tns fibres , rm according io the present invention relaxes to the single structure forming th =
However, the impregnation may still be performed directly on the garment o> > .m fabric. : ne we -ed notunqs according _ ne present invention is in cne examine. a net made of 36 knitted to s invention Is resulting in eras ett 3.01 mm which» Is spun to a fibre. Subsequently v r - ~ :-u w .or. m a fabric. The polymer used a, - ‘rc;
>_ ·. w smrma,,v·.. . t ass the filaments or spun fibres o , ub · from ·-·.-.:: off and ai the same time allowing „ I-.—ΑΡ ν Ο 1 3 ΐ 7 ingredient to be released in an amount sufficient te perform the insect killing or repellent effect.
Examples
TABLE 1
Process temperature and +/- protective agent. | Data before washing | Data after 3 washes | Data after 6 washes | |||
KD at 60 min | Mortality at 24 hours | KD at 60 min | Mortality at 24 hours | KD at 60 min | Mortality at 24 hours | |
200°C, - | 10 | 5 | 0 | 0 | ||
200°C, + | 20 | 5 | ||||
:SC°C, + | 0 | 5 | ||||
150°C,+ | 5 | 0 | ||||
120°C,+ | 100 | 35 | 0 | 0 | ||
80°C, + | 100 | 100 | 100 . | 100 | 100 | 100 |
60°C,+ | 100 | 100 | 100 | 100 | 100 | 100 |
40°C,+ | 100 | 100 | 100 | 100 | 100 | 100 |
20°C,- | 100 | 100 | 100 | 95 | 100 | 55 |
20°C,+ | 100 | 100 | 100 | 100 | 100 | 100 |
KD: Knock down, percentage mosquitoes paralysed after 60 minutes
U»
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py.
py o
-W*
The washing procedure is a standard procedure recommended by WHO and is performed 10 by WHO's reference laboratory.
The effect of adding protective agent and proper process temperature is shown in Table 1. The pesticide tested was 0.20 g alphacypermethrin, the protecting agent was a reactive ethyl-hydrogen-silicone macroemulsion, and the process temperature was as indicated.
All ingredients were added in one process, then dried at the temperature indicated. 200°C was used after complete drying at 60°C.
Aiphacypermetnnn | 0.20 g |
Silicon oil | 0.18 g |
Polypropylene gsycoi | 0.20 g |
Acetone | 2.50 g |
FothanC'S | 7.50 g |
Detergent | 0.02 g |
Preservative | 0.01 g |
Water to 100 g | |
TABLE 2 |
)
Process tern- s Data before washing perature and j ί +/- protective { agent ; | Data after 3 washes | Data ary > \ashes | ||
i KD at 60 ri ϊ m;n ι | Mortality at 24 hours | KD at 60 min | Mortality at 24 hours | KD at 60 j Mortality min ί at 24 i ! hours i |
200cG + i 19 I | 0 | |||
18O’C.+ \ 10 | 5 | : | ||
150°C.+ j 75 | 25 ; | 5 i | ||
120eC+ j 100 3 | 95 ’ | Ί5 7 | 0 | ? Ϊ |
80“C.+ ! 100 i | 100 | 100 | 100 | ! |
60“C,+ j 100 | 100 | 100 | 100 | : |
20°C,+ j 100 | 100 | 100 _ | 100 |
The same procedure as used above, :, r .iiohacypermethrin is replaced by „ r
This insecticide tolerates better higher temperature regimes.
ru'd >n 'criri cri
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TABLE 3
Pesticide | Protecting aaent | Process temp. | Curing temp. | Before Wash | After 3 washes | ||
KD at 60 min | Mortality at 24 hours | KD at 60 min | Mortality at 24 hours | ||||
Alphacyper methrin | none | 80°C | 200°C | 10% | 5% | ||
Alphacyper methrin | Epoxideresin stabilised silicone oil | 80°C | 200°C | 100% | 40% | 0% | 0% |
Alphacyper methrin | Epoxideresin stabilised silicone oil | 80°C | none | 100% | 100% | 20% | 60% |
Alphacyper methrin | Zirconium stabilized Parafin | 80°C | 200°C | 85% | 20% | I j | |
Alphacyper methrin | Zirconium stabilized Parafin | 80°C | none | 100% | 100% | —Ί |
U5
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O ii
When impregnation is carried out in two steps, the protection against elevated temperatures is often better than in a one step process. Still, high temperatures are destructive. In this table, insecticide impregnation was carried out at room temperature, followed by a drying process at 80°C to evaporate solvents, then by an impregnation with an emulsified protecting agent, then by a drying process at 80°C to evaporate solvents and water, and finally by a curing process at 200°C or no (extra) curing process. The last two columns shows that the curing obtained at the higher temperature is not good enough to retain the residual activity and overall, it gave better results avoiding a final curing at high temperature.
