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Title:
INSECTICIDE MEANS FOR WOOD PROTECTION
Document Type and Number:
WIPO Patent Application WO/2021/047700
Kind Code:
A1
Abstract:
The insecticide means that is in the form of at least one solid fiber carrier that comprises nanofibers containing at least one synthetic polymer selected from the group containing polyamide, polyurethane, polyvinyliden fluoride, polyvinyliden difluoride, cellulose acetate, polylactide, polycaprolactone, polyvinyl butyral, polylactic acid or mixtures thereof and at least one active agent or mixture thereof; whereas the fiber carrier is attached to at least one side of the textile carrier by lamination.

Inventors:
MUNZAROVA MARCELA (CZ)
Application Number:
PCT/CZ2020/050068
Publication Date:
March 18, 2021
Filing Date:
September 11, 2020
Export Citation:
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Assignee:
NANO MEDICAL S R O (CZ)
International Classes:
A01N25/34; A01N53/00; A01P7/04; B32B27/00; D06M13/348; D06N3/00
Domestic Patent References:
WO2008032844A22008-03-20
WO2008118955A12008-10-02
WO2013171118A22013-11-21
WO2010012671A22010-02-04
Foreign References:
US20120270942A12012-10-25
CZ2017402A32019-01-23
Other References:
BEHNAD ROSHANI ET AL: "Controlled release of thiram pesticide from poly (L-lactic acid) nanofibers", THE JOURNAL OF THE TEXTILE INSTITUTE, vol. 108, no. 9, 21 November 2016 (2016-11-21), GB, pages 1504 - 1509, XP055620141, ISSN: 0040-5000, DOI: 10.1080/00405000.2016.1258950
SENEM AVAZ SEVEN ET AL: "Abstract", BIORXIV, 31 July 2018 (2018-07-31), XP055621707, Retrieved from the Internet DOI: 10.1101/381426
CHUNHUI XIANG ET AL: "Structure and Properties of Polyamide Fabrics with Insect-Repellent Functionality by Electrospinning and Oxygen Plasma-Treated Surface Coating", POLYMERS, vol. 12, no. 10, 1 October 2020 (2020-10-01), CH, pages 2196, XP055761464, ISSN: 2073-4360, DOI: 10.3390/polym12102196
Attorney, Agent or Firm:
KANIA, SEDLAK, SMOLA S.R.O. (CZ)
Download PDF:
Claims:
CLAIMS

1. An insecticide means, characterized in that, it is in a form of at least one solid fiber carrier that comprises nanofibers containing at least one synthetic polymer selected from the group containing polyamide, polyurethane, polyvinyliden fluoride, polyvinyliden difluoride, cellulose acetate, polylactide, polycaprolactone, polyvinyl butyral, polylactic acid or the mixtures thereof and at least one active agent or mixture thereof; whereas the fiber carrier is attached to at least one side of the textile carrier through lamination.

2. The insecticide means according to claim 1, characterized in that, the active agent is insecticide agent and is preferably adulticide selected from the group containing of synthetic or natural pyrethroides, more preferably it contains cypermethrin, zeta-cypermethrin, alpha-cypermethrin, cyfluthrin, deltamethrin, ethofenprox, permethrin, bifenthrin, chlorfenapyr, and fipronil or mixtures thereof, most preferably alpha-cypermethrin, zeta-cypermethrin, cypermethrin.

3. The insecticide means according to claim 1 or claim 2, characterized in that, it further preferably contains a pheromone, preferably a synthetic pheromone selected from the group containing (S)-cis-verbenol, ipsdienol or mixture thereof.

4. The insecticide means according to any of claims 1 to 3, characterized in that, nanofibers of at least one solid fiber carrier contain the active agent in the whole volume.

5. The insecticide means according to any of claims 1 to 4, characterized in that, diameters of nanofibers in fiber earner are in the range 90 to 450 nm, preferably 120 to 150 nm.

6. The insecticide means according to any of claims 1 to 5, characterized in that, the content of the active agent in the fiber earner is 0.001 to 0.05 g/m2, preferably 0.005 to 0.02 g/m2, more preferably 0.01 to 0.02 g/m2.

