CZ2019573A3 - Insecticide for protecting wood from pests - Google Patents

Abstract

An insecticidal composition in the form of at least one solid fibrous carrier comprising nanofibers comprising at least one synthetic polymer selected from the group consisting of polyamide, polyurethane, polyvinylidene fluoride, polyvinylidene difluoride, cellulose acetate, polylactide, polycaprolactone, polyvinyl butyral, polylactic acid or a mixture thereof; at least one active substance or a mixture thereof; wherein the fibrous carrier is attached to at least one wall of the textile carrier by lamination.

Description

Insecticide for the protection of wood against pests

Field of technology

The present invention relates to an insecticidal textile composition comprising at least one polymeric nanofiber layer as a carrier for a substance effective in controlling wood-destroying and subcutaneous insects infesting deciduous and coniferous stands.

Prior art

Various methods and active substances can be used to control wood-destroying and sub-insect insects in forest stands. The oldest method is the use of poisoned traps. In the 1970s, aggregation pheromones attracting insects to traps began to be applied to traps. Barking of infested wood is also effective before it reaches the adult developmental stage. Although both of these methods are effective, they are insufficient in times of calamity.

Newer methods use insecticides applied in water to spray landfills or to store wood in water with insecticides. These methods are economically demanding and also pose a significant environmental risk associated with the penetration of insecticides into the soil or with poisoning of small forest animals.

Recently, the insecticidal networks Storanet have appeared on the market, which contact pests in the developmental stage of an adult. This network can be used to protect landfills of uninfested wood, to clean up infested wood and at the same time as poisoned traps. This solution is described in WO / 2010/012671. The described net is impregnated with an insecticide, essentially wrapped on all sides, which is disadvantageous when handling the net for the operator, which is exposed to the toxic effects of the insecticide. The net also kills other forest insects that land on the surface of the net. To ensure functionality, it is impregnated with a high dose of insecticides, the production process produces a high amount of toxic waste. Workers who apply it must be trained, equipped with protective equipment and the total time of network installation is therefore long. The disadvantage is also the low resistance of the network, it often breaks and does not have stable properties in the long term of the season.

In recent years, fumigation technology has been used, which uses ethanedinitrile (EDN) to remediate landfills of infested wood. EDN is a fumigant, a volatile pesticide used in the gaseous state to control diseases and pests. This method is currently allowed as an exception and is in terms of cost especially suitable for large wood dumps (at least 350 m ³ ), another disadvantage of this method is the fact that it can be performed only by a specialized company, as it is a volatile, toxic substance. The applicability of this method is very limited to large landfills and deadlines for specialized companies that have the appropriate permits for the management of toxic and hazardous waste. However, a major problem is the possibility of contamination of soil and subsequently water resources in the locality.

Another method of remediation of infested wood is the MARCATA technology, which combines the application of an insecticide by spraying on the surface of the ridge and covering the treated landfill with non-woven fabric. This technology is protected by the utility model UV 32 889.

The practical disadvantage of this technology is the fact that such an applied insecticide loses its effectiveness after 4-6 weeks and some adults developed from larvae remain under tarpaulin after this period and after a certain time they manage to find an escape route.

Technologies for the production of nanofiber structures (layers) enable the production of nanofiber layers on an industrial scale. Since the beginning of the 21st century, they have been introduced into industrial production in the field of production of filter media, functional textile materials, and separation membranes.

- 1 CZ 2019 - 573 A3

In the fields of technical and medical applications, these structures are used as carriers of active active substances, for example antimicrobial substances, pharmacologically active substances, etc.