As
TABLE 4
Concentration of i | Temp 1 | Time 1 | Temp 2 | Time 2 | KD % | Tunahsy | |||
protective agent ( in composition | Celsius | minutes | At 60 rnin | si 24 hr | |||||
6% . | 120 | 20 | 120 | 50 | 76 | ||||
16% | 120 . | 40 | 120 | 60 | 57 | ... c fo | |||
)6% s ... | 120 | 60 | 120 | 60 | 38 | ||||
6% | 120 | 40 | 120 | 60 | 57 | 2 * | |||
!s% | 120 | 40 | 120 | 40 | 95 | 2X7 | |||
6% | 120 | 40 | 120 | 60 | 57 | 24 | |||
6% | 120 | 40 | 150 | 60 | 0 | 2 | |||
6% | 120 | 40 | 180 | 60 | 0 | 0 | |||
3% j 120 „ ... .......... .. . ............. .. ....L. ...... ...________ | 40 | 120 | 60 | 91 | -,« | ||||
3% | 20 | 40 | 150 | 60 | 5 | A | ..... | ||
3% | 120 | 40 | 180 | 60 | 0 | ||||
1.5% | 120 | 40 | 120 | 60 | 100 | 60 . | |||
1.5% | 120 | 40 | 1 150 ί | 60 | 10 | .. . | |||
1.5% w. .. ________________ .. | 120 | 40 | 180 | 60 | 0 | 0 |
UT
CA
Table 4 shows the results of various temperatures and concentrations regimes in a two step impregnavon process. The tested insecticide is alphacypermethrin and the protective agent is a polysiloxan The percentages given for the protective agent are concentrations of the polysiloxan emulsion in the impregnation solution. The results show that nigh .0 temperature is most critical for the first phase of impregnation, and less for :· ,:ond.
However, increasing exposure time at high temperatures in the second prr.;-. . ;o results in reducing insecticidal effect.. The high concentration of the protective spent (6 % in solution) gives low pesticidal effe-c. · . tuch protection), and the lower c Simeons are better r; . cue to a too high protection of (or too much dilution of) to* cc at hiqher concsnrmiions of D'otective ;
O
AP> 0 13 8 7
TABLE 5
Protective Agent | Final curing at 200°C | One Step Process | Two Step Process |
Mortality at 24 hours | Mortality at 24 hours | ||
Polyflouro- carbon | No | 91 | 100 |
Polyflourocarbon | Yes | 80 | 20 |
The above table shows test with a kationic, urethane amplified polyflourocarbon and the pesticide alphacypermethrin, that is more temperature sensitive and therefore suited for temperature stress test. Contrary to other wash resistant agents tested, the polyfiour carbons provided better protection against heating in the curing process after mixing of the dissolved pesticide into the protecting composition (a one-step process) than in a two ' step process. This may be due to the formation of a poiyflourcarbon film on top of the up layer of pesticide that allows little pyrethroid to penetrate to the surface. The film formation AM is not so effective at lower temperature. . θ
CM
TABLE 6 «ο
Cone. Of Prot. | No wash | After 3 washes | After 6 washes | After 9 washes | After 12 washes | |||||
KD | Mort | KD | Mort | KD | Mort | KD | Mort | KD | Mort | |
% 60min | 24 hr | % 60min | 24 hr | % 60min | 24 hr | % 60min | 24 hr | % 60min | 24 hr | |
0.6 %, 40°C | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 80 | 50 | 0 |
0.6 % 60°C | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 80 | 55 | 25 |
0.3 % 40°C | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 95 | 40 |
0.3 % 60°C | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 70 |
Tne above Taile 6 shows the results oi lest where the protective agent ic jc i poiyiiouralky! emulsion with a parannic oh -metal salt complex added. These , . res are tested at two concentrations and two temperatures for the process and the pesticide deltamethrin. The impregnation is made in a one step process without high temperature curing . Wasn resistance is obtained with 100 % effect for 3 washes and >u. : py reduced for 12 washes, the resistance rs slightly better at 40°C than at 60Ά ably due to better curing ot the protective agent since other test showed that deltamethrin without any protection is not influenced by temperatures in the regime 80°ί ' 0 Ό
The key point here is the mixture of the wash resistant agents. The paraiinic cl-meta) salt complex alone does not provide sufficient wash off protection as shown in mr.::- .·. The flouro-poiycarhon impregnation alone is. very effectively protecting against wash off, but
J also has oii-repeliant abilities and allows for very little migration of the insec-i ·... e As a result, very liit'e insecticidal activity is obtained after washing that removes the pyrethroid already at the surface. The combination of the two provides at the same time a very
effective wash-resistance and allow the pyrethroid to migrate. | |||||
TABLE 7 | |||||
Polyflour- | i Polysiloxan | Cai.alysat.or | UV- | Stability of I | cnber of |
alkyl | j | absorbant | Emulsion j | wash cycles | |
ι | j | resisted | |||
4% | i 1 % ί | 0.3 | Stable s | v G | |
3.5% | 0.3 | Separates i | T; | ||
2.5 % | 0 | Stable { | 1.1 | ||
3.0 % .... . | ; 0 j 0 | Stable i | f | ||
3.0 | j 1.0 | 0.3 | 0,5 | Stable i | |
r, .. 3.0 0 | 1 1.0 | 0.3 | 1,0 | Unstable | 7 |
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The above Table 7 shows the resets . ·?υ!β emulsions versus unstable e.
where adartives make tne emulsion - 1 .-he at certain concentrations. Er m mabii s; g · -,. ett ..ro n the 0/-:0- :e. on must be compatible wrw er m emulsify the protective agents and .w . m water. Proper stabilised ar,J . stable polyfloio-aikyhpdysiloxan co .. give resistance tc 15-27 washes
Examples of ranges of the ingredients used in the compositions according to the present invention are shown in the following:
With increasing concentration of insecticide, the concentration of polymer should also bs 5 increased so that the ratio between polymer and insecticide is substantial the same.
