KR101695743B1

KR101695743B1 - Polyketone geotextile including polyketone fiber

Info

Publication number: KR101695743B1
Application number: KR1020150074072A
Authority: KR
Inventors: 황순동; 이득진
Original assignee: 주식회사 효성
Priority date: 2015-05-27
Filing date: 2015-05-27
Publication date: 2017-01-12
Also published as: KR20160139385A

Abstract

To provide a polyketone solution from carbon monoxide, an ethylene and a propylene copolymer, and to provide a polyketone fiber having excellent strength, elongation and toughness from the polyketone solution and a geotextile comprising the same. The polyketone geotextile produced according to the present invention is excellent in strength and toughness, and is suitable for use in a geotextile style.

Description

[0001] POLYKETONE GEOTEXTILE INCLUDING POLYKETONE FIBER WITH POLYKETONE FIBERS [0002]

The present invention relates to a high strength polyketone yarn for use in geotextiles, and more particularly to a geotextile comprising polyketone fibers that significantly improve impact absorption performance and have excellent mechanical properties and work performance .

Generally, geotextile for civil engineering construction is constructed and installed in a soft ground for the improvement of the ground of softness such as road, railway, airport, dredging, improvement of landfill, harbor site improvement, horizontal draining, , Which is composed of a vertical drainage pipe installed in soft ground, and a synthetic fiber non-woven filter or soil protection reinforcement and horizontal ship which constitutes the outer surface of a horizontal drainage pipe. Refers to a water-impermeable nonwoven mat.

Generally, soft ground refers to a vulnerable ground in a state where it is impossible to support the upper structure. For example, soft clay, loose sand, and organic soil of dredged soft soil are included.

In Korea, about 70% of the whole country is mountainous area and about 30% of the rest of the country is farmland. Most of these plains are developed along a large river basin and the coast. Most of these plain areas are composed of soft strata that are not deposited and solidified in the Quaternary alluvial deposits. Typically, soft grounds are artificial grounds such as soft ground and dredged landfill formed on the coast or the river. . If the soft ground is left as it is, the settlement amount becomes excessive and the bearing capacity becomes insufficient, resulting in a safety problem.

In particular, in order to install roads, harbors, or structures such as harbor constructions on the upper part of the soft ground such as dredged soil, the water (water) contained in the soft ground is dewatered to improve the soft ground.

Typically, as a typical method of dewatering water (water) such as pore water or excess water in a soft ground, it is necessary to perform a soil protection reinforcement and a horizontal drainage mat in order to separate the surface portion of the soft ground and the horizontal drainage layer, A non-woven geotextile mat is horizontally laid horizontally, a horizontal drainage pipe composed of horizontal drainage pipes and sand having good drainage is formed, and then a vertical drainage pipe is installed in the soft ground, (Water) such as a pore water or an excess water in soft ground is promoted by applying a predetermined pressure necessary for accelerating dehydration and consolidation by load consolidation or vacuum consolidation by laminating embankment layers .

Conventionally, a typical load consolidation method or a vacuum consolidation method for a soft ground uses a dehydration improvement principle. As a typical construction structure, a sand drain, a paper drain, and a plastic drain are used .

The above-mentioned sand drain, paper drain, and plastic drain have been pointed out as disadvantages such as lack of strength, clogging, lack of permeability and drainage, and lack of durability. For example, the plastic drain method uses a plastic drain board composed of a core material and a vertical drainage non-woven geotextile filter that surrounds the core material. The core material of the plastic drain board is a plastic resin, typically polypropylene 50 m, and 70 m, formed of polypropylene (PP) or polyethylene (PE) or the like, and having a plurality of cruciform main parts formed on the outer periphery thereof, for supporting the plastic drain board The non-woven geotextile filter is formed to surround the core material and performs the most important absorption and drainage functions in the plastic drain board. The core and the non-woven geotextile filter mesh The flow path formed in the non-woven type geotextile filter Functions as a conduit for discharging pulled up the pore of the abundant number to the vertical.