The essence of the invention

The above-mentioned disadvantages of the prior art are overcome by an insecticidal composition in the form of at least one solid fibrous carrier comprising nanofibers comprising at least one synthetic polymer selected from the group consisting of polyamide, polyurethane, polyvinylidene fluoride, polyvinylidene difluoride (PVDF), cellulose acetate , polylactide, polycaprolactone, polyvinyl butyral (PVB), polylactic acid (PLA) or a mixture thereof and at least one active ingredient or a mixture thereof; wherein the fibrous carrier is attached to at least one wall of the textile carrier by lamination. By synthetic polymer is meant any type of organic polymer from which nanofibers can be made by known technologies, preferably by electrostatic spinning.

The connection between the fiber carrier wall and the (inner) wall of the textile carrier is ensured either by the presence of bicomponent fibers in the textile carrier which are melted during lamination and allows the connection between the walls and / or by an adhesive applied before lamination to the textile carrier. in the form of a dot grid or sieve.

Nanofibers can be produced by the principle of electrospinning from a polymer spinning solution with a concentration of 10 to 18% by weight, preferably 12 to 14% by weight, of synthetic polymer per total solution volume.

The active substance is an insecticidal substance which acts in a contact manner on adult bark beetles. These are preferably immunocides. The active substance may be at least one insecticide, an immunocide selected from the group consisting of synthetic or natural pyrethroids, preferably comprising cypermethrin (3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano (3-phenoxyphenyl) methyl ester), zeta-cypermethrin ((1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea), alpha-cypermethrin ((IR) -cis- (alphaS) -cypermethrin), cyfluthrin ( [(R) cyano- [4-fluoro-3- (phenoxy) phenyl] methyl] (1R, 3R) -3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropane-1-carboxylate), deltamethrin ([(S ) cyano (3-phenoxyphenyl) methyl] - (1R, 3R) -3 (2,2-dibromoethenyl) -2,2-dimethylcyclopropane-1-carboxylate), ethofenprox (1-ethoxy-4- [2-methyl - ([3- (phenoxy) phenyl] methoxy) propan-2-yl] benzene), permethrin (2,2-dimethyl-3- (2,2-dichloroovinyl) -cyclopropanecarboxylic acid methyl ester), bifenthrin (2-methyl-3-phenylphenyl) methyl (1S, 3S) -3- | (Z) -2-chloro-3,3,3-trifluoroprop-1-phenyl | -2,2-dimethylcyclopropanecarboxylate), chlorfenapyr (4-bromo-2- (4-chloro phenyl) -1-ethoxymethyl-5-trifluoromethyl-1H-pyrrole-3-carbonitrile) and fipronil (5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4 - [(R5) · trifluoromethanesulfinyl] (1H-pyrazole-3-carbonitrile) or mixtures thereof. The best are alphacypermethrin, zeta-cypermethrin, cypermethrin.

Furthermore, it can also be a pheromone, preferably a synthetic pheromone selected from the group consisting of (S) cis-verbenol (4,6,6-trimethylbicyclo [3.1.1] hept-3-en-2-ol), ipsdienol ((4S) -2-methyl-6-methylideneacta-2,7-dien-4-ol) or a mixture thereof.

The active substances contained in the nanofibers of the fiber carrier according to the invention act against pests selected from the group comprising pests of the genus: bark beetles, beauties, carpenters.

The active substance is in nanofibers resp. The fiber carrier according to the invention applied during their preparation by electospinning from the spinning solution to which it is dissolved is therefore present in the entire volume of nanofibers. Alternatively, it may be additionally applied to the nanofiber support by impregnation, for example by spraying, wetting or spraying. After impregnation, the active substance is only on the surface of the fibers.

- 2 CZ 2019 - 573 A3

The diameters of the nanofibers in the fiber carrier according to the invention are in the range of 90 to 450 nm, preferably 120 to 150 nm.

The insecticidal textile composition according to the invention serves as a contact layer for contact with adult pests in order to kill them.