The amount of insecticide relative to the fabric is preferable in the range of 0.01% to 10% insecticide (weight insecticide/weight of fabric). The most effective insecticides are represented by deltamethrin and a less effective insecticide is represented by bendiocarb.
Specific compositions is shown in the following where Composition A represents a formulation wherein the fabric is impregnated with the insecticide before addition of the polymer composition. Composition B represents a composition wherein the pesticide is integrated into the polymer
However, the specific ranges may be varied according to the specific properties of the invention, in general the silicon oils is very effective and may used in lower dosages than the other polymers. The specific effectiveness of the insecticides is well known and is measured by the specific activity (mg insecticide/g insect)
Composition A
Deltamethrin
Silicon oil
Polypropylonglycol
Detergent,
Preservative
Water to 100 g
Composition B
Deltamethrin
Acetone
Ethanol
Silicon resin cil
Polypropylenglycol
Detergent,
CM
Ό
0.30 g 0.18 g 0.20 g 0.02 g 0.01 g
0.30 g 2.50 g 10.00 g 0.18 g 0.20 g 0.02 g
Preservative Water to 100 g
0.01
Composition G
OS Lambdacyhaloinrin
Polyflourcarbon
Ethano!
Xyisns
Acetic acid (o. > p 10 Aluminium sail of paraffin oil
Detergent, emulsifiers and stabilizers
-) Poiypropyiengiycoi
Water to 100 c 15
Composition D
Deltamethrin
Polyflourcarbon
Ethanol 20 Acetone
Acetic acid (60%)
0.30 g 0,10 a 10.00 g 2.00 g 0.60 g 0.50 g d vOg .· .6 3 ' 0 0,30 g 5.00 g 9
0.10 g
Im
Detergent, emulsifiers, UV reflectant and stabilizers Water to 100 g
Use of additional ingredients, stabilisers, softeners, preservatives, UV pro:·- · ,y ts, curing, fixative and anti-migration agents, may be added individually deer · · Ή · desired properties of the formulation and may be performed by the skilled pm son
The impn ο ..'buns are used in the concentration in the rangr in the solvent. The presently preferred solvent is water.
601387
References
Hodjati, Μ. H. And Curtis, C.F. 1999. Evaluation of ths effect of mosquito age and prior exposure to insecticide on pyrethroid tolerance in Anopheles mosquitoes (Diptera:
Culicidae). Bull. Entomoi. Research. 89, 329-337.
Lines, J. D. 1996. Technical issues regarding insecticide treated fabrics. Insecticidetreated Nets: the technology, its implementation, promotion and new research priorities (eds. C. Lengerer, J.A. Cattani, and D. de Savigny) IDRC Books , Ottawa.
Claims (21)
- CLAIMS ,,ί’ίΝCjI. An impregnated netting or fabric for killing and/or repellence of insects or ticks, 5 comprising:a) sn. insecticide and/or a repellent, andb) a 51m forming component reducing wash off and degradation ox the insecticide component from the netting or fabric by forming a water and optionally oil resistant film, the film being a molecular shield around the fibres incorporating the insecticide10 and/or repellent, either by integrating the insecticide/repellent in.the film or by forming a substantial continuous Sint surrounding the insecticide/repellent ana the fibre, characterized in that said film forming component comprises i) one cr more components selected from paraffin oils or waxes, silicons, silicon oils or waxes, and poly-fluorocarbons, or derivatives thereof and ii) a polymeric backbone fixative.
- 2. An impregnated netting or fabric according to claim 1, wherein the said film forming component of i) comprises a mixture of components selected from paraffin oils or waxes, silicons, and silicon oils or waxes, and polyfiuorocarbon, or derivatives thereof preferably a mixture of a polyfiuorocarbon and a paraffinic oil or a mixture of a20 . poiyfiuorodkyl and a polysiloxan.
- 3, An. impregnated netting or fabric according to claims 1 or 2, wherelr rise silicon oil or wax is a polysiloxan.in tnCs·C3 na oa.
- 4. An impregnated netting or febnc according to any of the claims 1 p w; ,»xxrerei paraffin oii or wax, silicon, silicon oil or wax. or der o ' - ’ .ir:'.. .. thepoimr > ...One.x wnerein me rerives thereof
- 5. . . re..:...t ? xemre . , according to any of the ciaims } polymenc oackoone fixer., ~.-, , , polyurethane or polyacrel.re me·. fiEHDED SHEET
- 6. An impregnated netting or fabric according to any of the preceding claims further comprising one of more components selected from water, solvents , preservatives, detergents, stabilisers, agents having UV protecting properties, spreading agents, antimigration agents, preservatives, foam forming agents, and soiling reducing agents.
- 7. An impregnated netting or fabric according to any of the preceding claims comprising from about 0.001 to 95 %, by weight, of an insecticide.