Generally, non-woven geotextile filter or mat for soft ground is almost finished to absorb water for drainage after about 6 months after construction. After about 3 years, it is shredded through grounding process, It will be used for the intended land use.

However, the above-mentioned non-woven geotextile filter or mat is usually made of polyester or polypropylene filaments having a monofilament fineness of 6 to 24 denier, and nonwoven fabric and nonwoven fabric entangled fibers are combined with a binder resin and heat Because of the chemical fiber bonded by the adhesive method, after the compaction process through the drainage of the soft ground is performed according to the civil engineering purpose, it is not decomposed in the ground for hundreds of years, and remains almost intact. As a result, And thus the cohesion of the soil is lowered. Therefore, it is an obstacle to strengthening the soil, and the permeability of the soil particles is lowered, thereby causing deterioration or contamination of the ground environment.

On the other hand, a polyketone having a structure in which repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are substantially alternately linked has excellent mechanical and thermal properties, and has high abrasion resistance, chemical resistance and gas barrier properties, Is expected to evolve. For example, polyketone is a useful material for resins, fibers and films with high strength and high heat resistance. Particularly, when a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more is used as a raw material, a fiber or a film having a very high strength and an elastic modulus can be obtained. Such fibers and films are expected to be widely used for building materials and industrial materials such as belts, rubber reinforcements such as hoses and tire cords, geotextiles, ropes and concrete reinforcements.

It is a known fact that olefins such as carbon monoxide and ethylene and propylene are polymerized by using a transition metal complex such as palladium or nickel as a catalyst to obtain a polyketone in which carbon monoxide and olefin alternate.

Polyketone is preferably thermally crosslinked when it melts, so it is preferable to use wet spinning in the case of fiberization. Particularly, polyketone (poly (1-oxotrimethylene)) fibers having substantially excellent physical properties and substantially containing only carbon monoxide and ethylene are apt to undergo thermal crosslinking. Thus, the fibers are very difficult to produce by melt spinning and can only be obtained substantially by wet spinning.

When the polyketone is wet-spun, examples of the solvent to be used include hexafluoroisopropanol and an organic solvent such as m-cresol, phenolic solvent such as resorcinol / water, and resorcinol / carbonate 2-112413, 4-228613, and 7-508317). However, the fibers obtained by wet spinning using such a solvent tend to be easily dispersed, and fatigue resistance and workability are insufficient for use as an industrial material. In addition, such a solvent has high toxicity and flammability, and there is a problem that a large measure against the toxicity and flammability of a solvent is required to make a spinning facility of an industrial scale.

Further, a method of radiating using a polyketone solution prepared by dissolving a polyketone in an aqueous solution containing zinc chloride at a specific concentration, zinc halide such as zinc bromide, or lithium salt such as lithium chloride, lithium iodide and lithium thiocyanate (WO99 / 18143, USP5955019). These aqueous solutions are relatively inexpensive, have low toxicity and are non-flammable and are excellent as polyketone solvents.

In order to solve the above problems, the present invention provides a polyketone copolymer comprising carbon monoxide and a polyketone copolymer composed of at least one olefinically unsaturated hydrocarbon. In the process of producing the multifilament, the pre- To thereby provide a polyketone geotextile having improved strength and toughness.

In order to attain the above object, the present invention provides a poly (methyl methacrylate) having a y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g, which is composed of the repeating units represented by the following general formulas (1) and Wherein the ketone copolymer is produced by a spinning process, a water washing process, a drying process, and a stretching process.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

At this time, the polyketone geotextile may include a step of forming a web with the polyketone fibers; And combining the formed web.

The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, an elongation of 2.5 to 3.5% at 10.0 g / d, and elongation of at least 0.5% at 19.0 g / d or more.

Here, the monofilament of the polyketone fiber preferably has a fineness of 0.5 to 8.0 denier.

Further, the present invention is characterized in that it is 1.0 to 2.0 times in the washing step, and the drying step is hot-roll drying at 100 to 230 ° C, and preferably 1.0 to 2.0 times.