7. The insecticide means according to any of claims 1 to 6, characterized in that, areal mass of the fiber earner is 0.1 to 5.0 g/m2, preferably 0.2 to 1.0 g/m2.

8. The insecticide means according to any of claims 1 to 7, characterized in that, the textile earner are textiles of areal mass from 20 to 120 g/m2, preferably 50 to 60 g/m2.

9. The insecticide means according to any of claims 1 to 8, characterized in that, the textile carrier is selected from the group containing polyester textiles, raschel wovens, geotextiles, nonwoven textiles, preferably polypropylene (PP) spunbond textiles with UV stabilized structure, polyamide nonwoven textiles.

10. The insecticide means according to any of claims 1 to 9, characterized in that, the textile earner is on the side adjacent to the fiber carrier provided with adhesive that is selected from the group containing of powder adhesive, hot melt adhesive, hot melt adhesive mesh.

11. The insecticide means according to any of claims 1 to 10, characterized in that, upon the contact outer side of the fiber carrier is attached the cover layer, preferably hot melt adhesive mesh based on copolymers of low melting polyethylene.

12. The insecticide means according to claim 11, characterized in that, the fiber carrier, the textile carrier and the cover layer are attached by lamination.

13. The insecticide means according to any of claims 1 to 12, characterized in that, it is in the form of a taipaulin intended for covering of wood.

Description:
Insecticide means for wood protection Field of invention

The present invention relates to an insecticide textile means for wood protection containing at least one polymer nanofiber layer as a carrier of an agent for elimination of wood-destroying and bark insects attacking deciduous and coniferous growth.

Background of the invention

Various approaches and active agents may be used for elimination of wood-destroying and bark insect in wood growth. The oldest method is the use of poisoned traps. Since the 70s of the 20 th century, aggregation pheromones attracting insects into the traps have been applied. Debarking of infested wood before reaching the developmental stage of an adult is also effective. Although both methods are efficient, they are insufficient at times of calamity.

More recent processes use insecticide applied in water, with which the wood piles are sprayed or the wood is stocked in water with insecticides. These methods are costly and represent also significant environmental risk related to insecticides penetration into soil or to poisoning of small forest animals.

Recently, insecticide nets Storanet appeared on the market, that through contact eliminate pests in the developmental stage of an adult. This net may be used for protection of non-infested wood piles, for sanitation of infested wood as well as for poison traps. This solution is described in WO/2010/012671. The described net is impregnated with the insecticide, it is in fact wrapped on all sides, which is disadvantageous during manipulation with the net by workers that are exposed to toxic effects of the insecticide agent. The net eliminates also other forest insects that rest on the surface of the net. To ensure functionality, the net is impregnated with high dose of insecticide, the manufacturing process produces high amount of toxic waste. Workers that apply the agent must be trained, equipped with protective equipment and the total time of net installation is long. Disadvantageous is also small duration of the net, it often tears and does not possess stabile properties in the long-time horizon of the season.

Recently, the technology of fumigation is used that uses preparation ethandinitril (EDN) for sanitation of piles of infested wood. EDN is a fumigant, i.e. volatile pesticide preparation used in gaseous state for extermination of diseases and pests. This method is so far allowed for exception and is, regarding its cost, suitable especially for large wood piles (at least 350 m 3 ), another disadvantage of this method is the fact that it can be performed only with specialized company, since it relates to a volatile, toxic agent. The usage of this method is very limited to large wood piles and terms of free capacity of specialized companies that have necessary appropriate authorization for handling toxic and dangerous waste. Fundamental problem is, however, the possibility of soil contamination and following contamination of water sources in the locality.

Another process of sanitation of infected wood is technology MARCATA that combines application of insecticide by spraying on the surface of a timber stack and covering the pile with nonwoven fabric. This technology is protected by utility model UV 32 889.

Practical disadvantage of this technology is the fact that so applied insecticide loses its efficiency after 4-6 weeks and a portion of adults developed from larvae after this period remains under the tarpaulin and after a while they find their way out.

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

In the field of technical and medicinal applications are these structures used as carriers of active agents, for example, antimicrobial agents, pharmacologically active agents, etc.