- 8. An impregnated netting or fabric according to any of the preceding claims, wherein 10 the insecticide is selected from the group comprising:pyrethroid compounds such asEthofenprox: 2-(4-ethoxyphenyI)-2-methylpropyl-3-phenoxybenzyl ether,Fenvalerate: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3 methylbutyrate,Esfenvalerate: (S)-alpha-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3methylbutyrate,Fenpropathrin: (RS)-alpha-cyano-3-phenoxybenzyl 2,2,3,3tetramethylcyclopropanecarboxylate,Cypermethrin: (RS)-alpha-cyano-3-phenoxybenzyI (IRS)-cis, trans-3-(2,2dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,Permethrin: 3-phenoxybenzyl (lRS)-cis,trans-3-(2,2-dichlorovinyI)-2,2- di methylcyclopropanecarboxylate,Cyhalothrin: (RS)-alpha-cyano-3-phenoxybenzyl (Z)-(lRS)-cis-3- (2-chloro-3,3,3trifluoroprop-l-enyI)-2,2- dimethylcyclopro pariecarboxylate,Deltamethrin: (S)-alpha-cyano-3-phenoxybenzyl (lR)-cis-3-(2,2-dibromovinyl) 2,2-dimethyicyclopropanecarboxylate,Cycloprothrin: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2,2-dichloro -1-(4ethoxyphenyl)cyclopropanecarboxylate,LOCM <OCM <oFluvalinate: (alpha-cyano-3-phenoxybenzyl N-(2-chloro-alpha, alpha, alphatrifluoro-p-tolyl) -D-valinate),Bifenthrin: (2-methylbiphenyl-3-ylmethyl)0(Z)-(lRS)-cis-3-(2-chloro-3,3,3trifluoro-l-propenyl) -2,2-dimethylcyclopropanecarboxylate, 2AMENDED SHEETTralomethrin:Silafluofen:D-fenotltrin:Cyphenoihrin:D-resmethrin:Acnnathrin:Cvfiuthrin.:Tenuthrin:Transfluthrin:Tetramethrin:Allethrin:Praliethrin:Enipenthrin:Iniiprothna:<·*’ ... ..methyi-2-(4-bromodifluoromethoxyphenvi)propyi .'· uhenoxybenzyi) ether, (S)-a!pha-cya:ao-3-phenoxybenzyl (lR-cis)3((I'RS)(:)2*,2',2'~ tetrabromoethyl)) -2,2-dimethylcyclopropanecarboxy!aie,4- ethoxypheayl (3-(4-fiuoro-3-phenoxyphenyl)prc_ -methylsilane,3-phenoxybenzyl (IR)-cis, trans)-chrysanthemate, (RS)-alpha-cyan.o-3-phenoxybenzyI (lR-cis, trans)-chrysanthemate,5- benzyl-3-finylmethyl (IR-cis, trans)-chiysanthem3.te, (S)-alpha-cyano-3-phenoxybenzyl (lR-cis(Z))-(2,2-dvnethyl-3-- (oxo3-(1,1,1,3,3,3 -hexafiuoropropyloxy)propenyl (cyclopropanecarboxylate, (RS)-alpha-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyi)2.2- dimethyicycloprOpanecarboxylate,2.3.5.6- tetrafluoro-4-methyJbenzyi (IRS-cis (Z))-3-(2-crdoro-3,3,3trifluoroprop-ί -enyl)-2,2-dimethyIcy dopropanecarbo xy late,2.3.5.6- 1etrafluorobenzyl (1 R-trans)-3 -(2,2-dichlorc vmyi) -2,2dimethyicyclopropanecarboxylate,3,4,5,0-tetrahydrophthaliniidomethyl (IRS)-cis, trans-, chrysanthemate, (RS)-3-ailvi-2-methyl-4-oxocyclopent-2-enyl (IRS ;ai „ chiysanthemate, (S)-2-methyi-4-oxo-3-(2-propynyi)cyclopent-2-enyi. u.R)~cis, transchrysanthemate, (RS)-l-ethynyi-2-methyl-2-pentenyl (lR)-cis,trans-. ·· m ihuca:·:·, 2,5-dioxo-3-Qfop-2-ynyl)irnidazolidin-l-ylmethyl \ 1A,-ci3, trans2.2- dimethyi-3-(2-methyl-l-propenyi)-cyclopropa;. · . xyiate,5-(2-propynyi)-furfuryI (lR)-cis, trans-chrysantheir- · r>2--C~ prop\r.vii - _ 2,3,3-tetramethylcyclocrcpane.CMO>OJIt k'W» . . 5 inds such asS-methyi-Y ’E:xi.thyl-N-[N-benzyl-N(2-e:b ' '· ear.nothiolcarbanioyijthioacetimidate,AMENDED SHEET ?9AT*Bendiocarb: 2,2-dimethyl-l,3-benzodioxol-4yl- methylcarbamate),Carbaryl; (1 -naphthyl N-methylcarbamate,Isoprocarb: 2-(l-methylethyl) phenyl methylcarbamate,Carbosulfan: 2,3 dihydro-2,2-dimethyl-7-benzofuranyl5 [(dibutylamino)thio]methylcarbamate,Fenoxycarb: Ethyl[2-(4-phenoxyphenoxy)ethyl] carbamate,Indoxacarb: Methyl-7-chloro-2,3,4a,5-tetrahydro-2-[methoxycarbonyl (-4trifluoromethoxyphenyl)]Propoxur: '2-isopropyloxyphenol methylcarbamate,10 Pirimicarb: 2-dimethylamino-5,6-dimethyl-4-pyrimidinyl- dimethylcarbamate,Thidiocarb: Dimethyl N,N’(thiobis((methylimino)carbonoyloxy) bisethanimidiothioate),Methomyl: S-methyl N-((methyIcarbamoyl)oxy)thioacetamidate,IEthiofenearb: 2-((ethylthio)methyI)phenyI methylcarbamate,15 Fenothiocarb: S-(4-phenoxybutyI)-N,N-dimethyl thiocarbamate,Cartap: S,S’-(2-5dimethyIamino)trimethylene)bis (thiocarbamate) hydrochloride,Fenobucarb: 2-sec-butylphenylmethyl carbamate,XMC: 3,5-dimethylphenyl-methyl