In addition, it is preferable that the stretching process is a method of passing through a heating chamber at 230 to 300 ° C.

The present invention also provides a polyketone geotextile characterized by treating the heat stabilizer before drying and before stretching.

In addition, the present invention provides a polyketone geotextile characterized by a strength of at least 15 g / d.

The present invention is to provide a geotextile comprising a polyketone solution from carbon monoxide, ethylene and propylene copolymer, and polyketone fibers having excellent strength and elongation and excellent toughness from the polyketone solution.

1 is a view schematically showing the role of a heat-resistant stabilizer according to the prior art.
2 is a schematic view of a conventional hot air drying type dryer.
3 is a schematic view of a hot roll drying method according to the present invention.
Fig. 4 is a cross-sectional view of the dry irradiation according to the conventional hot air drying method.
Fig. 5 is a cross-section view of a dry-type drying method according to the present invention.

Hereinafter, the present invention will be described.

The present invention relates to a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), having a y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g, The polyketone geotextile is produced through a process, a drying process, and a stretching process.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

In addition, it is characterized in that it is stretched 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step.

In addition, the drying step may be hot-rolled at 100 to 230 ° C, and the stretching step may be a heating chamber stretching method at 230 to 300 ° C.

In addition, it is preferable to treat the heat stabilizer before the drying step and the stretching step.

Hereinafter, the polymerization method of the polyketone used in the present invention will be described in detail.

One or more olefinically unsaturated compounds (simply referred to as " A "), wherein the monomer units are alternating, and thus the polymer is composed of units of the formula - (CO) -A'- wherein A 'represents the monomer units derived from the applied monomer A ) And a high molecular weight linear polymer of carbon monoxide can be prepared by contacting monomers with a solution of a palladium-containing catalyst composition in a dilute solution in which the polymer does not dissolve or actually dissolve. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.

The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.

In the present invention, not only methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, but also mixed solvents comprising acetic acid and water, ethanol, propanol, and isopropanol can be used as the liquid medium. Particularly, when a mixed solvent of acetic acid and water is used as a liquid medium in the production of polyketone, the catalyst activity can be improved while reducing the production cost of polyketone. Further, since the use of methanol or a dichloromethane solvent forms a mechanism for causing a stopping reaction during the polymerization step, the use of acetic acid or water other than methanol or dichloromethane in the solvent does not have an effect of stopping the catalytic activity stochastically, It plays a big role in improvement.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the effect of the catalyst is less affected. When the concentration of water is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, It is most preferable to use palladium acetate.

Examples of ligands (b) having a Group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) Bis [di (2-methylphenyl) phosphino] propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine, ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) Bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) ) Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

The ligand (b) having a group 15 atom preferred in the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, is 1,3-bis- [di (2-methoxyphenyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and more preferably 1,3-bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- ) Phosphine) is better.

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

Particularly, the anion (c) of the acid having a pKa of 4 or less, which is preferred in the present invention, is p-toluenesulfonic acid, which, when used together with a mixed solvent of acetic acid and water as a liquid medium, not only has a high catalytic activity, It becomes possible to produce a polyketone having a suitable high intrinsic viscosity.

The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.

The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.

In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, C2-C20-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are -olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 5 mol% or more than 95 mol%, the reactivity is poor and the physical properties of the produced polyketone may be deteriorated.

On the other hand, the polyketone copolymer used as the fiber may be composed of ethylene, propylene and carbon monoxide. The larger the molar ratio of propylene is, the more unsuitable as the geotextile. The molar ratio of ethylene to propylene is preferably 100: 0 to 90:10 Do.

On the other hand, the molecular weight distribution of the polyketone is preferably in the range of 1.5 to 4.0, and if it is less than 1.5, the polymerization yield is lowered. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 or more, the molecular weight distribution becomes large. The molecular weight distribution of the most preferred polyketones is 2.5 to 3.5.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 to 300 占 폚, and is generally 210 to 270 占 폚. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, and preferably 5.0 dl / g to 7.0 dl / g . At this time, when the intrinsic viscosity of the polyketone polymer is less than 5.0, the mechanical strength is lowered in production of the fiber, and when it exceeds 7.0, the workability is lowered.