Summary of the invention

Above stated disadvantages in the prior art are overcome by insecticide means the subject-matter of which it is in the form of at least one solid fiber carrier that comprises nanofibers containing at least one synthetic polymer selected from a group containing polyamide, polyurethane, polyvinylidene fluoride, polyvinylidene difluoride (PVDF), cellulose acetate, polylactide, polycaprolactone, polyvinyl butyral (PVB), polylactic acid (PLA) or mixture thereof and at least one active agent or mixture thereof; the fiber carrier being attached to at least one side of the textile carrier by lamination. It is understood by the synthetic polymer any type of organic polymer, from which nanofibers may be produced using known technologies, preferably electrostatic spinning.

Attachment between wall of the fiber carrier and an (inner) wall of the textile carrier is ensured either by the presence of bicomponent fibers in the textile earner, that are during lamination partially melted and enable attachment between the walls and/or by using an adhesive that is applied before lamination upon the textile carrier across the area or in the form of a dot grid or a sieve.

Nanofibers may be produced using principle of electrostatic spinning of polymer spinning solution of concentration 10 to 18 wt.%, preferably 12 to 14 wt.% of synthetic polymer per the total solution volume.

The active agent is an insecticide agent that acts through contact on an adult of bark beetle. Preferably, it relates to an adulticide. The active agent may be at least one insecticide, adulticide, that is selected from a group containing synthetic or natural pyrethroides preferably containing cypermethrin (cyano(3-phenoxyphenyl)methylester of 3 -(2,2- dichloroethenyl)-2,2-dimethyl~cyclopiOpancarboxylic acid), zeta-cypermethrin ((l-(3,5- dichloro-2,4-difluoiOphenyl)-3~(2,6-difluoiObenzoyl) urea), alpha-cypermethrin ((lR)-cis- (alphaS)-cypermetlnin), cyfluthrin ([(R)-cyano-[4-fluoro-3~

(phenoxy)phenyl] methyl] ( lR,3R)-3 -(2,2-dichlorethenyl)-2,2-dimethylcyclopropan- 1 - carboxylate), deltamethrin ([(5)-cyan(3-phenoxyphenyl)methyl]-(lR,3R)-3-(2,2- dibiOinethenyl)-2,2-dimethylcyclopropan- 1 -carboxylate), ethophenprox ( 1 -ethoxy-4- [2- methyl-l-([3-(phenoxy)phenyl]methoxy)propan-2-yl]benzen), permethrin ((3- phenoxyphenyl)methylester of 2,2-dimethyl-3 -(2,2-dichlorovinyl)-cyclopropancarboxylic acid), bifenthrin (2-methyl-3 -phenylphenyl)methyl( 1 S,3S)-3 - [(Z)-2-chloro~3 ,3,3- trifluoroprop- 1 -enyl] - 2,2-dimethylcyclo-propan- 1 -carboxylate), chlorophenapyr (4-brom-2- (4-chloiOphenyl)-l-ethoxymethyl-5-trifluormethyl-lf7-pyiTol- 3-carbonitril) a fipronil (5- amino-1 -[2,6-dic]dor-4-(trifluormethyl)phenyl]-4-[(/fS')-trifluorme thansulIinyl]-l//-pyrazol-3- carbonitril) or mixtures thereof. Most preferably, they are alpha-cypermethrin, zeta- cypermethrin, cypermethrin.

Further, it may be also a pheromone, preferably synthetic pheromone selected from the group containing (S)-cis-verbenol (4,6,6-trimethylbicyclo[3.1.1]hept-3-en-2-ol), ipsdienol ((45 -2-methyl-6-methylidenocta-2,7-dien-4-ol) or mixtures thereof.

Active agents contained in nanofibers of the fiber carrier according to the present invention act against pests selected from the group containing pests of genus: bark beetle, Buprestidae, Cerambycidae.

The active agent is applied into nanofibers, or the fiber earner according to the present invention during their preparation by electrospinning from the spinning solution in which it is dissolved, thus it is contained in the whole volume of nanofibers. Or, it may be applied onto the nanofiber earner additionally by impregnation, for example, by spraying, soaking or jetting. The active agent is present only on the surface of the fibers following the impregnation.