The solid fiber support of the invention is a layer of nanofibers as described above. In case the composition according to the invention comprises two or more fibrous carriers, these are arranged in layers on top of one another and the active substance is contained in the nanofibers of any of the fibrous carriers. Preferably, the active substance is contained in the nanofibers of the contact fiber carrier, which represents the outer, contact side of the composition according to the invention. By contact fiber carrier is meant a fiber carrier which, after use, comes into contact with the pest. Thus, the fibrous carrier of the composition according to the invention has an extremely high specific surface area. This can be used as a carrier for the active substance. By choosing a synthetic polymer, it is possible to influence the stability of the fibrous carrier from a very rapidly soluble to a long-term stable carrier from which the active substances are not released. A variant of degradable synthetic polymers is Polycaprolactone (PCL) or polylactic acid (PLA) polymer. Non-degradable polymers include polyamide. Prior to spinning, the polymers are dissolved in acids, for example in a 2: 1 mixture of acetic acid / formic acid.

The long-term stability of the solid fiber carrier according to the invention in the outdoor environment is at least 6 to 7 months (for at least one season) and significantly lower concentrations of toxic / active substance are advantageous parameters of the invention which can only be achieved using the composition according to the invention.

The content of active substance (preferably zeta cypermethrin) in g per m ^{2 of the} fibrous carrier of the insecticidal composition according to the invention is 0.001 to 0.05 g / m ² , preferably 0.005 to 0.02 g / m ² , more preferably 0.01 to 0.02 g / m ² .

The basis weight of the fibrous carrier in the composition according to the invention is 0.1 to 5.0 g / m ² , preferably from 0.2 to 1.0 g / m ² .

^{A layer of polyamide 6 nanofibers with a basis weight of 0.2 g / m 2} , which contained zeta cypermethrin in an amount of 0.002 g / m ^2, proved to be an already effective layer (mortality of individuals of the pest occurred 4 hours after the first contact). A layer with a basis weight of 0.2 g / m ² containing zeta cypermethrin at a concentration of 0.01 g / m ² was highly effective, at which the mortality of the individuals of the pest occurred in the range of 10 to 60 minutes from the first contact. The fibrous carrier according to the invention of said basis weight (0.2 g / m ² ) is in itself a mechanically unstable, non-manipulable structure, for the production of which the substrate on which it is applied is necessary by electrospinning. This substrate can also be a textile carrier which is part of the insecticidal textile composition according to the invention. Sufficient mechanical reinforcement, i.e. the textile carrier in the composition according to the invention, is fabrics with basis weights of from 20 g / m ² to 120 g / m ² , preferably 50 to 60 g / m ² . The textile carrier is selected from the group consisting of polyester fabrics, raschel fabrics, geotextiles, nonwovens, preferably polypropylene (PP) spunbond fabrics with a UV-stabilized structure, polyamide nonwovens.

The fibrous carrier can also be applied to the textile carrier additionally in the process of transferring the fibrous carrier from the substrate used for production to a suitable textile carrier.

The functionalization of the nanofibers of the fibrous carrier with an insecticidal substance is performed by adding an active substance, for example zeta cypermethrin, to the polymer solution from which the nanofibrous structure (carrier, layer) is subsequently produced by electrospinning. The active substance, for example zeta cypermethrin, can be added to the spinning solution in the form of a solution (variants are given in points 1 and 2 below in the Examples, where its concentration in the added solution is in the range of 20 to

- 3 CZ 2019 - 573 A3

100 g / liter), optionally this substance can be added directly to the polymer solution, the final concentration of active substance, for example alpha cypermethrin in the spinning solution polymerizing in the range 0.001 to 1.5% w / v. to the total volume of the spinning solution.

The combination of a nanofiber carrier and a textile carrier in the insecticidal textile composition of the invention provides mechanical resistance and manipulability of the composition.

The resulting composite (composition according to the invention) is preferably in the form of a tarpaulin intended to cover wood, more preferably intended to cover freshly cut wood to protect it from bark beetle infestation or to cover infested wood before adult bark beetle trips to reduce pest status in forest stands. Upon contact of an adult with the outer surface of the fibrous carrier of the composition of the invention, it is killed. The composition of the invention provides highly effective pest control in the adult developmental stage. This contributes to the protection of a healthy forest stand.