In addition, the strength of the geotextile made of polyketone is preferably 10 to 20 g / d.

The production method of the polyketone fiber of the present invention will be described.

First, the solution extruded from the spinning nozzle passes through an air gap in a vertical direction and solidifies in a coagulating bath. At this time, the air gap is radiated within a range of about 1 to 300 mm in order to obtain a dense and uniform fiber and to provide a smooth cooling effect.

Thereafter, the filament passing through the coagulation bath passes through the water bath. At this time, the temperature of the coagulation bath and water bath is maintained at about 0 to 80 ° C to prevent the deterioration of physical properties due to the formation of pores in the fiber structure due to rapid desolvation.

The fibers having passed through the water-washing tank were subjected to acid washing in an aqueous solution containing the acid, passed through a second water-washing bath to remove the acid, passed through a dryer, and then emulsified in an emulsion- do.

In addition, in order to improve the flatness and improve the property of the housing, it passed the interlace nozzle. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm 2, and the number of entanglement per filament was 2 to 40.

Thereafter, the filament yarn passed through the interlace nozzle is dried while passing through the drying device. In this case, the drying temperature and the drying method have a great influence on the post-processing and physical properties of the filament.

The filament that has passed through the drying device is finally wound in a winder through a secondary emulsion treatment device.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance. In the drawing method, hot air heating method and roller heating method are used, but since the filament is in contact with the roller surface in the roller heating method, the fiber surface is likely to be damaged, so that hot air heating method is more effective in manufacturing high strength polyketone fiber. However, the inventors of the present invention have found that by applying a heat-resistant stabilizer while applying a roller heating method, especially a hot-roll drying method, and performing a stretching process of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, High strength multifilament could be obtained. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

That is, in the present invention, the stretching process is performed using a method of passing through a heating chamber at 230 to 300 ° C.

On the other hand, as the solvent for dissolving the polyketone, it is preferable to use an aqueous solution containing at least one metal salt selected from the group consisting of zinc salts, calcium salts, lithium salts, thiocyanates and iron salts. Specific examples of the zinc salt include zinc bromide, zinc chloride and zinc iodide. Examples of the calcium salt include calcium bromide, calcium chloride and calcium iodide. Examples of the lithium salt include lithium bromide, lithium chloride, lithium iodide . Examples of the iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in terms of the solubility of the raw material polyketone and the homogeneity of the polyketone solution.

The concentration of the metal salt in the metal salt aqueous solution of the present invention is preferably 30 to 80% by weight. If the concentration of the metal salt is less than 30% by weight, the solubility decreases. If the concentration of the metal salt is more than 80% by weight, the cost for concentration increases, which is disadvantageous in terms of economy. As the solvent for dissolving the metal salt, water, methanol, ethanol and the like can be used. In particular, water is used in the present invention because it is economical and advantageous in solvent recovery.

In order to obtain a polyketone fiber having high strength and high fatigue resistance and dimensional stability as a core technical matter in the present invention, an aqueous solution containing zinc bromide is preferable, and the composition ratio of zinc bromide in the metal salt is an important factor. For example, in an aqueous solution containing only zinc bromide and calcium bromide, the weight ratio of zinc bromide to calcium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40. Further, in the aqueous solution containing zinc bromide, calcium bromide and lithium bromide, the total weight ratio of zinc bromide, calcium bromide and lithium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40, , The weight ratio of calcium bromide to lithium bromide is 40/60 to 90/10, preferably 60/40 to 85/15.

The production method of the polyketone solution is not particularly limited, but an example of a preferable production method will be described below.

The metal salt aqueous solution maintained at 20 to 40 캜 is defoamed at a pressure of 200 torr or less, the polyketone polymer is heated to 60 to 100 캜 under a vacuum of 200 torr or less, and stirred for 0.5 to 10 hours to prepare a sufficiently dissolved homogeneous dope .