carbamate,20 Xylylcarb: 3,4-dimethylphenylmethylcarbamate,UTS organophosphorous compounds such asFenitrothion: Ο,Ο-dimethyl 0-(4-nitro-m-tolyl) phosphorothioate,Diazinon: 0,0-diethyl-0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate,Pyridaphenthion: 0-(l,6-dihydro-6-oxo-l-phenylpyrazidin-3-yl) 0,0-diethyl phosphorothioate,Pirimiphos-Etyl: 0,0-diethyl 0-(2-(diethylamino) 6-methyl-pyrimidinyl) phosphorothioate,Pirimiphos-Methyl: 0-[2-(diethylamino)-6-methyl-4pyrimidinyl] 0,0-dimethyl phosphorothioate,Etrimphos: 0-6-ethoxy-2-ethyl-pyrimidin-4-yl-0,0-dimethyl-phosphorothioate,Fenthion: 0,0-dimethyl-0-[-3-methyl-4-(methylthio) phenyl phosphorothioate,AP/P/0 2 / 0 2 5 1AMENDED SHEET a a' - ύ 1 : , / 40Phoxim: 2-(diethoxyphosphinothoylox5dnuno)-2-phenylaceiordrilesChiorpyrifos; 0,0-diethyi-0-(3,5,6-trichioro-2-pyrinyl) phosphorothioate,Chlorpyriphos-methyi: 0,0-dimethyl 0-(3,5,6-trichloro-2-pyridinyl) phosphorothioate,
Cyanophos; 0,0-dimethyi 0-(4cyanophenyl) phosphorothioate, 5 Pyradofosi (KS)[4-ch!orophenyl)-pyrazoi-4-yi] -O-ethyl-S-n-propyj phosphorothioate, Acephate: 0, S-dimethyl acetylphosphoroamidothioate, Azamethiphos: S-(6-chloro-2,3-dihydro-oxo-l,3-oxazolo [4,5-b] pyridin-3-ylmethyl phosphorothioate, 10 Malathion: 0,0-dimethyi phosphorodithioate ester of diethyl mercaptosuccinate, Ternephos: (Q,0’(thiodi~4-i-phenylene) 0,0,0,0-tetramethyI phosphorodithioate, Dimethoate: ((0,0-dimethyl S-(n-methylcarbamoyhnethyl) phosphorodithioate, Ϊ.Ο Fonnothion: S[2-formylme£hyiamino]-2-oxoethyl]-0,0-dimethyl phosphorodi thioai e, i CM 15 Phenihoate: 0,0-dimethyi S-(alpha-ethoxycarbonylbenz\4)-phospnorodithioate; co insecticides with a sterilising effect on adult mosquitoes such as; CM •O 1 -(alia-4-( cHoro-alpha-cyciopr opylbenzylid enamino-oxy)-p-t oly 1)-3 -(2,6- mA- difiourobenzoy iiurea, My 20 Diflubenzuron: N-(((3,5-di ehloro-4-( 1,1,2,2-tetrafiouroethoxy)phenylami no) . 1 %. carbonyl)!,6 diflouro benzamid, * Triflumuron: 2-Chloro-N-(( (4-(triflouromethoxy) phenyl)-amino- /carbonyl) benzamide, or a iriazin such as N-cydopropyl- 1,3,5 -triazine-2,4,6-trianiin; and the reoeilant is selected fromN,N-Diethyl-raeta-toluamide(DEET), N,N-disthylphenylacetamide (DEPA), l-(3-cyclohe>;en-I“yl-carbonyl)-2-methylpiperine, (2-hydroxymethyicyciohexyl) acetic acid lactone, (2-ethyl-l,3-hexandiol), indaione,Methy i ne og ec anamide (MND A), •E.,· A A SHEET a pyrethroid not used for insect control such as (+/-)-3-allyl-2-methyl-4-oxocyiopent2-(+)enyl-(+)trans-chiysantemate (Esbiothrin), a repellant derived fiom or identical with plant extracts like limonen, citronella, eugenol, (+)-Eucamalol (1), (-)-l-epi-eucamalol or crude plant extracts from plants like5 Eucalyptus maculata, Vitex rotundifolia, Cymbopogan mardnii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). - 9. A composition for the impregnation of fabrics or nettings so as to impart insect and/or tick killing and/or repellence properties, comprising:
- 10 a) an insecticide and/or a repelleng andb) a film forming component reducing wash off and degradation of the insecticide component from the netting or fabric by forming a water and optionally oil resistant film, the film forming a molecular shield around the fibres incorporating the insecticide and/or repelleng either by integrating the insecticide/repellent in the film or by15 forming a substantial continuous film surrounding the insecticide/repellent on the fi- ;-n bre, characterized m that said film forming component comprises i) one or more components selected from paraffin oils or waxes, silicons, silicon oils or waxes, and polyfiuorocarbons, or derivatives thereof and ii) a polymeric backbone fixative. '20 10. A composition according to claim 9, wherein the said film forming component of v /Xi) comprises a mixture of components selected from paraffin oils or waxes, silicons, / and silicon oils or waxes, and polyfluorocarbon, or derivatives thereof, preferably a mixture of a polyfluorocarbon and a paraffinic oil or a mixture of a polyfluoroalkyd and a polysiloxan.