Preferably, the composition according to the invention is provided on one side of the textile carrier with a contact fiber carrier. This arrangement of the device according to the invention is suitable for the production of tarpaulins, which can be used for the protection of landfills of uninfested wood, for the remediation of infested wood and at the same time as poisoned traps. The handling of tarpaulins in the outdoor environment when covering the landfill places demands on the mechanical properties of the composition according to the invention, resistance to weather conditions.

By having the contact fiber carrier on only one side of the device according to the invention, a high safety of the work of the application workers when handling the device is ensured. Unlike sprays, the composition of the invention can be applied close to water sources. There is no water contamination and no fish death. No other insects are killed.

It is necessary to ensure the necessary adhesion (cohesion) between the textile carrier and the fibrous carrier for subsequent handling. This can be ensured by various gluing technologies.

The simplest include the application of various types of adhesives (powder or hot melt adhesive, hot melt mesh (binder in the form of a mesh)) or the use of bicomponent fibers in a textile carrier, which are melted in the subsequent lamination process (one fiber component melts) and textile carrier and the fibrous carrier layer joined. An example of a bicomponent fiber is a polyester fiber whose core is meltable at temperatures above 190 ° C, but the fiber sheath melts at temperatures above 110 ° C.

The textile carrier is provided on the wall adjacent to the fibrous carrier with an adhesive which is selected from the group consisting of powder adhesive, hot-melt adhesive, hot-melt mesh.

The contact outer side of the fiber carrier must be mechanically reinforced to prevent abrasion during handling and application of the sheet. Therefore, a cover layer, preferably a fusible network based on copolymers of low-melting polyethylene, is preferably attached to the contact outer side of the fiber carrier. Reinforcement can be performed by tennobonding technology, ultrasonic bonding.

The combination of adhering the fibrous carrier to the textile carrier and at the same time reinforcing the outer contact side of the fibrous carrier represents a hotmelt bonding technology which can be used to transfer the fibrous carrier from the substrate to the textile carrier. For this technology, the limit value is the basis weight of 0.1 g / m ^{2 of} fiber carrier, carriers with a lower basis weight are not transferable in the industrial process of continuous production.

Another variant of mechanical reinforcement or protection of the surface of the fibrous carrier against abrasion is the application of low-melting nets to the surface of the fibrous carrier. Although the application of low-melting nets strengthens the surface and protects it from delamination and abrasion, it also removes the contact area needed to kill pests. Variants of melting networks are networks of adhesives based on polyamides (Spunfab PA) (co

- 4 CZ 2019 - 573 A3 polyamide) or based on copolymers of low - melting polyethylene LDPE / HDPE / LDPE fabric made of LDPE / HDPE / LDPE film.

A preferred arrangement of the layers in the composition according to the invention is that at least one side of the textile carrier is provided with at least one fibrous carrier, to which at least one cover layer in the form of a low-melting net abuts from the other (outer) side, the contact surfaces between the textile carrier and preferably provided with an adhesive and the outside of the fiber carrier is reinforced with a low-melting net. All layers of the composition according to the invention are preferably attached to each other by lamination. It is practically possible to use all kinds of textile lamination technologies using adhesives or technologies using heat (thermobonding).

Explanation of drawings

Giant. 1 Fiber carrier consisting of PA6 nanofibers with a basis weight of 1.0 g / m ² , containing zeta cypermethrin.