In the present invention, the polyketone polymer may be mixed with other polymer materials or additives. Examples of the polymer material include polyvinyl alcohol, carboxymethyl polyketone, and polyethylene glycol. Examples of additives include viscosity improvers, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method of producing a polyketone fiber including spinning, washing, drying and stretching the homogeneous polyketone solution of the present invention will be described in more detail. However, the polyketone fibers claimed in the present invention are not limited by the following process.

The spinning process of the method according to the present invention will be described in more detail. An orifice having a diameter of 100 to 500 μm and a length of 100 to 1500 μm, wherein the ratio of the diameter to the length (L / D) is 1 to 3 to 8 times , And the spinning stock solution is extruded and spun through a spinning nozzle containing a plurality of orifices having an orifice spacing of 1.0 to 5.0 mm so that the fiber spinning solution passes through the air layer to reach the coagulation bath, .

The shape of the spinning nozzle used is usually circular, and the nozzle diameter is 50 to 200 mm, more preferably 80 to 130 mm. When the nozzle diameter is less than 50 mm, the distance between the orifices is too short, so that the adhesion may occur before the discharged solution solidifies. If the nozzle diameter is too large, peripheral devices such as spinning packs and nozzles become large, If the diameter of the nozzle orifice is less than 100 탆, a large number of yarn breaks occur at the time of spinning, which adversely affects the spinnability. If the diameter exceeds 500 탆, the coagulation speed of the solution in the spinning coagulating bath is slow, Solvent removal and washing become difficult.

The number of orifices is set to 100 to 2,200, more preferably 300 to 1,400, in consideration of the orifice spacing for uniform cooling of the solution, taking into account the geotext style in use.

If the number of orifices is less than 100, the fineness of each filament becomes thick and the solvent can not sufficiently escape within a short time, so that the coagulation and flushing can not be completely performed. If the number of orifices is more than 2,200, adjacent filaments are likely to form close-contact with each other in the air layer section, resulting in deterioration of the stability of each filament after spinning, resulting in deterioration of physical properties. .

When the fiber stock solution passing through the spinning nozzle coagulates in the upper coagulating solution, the larger the diameter of the fluid becomes, the larger the difference in the coagulation speed between the surface and the inside becomes, and it becomes difficult to obtain a dense and uniform tissue fiber. Therefore, when the polyketone solution is spun, even if the same discharge amount is maintained, the spun fibers having a smaller diameter can be obtained in the coagulating solution while maintaining an appropriate air layer.

The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. It is difficult to increase the spinning speed because the too short air layer distance increases the micropore generation rate due to the rapid surface layer coagulation and desolvation process, and it is difficult to increase the spinning speed. On the other hand, the too long air layer distance is affected by the adhesion of the filament, It is difficult to maintain process stability.

The composition of the coagulating bath used in the present invention is such that the concentration of the metal salt aqueous solution is 1 to 20% by weight. The coagulating bath temperature is maintained at -10 to 60 캜, more preferably -5 to 20 캜. In the coagulation bath, when the filament passes through the coagulation bath of the multifilament, when the spinning speed is increased by 500 m / min or more, the coagulation of the coagulating solution becomes severe due to the friction between the filament and coagulating liquid. In order to improve the productivity by increasing the excellent physical properties and the spinning speed through the stretching orientation, such a phenomenon is a factor that hinders the process stability, so that it is necessary to minimize such a phenomenon.

In the present invention, the coagulating bath is characterized by a temperature of -10 to 40 ° C and a metal salt concentration of 1 to 30% by weight, and the water bath is preferably at a temperature of 0 to 40 ° C and a metal salt concentration of 1 to 30% The acid washing bath preferably has a temperature of 0 to 40 캜 and an acid concentration of 0.5 to 2% by weight, and the secondary washing bath for acid removal is maintained at a temperature of 30 to 70 캜.

Also, in the present invention, the temperature of the dryer is 100 ° C or higher, preferably 200 ° C or higher, and the emulsion, heat-resistant agent, antioxidant or stabilizer is added to the fiber passed through the dryer.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance.