- 11. A composition according io claims 9-10, wherein the silicon oil or wax is a polysiloxan.
- 12. A composition according to any of the claims 9-11, wherein the polvflurocarbon,30 paraffin oil or wax, silicon, silicon oil or wax, or derivatives thereof is/are attached to the polymeric backbone.AMENDED SHEETMW 1‘ ' 3 8 7
- 13. A composition according io any of the claims 9-12, wherein the polymeric backbone fixative resin is a resin, polyurethane or polyacryi.
- 14. A composition according to any of claims 9-13 further comprising one of more components selected from water, solvents, preservatives, detergents, stabilisers, agents having UV protecting properties, spreading agents, anti-migration Areots, preservatives, foam forming agents, and soiling reducing agents.
- 15. A composition according to any of the claims 9-14 comprising from about 0.001 to 95 %, by weight, of an insecticide.15. A composition according to any of the claims 9-15, wherein the insecticide is selected from the group comprising' pyrethroid compounds such as
Ethofenprox: 2-(4-ethoxyphenyi)-2-methylpropyi-3-phenoxybcnz7i . At-r, LAs AM Fenvalerate: (RS)-alpha-cyariO“3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3 O methylbuiyrate. .re Esfenvalerate: (S)-aipha-cyano-3-phenoxybenzyl (S)-2-(4-chloropheuyf)-5- •AA. * w: methylbuiyrate. 2^··** re.,: re Fenpropaihrin: (RS)-aIpha-cyaxiO“3-phenoxybenzyl 2,2,3,3- ’ · < S tetramethylcydopropanecarboxylate, . —c Cy’penrieihri.n: (RS)-aJpha-cyano-3-phenoxyben2yl (IRS)-cis, trans-3-(2,2- dichiorovinyI)-2,2-dimethylcyclopropanecarboxylate. # Permethrin: 3-phenoxybeiKyi (lRS)-cis,trans-3-(2,2-dichlorovii.' * · ώ methylcyciopropanecarboxylate, Cyhalothrin.; (RS)-a!pha~cyano-3-phenoxybenzyl (Z)-(lRS)-cis-3- (2-chloro-3,3,3tnfiuoroprop~i~enyl)-2,2- dimethylcyclopro panecar. yiate. Dekcniethnn: (S)-alpha-cya.fio-3-phenoxybenzyl (lR)-cis-3-( 2,2-,.. 2,2-aime;h\L· ,'iopanecarboxylate, Cydoprothnri: (RSi-ripha-cyano-S-phenoxybenzyl (RS)-2,2-dichloro 2.....(4., eth oxyphenyl) cy C opropanecarboxylate, FAvadnate: ialpha-cyanoA-phenoxybenzylN-(2-chloro-alpha.ari' -. .//:::- r. AAT: .SHEET trifluoro-p-tolyl) -D-valinate),Bifenthrin: (2-methylbiphenyl-3-ybnethyl)0(Z)-(lRS)-cis-3-(2-chloro-3,3,3trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, 2methyl-2-(4-bromodifluoromethoxypbenyI)propyl (3-phenoxybenzyl) ether,Tralometbrin: (S)-alpha-cyano-3-phenoxybenzyI (lR-cis)3 ((1 *RS)( 1 ',2',2',2'tetrabromoethyl)) -2,2-dimethylcyciopropanecarboxylate,Silafluofen: 4-ethoxyphenyl (3 -(4-fluoro-3-phenoxyphenyl)propyI} dimethylsilane,D-fenothrin: 3-phenoxybenzyl (lR)-cis, trans)-chrysanthemate,Cyphenothrin: (RS)-alpha-cyano-3-phenoxybenzyl (IR-cis, trans)-chrysanthemate,D-resmethrin: 5-benzyl-3-furylmethyI (IR-cis, trans)-chrysanthemate,Acrinathrin: (S)-alpha-cyano-3-phenoxybenzyl (lR-cis(Z))-(2,2-dimethyl-3- (oxo3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl (cyclopropanecarboxylate,Cyfluthrin: (RS)-alpha-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyl)2.2- dimethylcyclopropanecarboxylate,Tefluthrin: 2,3,5,6-tetrafluoro-4-methylbenzyI (IRS-cis (Z))-3-(2-chloro-3,3,3trifluoroprop-l-enyl)-2,2-dimethylcycIopropanecarbo xylate,Transfluthrin: 2,3,5,6-tetrafluorobenzyl (lR-trans)-3-(2,2-dichlorovinyl) -2,2dimethylcyclopropanecarboxylate,Tetramethrin: 3,4,5,6-tetrahydrophthaIimidomethyl (lRS)-cis, transchrysanthemate,Allethrin: (RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (IRS)-cis, transchrysanthemate,Pralletbrin: (S)-2-methyI-4-oxo-3-(2-propynyl)cyclopent-2-enyl (IR)-cis, transchrysanthemate,Empentbrin: (RS)-1 -ethynyl-2-methyl-2-pentenyi (lR)-cis, trans-chrysanthemate,Imiprothrin: 2,5-dioxo-3-(prop-2-ynyl)imidazolidin-l-ylmethyl (IR)-cis, trans2.2- dimethyl-3-(2-methyl-l-propenyl)-cyclopropanecarboxylate,D-flamethrin: 5-(2-propynyl)-furfuryl (lR)-cis, trans-chrysanthemate, and 5-(2propynyl)furfuryl 2.2,3,S-tetramethvlcyclopropanecarboxylate;in inCM o*>·..CM o(SlAMENDED SHEET carbamate compounds such asAlanycarb:Bendiocarb:Carbaryl:Isoprocarb:Carbosulfan:Fenoxycarb:Indoxacarb:Propoxur;Ptrimicarb:Thidtocarb:Msthomyl:EtHofencarb:Fenothiocarb;Cartap:Fenobucarb:Xb-lC.