Giant. 2 Fiber carrier consisting of PA6 nanofibers with a basis weight of 0,23 g / m ² , containing cypermethrin, in the background a fiber from a nonwoven substrate

Examples of embodiments of the invention

Preparations containing these layers:

1 / Non-woven polypropylene fabric (PP SB) stabilized against UV radiation with a basis weight of 50 g / m ² , a layer of powder adhesive EVA T06 (hot melt adhesive based on ethylene-vinyl acetate) is applied (poured and fused) to this carrier (granulation 80 to 200 μm) with a basis weight of 5 g / m ² . A fibrous carrier made of polyamide 6 (PA6) polymer (basic type of extruded polyamide) with a basis weight of 0.2 g / m ² containing the addition of zeta cypermethrin with a content of 0.001 g / m ² is applied to the nonwoven fabric with the application of a powder adhesive (Fig. 1). . Fury 10 EW containing zeta-cypermethrin (1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea) was added to a spinning solution containing PA6 at a concentration of 14% by weight. g / 1). The diameters of the nanofibers in the resulting support range from 90 to 250 nm (optimally 120 to 150 nm) depending on the concentration of the polymer solution and the conditions for the preparation of the fibrous support. The LDPE / HDPE / LDPE fabric is laminated to the fibrous carrier.

2 / Polyester nonwoven fabric with a basis weight of 60 g / m ² , a layer of EVA T06 powder adhesive (granulation 80 - 200 μm) with a basis weight of 5 g / m ² is applied (sprinkled and fused) to this carrier. A fiber carrier made of PA6 polymer with a basis weight of 0.2 g / m ² containing the addition of cypermethrin with a content of 0.001 g / m ² is applied to the nonwoven fabric with the application of a powder adhesive (Fig. 2). Nurelle D containing the active ingredient cypermethrin (50 g / l) was added to a spinning solution containing PA6 at a concentration of 14% by weight. The diameters of the nanofibers in the structure range from 90 to 250 nm (optimally 120 to 150 nm) depending on the concentration of the polymer solution and the conditions for the preparation of the nanofiber structure. The LDPE / HDPE / LDPE fabric is laminated to the fiber carrier.

Preparation procedure:

1a) To a polymer solution of PA6 polymer, 14% by weight of the polymer concentration in the acetic acid / formic acid solvent system in a ratio of 2: 1, a solution containing an insecticide is added to form a spinning solution. It is a solution of Fury 10 EW containing zeta-cypermethrin (100 g / l). The insecticide solution is added to the polymer solution in a concentration of 0.05 to 1.0 wt. % (optimally 0.5 wt.%).

To a polymer solution of polymer PA6, 14% by weight of the polymer concentration in the solvent system acetic acid / formic acid in a ratio of 2: 1, a solution containing an insecticide is added to form a spinning solution. This is a Nur: elle D solution containing the active substance cypermethrin (50 g / l). The insecticide solution is added to the polymer solution at a concentration of 0.075 to 1.5 wt. % (optimally 0.075 wt.%).

lc) To a polymer solution of polymer PA6, 14% by weight of the polymer concentration in the solvent system acetic acid / formic acid in a ratio of 2: 1, cypermethrin is added in an amount of 0.01 to 1.0% by weight (g / liter) of solution ( optimally 0.1 wt.% (g / liter).

2 / PP SB UV stabilized with a basis weight of 50 g / m ² is used as a textile carrier for the application of the fibrous carrier, another variant is the use of a non-woven fabric made of Novolin 80 gsm polyester (100% polyester with a weight of 80 g / m ² ).

3 / a layer of EVA T06 powder adhesive (granulation 80 to 200 μm) with a basis weight of 3 to 10 g / m ² is applied to the textile carrier and is melted on the textile carrier at a temperature of 110 to 120 ° C (optimally applied 5 g / m ² ).

4 / A fibrous carrier made of a spinning solution is applied to the textile carrier by an electrospinning process (NanospiderTM technology or other electrospinning technology) (see point 1). The fiber carrier has a basis weight of 0.1 to 5.0 g / m ² (a sufficient layer of 0.05 g / m ² acts to achieve a partial effect).

5 / LDPE / HDPE / LDPE fabric is used to stabilize the fiber carrier on the outside (contact side).