Hereinafter, the stretching process and drying method important in the present invention will be described.

The present invention provides a high-strength fiber by securing the heat stability of the polyketone during wet spinning and by directly drying the fiber. In the conventional spinning process, the maximum strength is 13 g / d even at the time of germination drying and optimization of the stretching temperature. However, the present invention optimizes the heating method and the temperature profile of the drying method to form a dense structure by fusion- As a result, the draw ratio and the strength are improved. Further, in order to prevent thermal deterioration of the polyketone at the time of heating, the stretching magnification and strength are improved by a process including a heat stabilizer during drying and stretching.

Polyketone fibers have oxidation or degradation mechanisms at high temperatures. As a radical oxidation mechanism, polyketone releases carbon dioxide and oxidative degradation occurs when exposed to oxygen at temperatures above 90 ° C. In addition, due to the radical deterioration mechanism, when the polyketone is exposed to a high temperature of 200 ° C or more, carbon monoxide and ethylene are released and thermal degradation occurs. A heat-resistant stabilizer is used to prevent oxidation and deterioration of the polyketone at such a high temperature. As the heat-resistant stabilizer, both of antioxidants capable of preventing radical oxidation and deterioration can be used.

Preferably, phenolic heat stabilizers are used, and one or more heat stabilizers may be used alone or in combination. Oxidation and deterioration prevention mechanisms prevent radicals by radicals by capturing radicals with heat stabilizers (alkyl radicals) generated by heat or ultraviolet rays (see FIG. 1). The heat stabilizer may be used before drying or before stretching, and the immersion or application method may be used alone or in combination. Specifically, in an embodiment of the present invention, 0.1% of a solution of a phenolic heat stabilizer prepared by mixing a phenolic heat stabilizer with a methanol solvent in a pre-drying step and a stretching step is applied in a pre-drying step and a drawing step, Of the heat stabilizer was 250 ppm, but after the drying and the stretching step, 25 ppm remained. The heat stabilizer should be used in an appropriate amount depending on the process. If the heat stabilizer is large, the workability is poor. If the heat stabilizer is small, the heat stabilization effect is not sufficient. The heat stabilizer may be used in one-pot or two-pot or more.

Meanwhile, in order to increase the strength of the fiber, the present invention uses a direct drying method of a hot roller drying method, rather than an indirect drying method of a hot air drying method. In the conventional hot air drying method, a hot air drying method as shown in FIG. 2 was used at a temperature of 180 ° C. for a retention time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the affixation, but it is difficult to generate fusion, loops, static electricity, and fusion structure, so that the structure is not as dense (see FIG. 4). The present invention uses a hot-roll drying method as shown in Fig. 3 for a retention time of about 1 minute and 30 seconds at a temperature of 220 to 230 ° C. When such a drying method is used, there is no entanglement, less static electricity is generated, and a fine structure is formed due to the formation of a fusion structure, which is easy to apply for commercialization (see FIG. 5).

In addition, the present invention is subjected to a stretching process in which the fibers are stretched 15 to 18 times. For stretching the polyketone fibers, stretching is carried out in one or more stages. In the case of multi-stage stretching, it is preferable to perform the temperature-raising stretching in which the stretching temperature gradually increases with an increase in the stretching magnification. Specifically, the stretching process is performed at a temperature of 240 to 270 ° C, and the residence time is within about 1 minute and 30 seconds, and the first and second stages are performed. Stretching is carried out from step 1 to step 7, second step to step 2.5, and step 2 is stepwise stretching in a 3 step form. After the first stage, the elongation of the polyketone fibers is 10% and the strength is 8 g / d. After the second stage, the elongation is about 5.2%, and the strength of the polyketone fibers is 20 g / d.

In addition, since the polyketone is thermally deteriorated at a high temperature due to the drying and stretching processes described above, a heat stabilizer is added. It is applied before drying or before stretching. In the present invention, both raw or dip can be used. In general, when the two-dip or more is performed, the elongation of the fiber is decreased independently of the increase in the strength, but in the case of the hot-roll drying method according to the present invention, there is little decrease in elongation.