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

Insecticide textile means according to the present invention serves as a contact layer for contact with adults of the pest for the purpose of their elimination.

The solid fiber earner according to the present invention represents the layer of nanofibers as described above. In the case that the means according to the present invention contains two or more fiber earners, are these arranged on top of each other in layers and the active agent is contained in nanofibers of any of the fiber carriers. The active agent is preferably contained in nanofibers of the contact carrier that represents outer, contact side of the means according to the present invention. By the contact fiber earner is understood the fiber carrier that is after use in the contact with the pests. The fiber carrier of the means according to the present invention has therefore extremely large specific surface. This may be used as the earner for the active agent. It is possible to influence the stability of the fiber carrier from very rapidly soluble to long-term stabile earner from which active agents do not release, by the selection of the synthetic polymer. A variant of the degradable synthetic polymer is polymer Polycaprolactone (PCL) or polylactic acid (PLA). Polyamide belongs among non-degradable polymers. Polymers are prior to spinning dissolved in acids, for example, in the mixture of acetic acid/formic acid in the ratio 2:1.

Long-term stability of a solid fiber earner according to the present invention in outdoor environment is at least 6 to 7 months (at least for one season) and significantly lower concentration of toxic/active agent are preferable parameters of the invention that may be achieved only by use of the means according to the present invention.

Content of the active agent (preferably zeta cypermethrin) in g per m 2 of fiber carrier of insecticide means according to the present 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 .

Areal mass of the fiber carrier in the means according to the present invention is 0.1 to 5.0 g/m 2 , preferably 0.2 to 1.0 g/m 2 . As effective layer (mortality of pest individuals occurred 4 hours after the first contact) was in laboratory testing proved the layer of nanofibers from polyamide 6 with areal mass 0.2 g/m 2 , that contained zeta cypermethrin in amount 0.002 g/m 2 . Highly effective was the layer of areal mass 0.2 g/m 2 with content of zeta cypermethrin in concentration 0.01 g/m 2 , at which the mortality of pest individuals occurred within 10 to 60 minutes after the first contact. The fiber carrier according to the present invention of stated areal mass (0.2 g/m 2 ) is in itself a mechanically instable, umnanipulable structure, for whose manufacturing is the use of electrospinning substrate necessary, upon which it is applied. This substrate may be at the same time textile earner that is part of insecticide textile means according to the present invention. Sufficient mechanical reinforcement, i.e. textile carrier in the means according to the present invention, are fabrics of areal mass 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 containing polyester fabric, raschel fabric, geotextile, nonwoven fabric, preferably polypropylene (PP) spunbond textile with UV stabilized structure, polyamide nonwoven textile.

The fiber earner may be applied upon the textile carrier also additionally during a transfer of the fiber earner from a substrate used for manufacturing upon the suitable textile carrier.

Functionalization of nanofibers of the fiber earner with the insecticide agent is performed by addition of the active agent, for example zeta cypermethrin into a polymer solution, from which is then the nanofiber structure (earner, layer) produced by the electrospinning. The active agent, for example, zeta cypermethrin, may be added to the spinning solution in the form of a solution (variants are stated in items 1 and 2 below in Examples, where its concentration in added solution is in the range 20 to 100 g/liter), eventually may be this agent added directly into the polymer solution, whereas resulting concentration of the active agent, for example alpha cypermethrin in the spinning solution of the polymer is in the range 0.001 to 1.5 % wt./vol. per total volume of the spinning solution.

The combination of the nanofiber carrier and the textile carrier in the insecticide textile means according to the present invention ensures mechanical endurance and manipulability with the means.

The resulting composite (means according to the present invention) is preferably in the form of a taipaulin for covering wood, more preferably meant for covering freshly cut wood due to its protection against infection by bark beetle or covering of infected wood before the adults of bark beetle fly out, to reduce number of the pest in wood growth. When the adult contacts the outer surface of the fiber carrier of the means according to the present invention it dies. The means according to the present invention ensures highly effective elimination of the pests in the stadium of an adult. It thus adds up to protection of healthy wood growth.