The selected EVA T06 powder adhesive has a low melting point of 100 to 120 ° C, as do the LDPE / HDPE / LDPE stabilizing fabrics. At the same time, this temperature is lower than the melting temperature of the selected substrate (PP SB or PES nonwoven fabric). Thanks to this combination, the structure of the textile carrier and the fibrous carrier will not be destroyed when all the layers are joined.

6 / The connection of all layers is ensured in one step when passing through the laminating machine. The lamination temperature is in the range of 100 to 120 ° C, optimally 110 ° C. The connection occurs by a combination of temperature and pressure. It is practically possible to use any lamination technology working on this principle.

7 / It is possible to produce tarpaulins of any size from the produced material (fabric wound on rolls in the width of 1.6-2.4 meters).

Claims (13)

An insecticidal composition in the form of at least one solid fibrous carrier comprising nanofibers comprising at least one synthetic polymer selected from the group consisting of polyamide, polyurethane, polyvinylidene fluoride, polyvinylidene difluoride, cellulose acetate, polylactide, polycaprolactone, polyvinyl butyral, polylactic acid or a mixture thereof and at least one active ingredient or a mixture thereof; wherein the fibrous carrier is attached to at least one wall of the textile carrier by lamination. Insecticidal composition according to claim 1, characterized in that the active substance is an insecticidal substance, preferably an immunocide selected from the group consisting of synthetic or natural pyrethroids, more preferably cypermethrin, zeta-cypermethrin, alpha-cypermethrin, cyfluthrin, deltamethrin, ethofenprox, permethrin, bifenthrin, chlorfenapyr and fipronil or mixtures thereof, preferably alpha-cypermethrin, zeta-cypermethrin, cypermethrin. The insecticidal composition according to claim 1 or claim 2, further preferably comprising a pheromone, preferably a synthetic pheromone selected from the group consisting of (S) -cis-verbenol, ipsdienol or a mixture thereof. Insecticidal composition according to any one of claims 1 to 3, characterized in that the nanofibers of the at least one solid fibrous carrier contain the active substance in their entire volume. Insecticidal composition according to any one of claims 1 to 4, characterized in that the diameters of the nanofibers in the fibrous carrier are in the range of 90 to 450 nm, preferably 120 to 150 nm. Insecticidal composition according to any one of Claims 1 to 5, characterized in that the active substance content of the fibrous carrier is 0.001 to 0.05 g / m ² , preferably 0.005 to 0.02 g / m ² , more preferably 0.01 up to 0.02 g / m ² . Insecticidal composition according to any one of claims 1 to 6, characterized in that the basis weight of the fibrous carrier is 0.1 to 5.0 g / m ² g / m ² , preferably from 0.2 to 1.0 g / m 2. m ² . Insecticidal composition according to any one of claims 1 to 7, characterized in that the textile carrier is a fabric with basis weights of from 20 to 120 g / m ² , preferably 50 to 60 g / m ² . Insecticidal composition according to any one of claims 1 to 8, characterized in that the textile carrier is selected from the group consisting of polyester fabrics, raschel fabrics, geotextiles, nonwovens, preferably polypropylene (PP) spunbond fabrics with UV stabilized structure, polyamide nonwovens textile. Insecticidal composition according to any one of claims 1 to 9, characterized in that the textile carrier is provided on the wall adjacent to the fibrous carrier with an adhesive selected from the group consisting of powder adhesive, hot-melt adhesive, hot-melt net. Insecticidal composition according to any one of claims 1 to 10, characterized in that a cover layer, preferably a melting network based on copolymers of low-melting polyethylene, is attached to the contact outer side of the fiber carrier. Insecticidal composition according to Claim 11, characterized in that the fibrous carrier, the textile carrier and the cover layer are joined by lamination. - 7 CZ 2019 - 573 A3 Insecticidal composition according to any one of claims 1 to 12, characterized in that it is in the form of a tarpaulin intended to cover wood.