The multifilament produced by the method according to the present invention is a polyketone multifilament with a total denier range of 500 to 3,500 and a breaking load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2,200 individual filaments with a fineness of 0.5 to 8.0 denier.

The fiber density of the monofilament is 1.295 to 1.310 g / cm < 3 > by the hot-roll drying method of the present invention and the step of adding the heat stabilizer, and the structure thereof is as shown in Fig. As a result, the initial modulus value of the polyketone monofilament prepared by the above process is 200 g / d or more, elongation at 2.5 g / d at 2.5 g / d and elongation at least 0.5% at 19.0 g / d or more.

The polyketone fibers produced by the present invention can be made in a geotextile style.

Hereinafter, a method of manufacturing a geotextile according to the present invention will be described in detail.

The method of manufacturing a geotextile according to the present invention comprises the steps of: forming a web with a polyketone filament manufactured as described above; And combining the formed webs.

On the other hand, a method using an embossing roll for high temperature heat treatment may be used for increasing the bonding strength to the web.

When heat bonding is performed by a high-temperature heat-treated embossing method using a high-temperature embossing roll to form a nonwoven web, crossing portions where the filaments intersect or portions to be bonded by embossing are strongly adhered, . In this case, the temperature applied by the hot embossing roll is in the range of 160 to 280 ° C. When the temperature is lower than 160 ° C, there is a fear that the binding force of the web becomes insufficient. When the temperature exceeds 280 ° C, May be destroyed.

On the other hand, the operation speed of the high-temperature embossing roll is preferably 20 to 80 m / min. If the operation speed is less than 20 m per minute, the weight of the web becomes high and workability and flexibility may be poor when combined with the drainage core material for vertical drainage If it exceeds 80 m per minute, the weight of the web may be lowered and the mechanical strength may be inferior.

Needless to say, in the present invention, the bonding strength of the nonwoven web can be increased by using the conventional needle punching method.

In addition, in the present invention, a binder aqueous suspension treatment may be performed to impart mechanical strength reinforcement, shape stability, and hydraulic characteristics to a thermally bonded or binder bonded web, or a web not subjected to the binder bonding, Is about 5 to 20 parts by weight based on 100 parts by weight of the non-woven fabric.

Examples of the binder usable in the present invention include polyacrylate esters, acrylic styrene copolymers, polyvinyl acetate, vinyl acetate ethylene copolymer, vinyl ethylene chloride copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl alcohol , Polyvinyl acetate, polyurethane, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, vinyl pyridine rubber and chloroprene rubber. If the content of the binder in the aqueous binder suspension is too small, it is difficult to obtain sufficient mechanical strength. On the other hand, if the binder content is excessively large, flexibility and workability of the web may be deteriorated, which is an optional matter in the present invention.

In addition, the binder suspension may be supplemented with an emulsifier or an antimicrobial agent, preservative, wetting agent, hardener or the like. For example, the curing agent is preferably a urea-based curing agent, and when added, the amount thereof is 3 parts by weight or less based on 100 parts by weight of the nonwoven fabric.

When the binder suspension is used, it can be applied to at least one side of the nonwoven fabric by a known method such as a floating knife such as an air knife, a comma coated knife, a roll coater, a gravure, a screen and the like.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example 1

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 30 캜 at an injection temperature of 25 캜 by a gear pump at a rate of 13,000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C and operating the screw at 110 rpm.

At this time, a circular nozzle having an odd number of nozzles of 667 and a diameter of 0.18 mm and an L / D of 1 was used, and an air gap was 10 mm. The concentration of the polyketone in the discharged solution was 8.2% by weight, and it was in a homogeneous state free of undissolved polyketone particles.

The fiber thus obtained is subjected to stretching at 1.2 times in the course of washing, and the heat stabilizer is dipped in a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer before drying. In the drying process, 1.2-fold stretching was performed by a hot-roll drying method, and then fibers were produced in a heating chamber method at a total stretching magnification of 16.8 times, stretched at a stretch ratio of 7 times at the first stretch, 2.4 times at the second stretch, 1.5, 1.3, and 1.23 times, and each step is performed at temperatures of 240, 255, 265, and 268 ° C.