··Xylyicarb:, ' ' V ίS-methyl-N[[N-methyl-N-[N-benzyl-N(2-ethoxy-carbonylethyi) mi nothio]carbamoyl]thioacetimidate,2,2-dimethyi-1,3-benzodioxol-4yl- methylcarbamate:, (1-naphthyl N-methylcarbamate,2-(l-methyleihyl) phenyl methylcarbamate,2,3 dihydro-2,2-dimethyl-7-benzofuranyl [(dibutylamino)tliiojmethylcarbamate, Ethyl[2-(4-pheaoxyphenoxy)ethyl] carbamate, Methyl-7-chloro-2,3,4a,5-tetrahydro-2-[methoxycarbonyl (-4trifluoromethoxyphenyl)]2-isopropyloxyphenol methylcarbamate, 2-dimethylamino-5,6-dimethyl-4-pyriniidinyl- dimethy Carbamate, Dimethyl N,N’(thiobis((methylimino)carbonoyloxy) bisethanimidiothioate),S-methyl N~((rneihylcarbamoyl)oxy)thioacetainidate,2-((ethylthio)methyl)phenyl methylcarbamate,S-(4-phenoxybutyl)-N,N-dimethyl thiocarbamate,S,S’-(2-5dimethylamino)trimethylene)bis (thiocarbamate) hydrochloride.2-sec-butyIphenylmethyl carbamate,3,5 -dimethvlpheny I-methy 1 carbamate,3,4-dimethylphenylmethylcarbamate, :ΛCM organophosphorous compounds such asFenitrotbion: Ο,Ο-dimethyi 0-(4-nitro-m-tolyl) phosphorothioate,Diazinon: CcO-diethyl-O-ph-iSopropyl-b-methyl-fi-pyrimidinyi) p,»Pyndaphemhioir 0-(1,6-dihv vo-l-phenylpyrazidin-3-yI) 0 -.'-di.phosphorothioaie,Piricnphos-Biyl· 0,0-diethyi 0-(2-(dieihylamino) 6-methyl-pyrimidiny>) phosphorothioate, ?c .u· -V.,2 0-[2-(diethyiaramo)-6-methyi-4pyrimidinyl] 0,0-dir, .· • .04 mm-HEETAP V 0Etrimphos:Fenthion:Phoxim:Chlorpyrifos:Chlorpyriphos·Cyanophos:Pyraclofos:Acephate:Azamethiphos:Malathion:Temephos:Dimethoate:FormotHion:Phenthoate:phosphorothioate, . 0-6-ethoxy-2-ethyl-pyrimidin-4-yl-0,0-dimethyl-phosphorothioate, 0,0-dimethyI-0-[-3-methyl-4-(methylthio) phenyl phosphorothioate,2-(diethoxyphosphinothoyloxyimino)-2-phenyIacetonitrile, 0,0-diethyl-0-(3,5,6-trichloro-2-pyrinyl) phosphorothioate,.•methyl: 0,0-dimethyl 0-(3,5,6-trichloro-2-pyridinyl) phosphorothioate, 0,0-dimethyl 0-(4cyanophenyl) phosphorothioate, (R,S)[4-chlorophenyl)-pyrazol-4-yl] -O-ethyl-S-n-propyl phosphorothioate,0, S-dimethyl acetylphosphoroamidothioate, S-(6-chloro-2,3-dihydro-oxo-l,3-oxazolo [4,5-b] pyridin-3-ylmethyl phosphorothioate,0,0-dimethyl phosphorodithioate ester of diethyl mercaptosuccinate, (0,0’(thiodi-4-l-phenyIene) 0,0,0,0-tetramethyl phosphorodithioate, ((0,0-dimethyl S-(n-methylcarbamoylmethyl) phosphorodithioate, S[2-formylmethyIamino]-2-oxoethyl]-0,0-dimethyl phosphorodithioate,0,0-dimethyl S-(alpha-ethoxycarbonylbenzyl)-phosphorodithioate;JT)'IDC\i o · *·-, oinsecticides with a sterilising effect on adult mosquitoes such as:1 -(alfa-4-(chloro-alpha-cyclopropyIbenzylidenamino-oxy)-p-tolyI)-3 -(2,6diflourobenzoyl)urea,Diflubenzuron: N-(((3,5-dichloro-4-( 1,1,2,2-tetraflouroethoxy)phenylamino) carbonyl)2,6 diflouro benzamid,Trifiumuron: 2-Chloro-N-(((4-(triflouromethoxy) phenyl)-amino-)carbony!) benzamide, or a triazin such as N-cycIopropyl- 1,3,5 -triazme-2,4,6-triamin; and the repellant is selected from30 N,N-DiethyI-meta-toIuamide(DEET),Ν,Ν-diethylphenylacetamide (DEPA),1 -(3-cyclohexen-1 -yl-carbonyl)-2-metnylpiperine,AMENDED SHEET s;kb artV (2-hydroxy'methylcyclohexyi) acetic acid lactone, (2-ethyi-i,3--hexandioI), indalone,Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as (+/-)-3-aflyl-2-niethyl-d~oxocylopent-25 (~)enyl-(-r-)irans-chrysantemate (Esbiothrin), a repeiiant derived from or identical with plant extracts like limonen, citronella, eugenol, (+)-Eucamalol (1), (-)-1-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratiis (lemon grass), Cymopogan aaridus (citranella). - 17. A composition according io any of the claims 9-16, which is pn . ’’ * 1 as 3 kit for impregnation by the end-user.IS, A composition according to claim 17, wherein the composition in the kit is adapted , .,., for preparing a solution or emuision by adding water.. C-u