The means according to the present invention is preferably equipped on one side of the textile carrier with the contact fiber carrier. This arrangement of the means according to the present invention is suitable for producing of the taipaulin, applicable to the protection of piles of uninfected wood, for sanitation of infected wood and at the same time as poison traps. Manipulation with the tarpaulins in the outdoor environment during covering the pile demands mechanical properties of the means according to the present invention, endurance against wind conditions.

By the fact, that the contact fiber earner is on one side of the means according to the present invention only, is high safety of application workers during the manipulation with the means ensured. Contrary to sprayers, the means according to the present invention may be applied in the vicinity of water sources. No water contamination and fish death occurs. No other insect is eliminated.

It is necessary to ensure sufficient adhesion between the textile earner and the fiber earner. This may be ensured by various technologies of gluing.

Among the easiest technologies belong application of various kinds of adhesives (powder or hot melt adhesive, hot melt adhesive mesh (connective in the form of a mesh)) or use of bicomponent fibers in textile carrier that are in the following process of lamination partially melted (melting of one component of the fibers occurs) and by pressure is the layer of the textile carrier and the layer of fiber carrier connected. An example of bicomponent fiber is a fiber of polyester whose core is meltable at temperature above 190 °C but the coat of the fiber is melted at temperature above 110 °C.

The textile carrier is on the side adjacent to the fiber earner equipped with adhesive that is selected from the group containing powder adhesive, hot melt adhesive, hot melt adhesive mesh.

A contact outer side of the fiber earner must be mechanically solidified so as not to undergo abrasion during the manipulation and application of the tarpaulin. Therefore, a cover layer is preferably applied on the contact outer side of the fiber earner, preferably the hot melt adhesive mesh based on copolymers of low melting polyethylene. Solidifying may be performed using technology of thermobonding, ultrasonic connecting.

Combination of gluing of the fiber earner to the textile carrier and at the same time solidifying of the outer contact side of the fiber earner is represented by technologies of hot melting connection, that may be used during transfer of the fiber carrier from the substrate to the textile earner. For this technology, the limit value of areal mass of the fiber earner is 0.1 g/m 2 , carriers with lower areal mass are not transferable in the industrial process of continuous production.

Another variant of mechanical solidifying and protection of the surface of the fiber carrier against abrasion is the application of low melting meshes upon the surface of the fiber carrier. The application of low melting meshes solidifies the surface and protects it against delamination and abrasion but at the same time it reduces the contact area needed for the elimination of the pests. Variants of low melting meshes are meshes of adhesives based on polyamides (Spunfab PA) (co-polyamide) or based on copolymers of low melting polyethylene LDPE/HDPE/LDPE textile produced from foil LDPE/FIDPE/LDPE.

Preferable arrangement of the layers in the means according to the present invention is that at least one side of the textile carrier is equipped with at least one fiber carrier, to which adjoins from the other side (outer) at least one cover layer in the form of the low melting mesh, whereas adjacent areas between the textile earner and the fiber carrier are preferably equipped with the adhesive and the outer side of the fiber carrier is solidified with the low melting mesh. All layers of the means according to the present invention are preferably fastened to each other by lamination. It is practically possible to use all kinds of technologies of textile lamination using adhesives or technologies using heat exposure (thermobonding).

Brief description of the drawings

Fig. 1 The fiber carrier comprising nanofibers PA6 of areal mass 1.0 g/m 2 , containing zeta cypermethrin.

Fig. 2 The fiber earner comprising nanofibers PA6 of areal mass 0.23 g/m 2 containing cypermethrin, in the background fiber from the substrate of the nonwoven textile.