- 19. A composition according to claim 18 wherein the composition in the kit is in the Cfo form of a dry composition such as a powder, a capsule, a tablet, or an effervescentCM tablet..
- 20. A process for the impregnation of a fabric or a netting so as to impart insect and/or tick killing and/or repellence properties, comprising:a) prep,arms a solution or a water emulsion of an insecticide and/or :, x.b-n and a film forming component red’,,., , vush off and degradation of the in·.-;· . -foe component coni the netting or fabric by forming a water and optionally oil resistant film around the fibres and passing the fabric or netting through the solution or emuision or · .a. n or emu,» m the fabric or netting at a tei.i ,-. : a or w ---. ‘/mate solution or water emulsion of an insecticide a penem anc mg cnccner separate .con or water emuision of a film :. .. _ <·' .,·? ·'Ν’ u oHEETAP ν 015 8 7 nent reducing wash off and degradation of the insecticide component from the netting or fabric by forming a water and optionally oil resistant film around the fibres and applying the solution or water emulsion of the insecticide and/or repellent on the fabric or netting and then passing the fabric through the solution or water emulsion of the film forming component, wherein said film forming component comprises i) one or more components selected from paraffin oils or waxes, silicons, silicon oils or waxes, and polyfluorocarbons, or derivatives thereof and ii) a polymeric backbone fixative resin.c) optionally removing surplus composition by pressing the fabric or netting, andd) passively or actively drying the fabric at a temperature within 20-150 °C.
- 21. A process according to claim 20, wherein the emulsion is in the form of a foam.t
- 22. A process according to claim 20, wherein the solution or emulsion comprises a composition as defined in any of the claims 9-19. * ’ ί ·
- 23. A process according to any of claims 20-22, wherein the impregnation is a reimpregnation of the fabric or netting.
Applications Claiming Priority (2)
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DKPA199901702 | 1999-11-25 | ||
PCT/DK2000/000649 WO2001037662A1 (en) | 1999-11-25 | 2000-11-24 | Composition for impregnation of fabrics and nettings |
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AP2002002515A0 AP2002002515A0 (en) | 2002-06-30 |
AP1387A true AP1387A (en) | 2005-04-13 |
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APAP/P/2002/002515A AP1387A (en) | 1999-11-25 | 2000-11-24 | Composition for impregnation of fabrics and nettings. |
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CN (1) | CN1209965C (en) |
AP (1) | AP1387A (en) |
AU (1) | AU1693101A (en) |
BR (1) | BR0015844A (en) |
WO (1) | WO2001037662A1 (en) |
ZA (1) | ZA200204114B (en) |
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Also Published As
Publication number | Publication date |
---|---|
BR0015844A (en) | 2006-06-06 |
ZA200204114B (en) | 2003-07-30 |
CN1209965C (en) | 2005-07-13 |
AP2002002515A0 (en) | 2002-06-30 |
WO2001037662A1 (en) | 2001-05-31 |
CN1414831A (en) | 2003-04-30 |
AU1693101A (en) | 2001-06-04 |
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