Examples of embodiments of the present invention

Preparations containing these layers: 1/ Non woven polypropylene textile (PP SB) stabilized against UV radiation of areal mass 50 g/m 2 , upon this earner is applied (poured and melted) layer of powder adhesive EVA T06 (hot melt adhesive based on ethylene-vinyl-acetate) (granulation 80 to 200 pm) of areal mass 5 g/m 2 . Upon nonwoven textile with application of the powder adhesive is applied fiber earner from polymer polyamide 6 (PA6) (basic type of extruded polyamide) of areal mass 0.2 g/m 2 containing addition of zeta cypermethrin of content 0.001 g/m 2 (Fig. 1). Into spinning solution containing PA6 of concentration 14 wt.% was added preparation Fury 10 EW with content of zeta-cypermethrin (l-(3,5-dichloiO-2,4-difluorophenyl)-3-(2,6~difluoiObenzoyl) urea) (100 g/L). Diameters of nanofibers in the resulting earner vary in the range 90 to 250 nm (optimally 120 to 150 mn) depending on the concentration of the polymer solution and conditions of the preparation of the fiber carrier. Upon the fiber carrier is the laminated textile LDPE/HDPE/LDPE.

2/ Polyester nonwoven textile of areal mass 60 g/m 2 , on this carrier is applied (poured or melted to) a layer of powder adhesive EVA T06 (granulation 80 - 200 mih) of areal mass 5 g/m 2 . The fiber carrier from polymer PA6 of areal mass 0.2 g/m 2 containing preparation of cypermethrin of content 0.001 g/m 2 (Fig. 2) is applied on nonwoven textile with application of powder adhesive. The preparation Nurelle D with content of active agent cypermethrin (50 g/L) was added into spinning solution containing PA6 of concentration 14 wt. %. The diameters of the nanofibers in the structure range from 90 to 250 nm (optimally 120 to 150 nm) depending on the concentration of polymer solution and conditions of the preparation of the nanofiber structure. The textile LDPE/HDPE/LDPE is laminated on fiber carrier.

Preparation procedure: la/ The solution containing the insecticide is added into the polymer solution of polymer PA6, 14 wt.% concentration of polymer in solvent system acetic acid/formic acid in ratio 2:1, resulting in the spinning solution. It relates to the solution Fury 10 EW with content of zeta-cypermethrin (100 g/L). The solution of insecticide is added to the polymer solution in the concentration 0.05 to 1.0 wt. % (optimally 0.5 wt. %). lb/ Solution containing insecticide is added into the polymer solution of polymer PA6, 14 wt. % concentration of polymer in solvent system acetic acid/formic acid in ratio 2:1, resulting in the spinning solution. It relates to solution Nunelle D with a content of active agent cypermethrin (50 g/L). Solution of insecticide is added to the polymer solution in the concentration 0.075 to 1.5 wt.% (optimally 0.075 wt.%). lc/ Cypermethrin in amount of 0.01 to 1.0 wt, % (g/liter) solution (optimally 0.1 wt. % (g/liter) is added into the polymer solution of polymer PA6, 14 wt. % concentration polymer in the solvent system acetic acid/formic acid in ratio 2:1.

2/ PP SB UV stabilized of areal mass 50 g/m 2 is used as textile earner for application of the fiber earner, another variant is use of nonwoven textile from polyester Novolin 80 gsm (100% polyester with mass 80 g/m 2 ).

3/ A layer of the powder adhesive EVA T06 (granulation 80 to 200 pm) of areal mass 3 to 10 g/m 2 is applied upon the textile carrier and it is smelt adhered to the textile earner (optimal deposit 5 g/m 2 ) at the temperature 110 to 120 °C.

4/ The fiber earner produced from spinning solution (see item 1) is applied on the textile earner is by the process of electrospinning (technology NanospiderTM or other technology of electrospinning). The fiber earner has and areal mass 0.1 to 5.0 g/m 2 (for achieving at least partial effect is sufficient a layer of 0.05 g/m 2 ).

5/ For stabilization of the fiber carrier on the outer side (contact side) is used the textile LDPE/HDPE/LDPE .

Selected the powder adhesive EVA T06 has low melting temperature of 100 to 120 °C, as well as the stabilization textile LDPE/HDPE/LDPE. At the same time is this temperature lower than the melting temperature of selected substrate (PP SB or PES nonwoven textile). Thanks to this combination, no destruction of the structure of the textile carrier and the fiber carrier occurs during attachment of all layers.

6/ Attachment of all layers is ensured in one step during the passage through lamination machine. The lamination temperature varies in the range 100 to 120 °C, optimally 110 °C. The attachment is achieved by combination of temperature and pressure. It is practically possible to use any lamination technology based on this principle.

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