A polyketone geotextile of 800g / in was prepared by heat treatment at 200 ° C with a high temperature heat-treated embossing roll at an operating speed of 35m / min to form a web of polyketone fibers obtained from the above process.

Example 2

except that the temperature of each step of the first and second steps in the heating chamber type stretching was adjusted to 240, 250, 260 and 268 캜.

Example 3

except that the temperature of each step of the first and second stages in the heating chamber type stretching was adjusted to 240, 255, 265, and 272 캜, respectively.

Example 4

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 30 캜 at an injection temperature of 25 캜 by a gear pump at a rate of 13,000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 5.7 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C and operating the screw at 110 rpm.

Example 5

The same as Example 4 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 / g.

Example 6

And the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 / g.

Example 7

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 30 캜 at an injection temperature of 25 캜 by a gear pump at a rate of 13,000 g / hour to obtain a polyketone powder having a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C and operating the screw at 110 rpm.

A polyketone geotextile of 800 g / in was prepared by heating the web at 200 ° C with a high temperature heat-treated embossing roll at an operating speed of 35 m / min to form a web of polyketone fibers obtained through the above process.

Example 8

The same as Example 7 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 9

And the molecular weight distribution of the polyketone polymer was adjusted to 3.5.

Example 10

The procedure of Example 1 was repeated except that a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer was subjected to 1 dip before drying.

Example 11

Example 1 was the same as Example 1 except that a 0.1% solution of AO80 and methanol of Adeka Co. as a phenolic heat stabilizer was subjected to two dipping before drying and before drawing.

Comparative Examples 1 to 3

The same procedure as in Example 1 was carried out except that polyester was used in the production of the geotextile, the stretching ratio in the washing step was 1.0 times, and the hot-air drying method was used instead of the hot-roll drying method. Respectively.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Hot air dryer temperature (캜) 240 260 280 The stretching ratio (times) 1.0 times 1.0 times 1.0 times

Property evaluation

(1) intrinsic viscosity

0.1 g of the sample was dissolved in a reagent (90 ° C) mixed with phenol and 1,1,2,2-tetrachloroethanol 6: 4 (weight ratio) for 90 minutes, transferred to a Ubbelohde viscometer, For 10 minutes, and use a viscometer and an aspirator to determine the number of drops of the solution. The number of drops of solvent The RV value and the IV value were calculated by the following equation obtained by the same method as described above

R.V. = Sample falling water / solvent falling water water

I.V. = 1/4 x [(R.V.- 1) / C] + 3/4 x (In R.V./C)

In the above equation, C represents the concentration (g / 100 ml) of the sample in the solution.

(2) Molecular weight distribution

A polyketone was dissolved in a hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate so as to have a polyketone concentration of 0.01% by weight and measured under the following conditions.

Device: SHIMADZU LC-10Advp

Column: Use the following columns in the order of (a), (b) and (c).

(A): Shodex GPCHFIP-G

(B): Shodex HFIP-606M

(C): Shodex HFIP-606M

Column temperature: 40 ° C

Mobile phase: hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate

Flow rate: 0.5 ml / min

Detector: differential refractometer

Injection volume: 30 μl

As a standard sample, polymethyl methacrylate (PMMA) having a monodispersed molecular weight distribution was used (concentration: 0.01% by weight), and the weight of the polyketone in terms of PMMA measured from the calibration curve of PMMA obtained under the same conditions as the above- The average molecular weight (Mw) and the number average molecular weight (Mn) were determined, and Mw / Mn was determined as a molecular weight distribution.

(3) Method of measuring modulus and strength

The yarn is left in a standard temperature condition, that is, in a constant temperature and humidity room at a temperature of 25 ° C and a relative humidity of 65% for 24 hours, and then the sample is measured by a tensile tester by ASTM 2256 method. The physical properties of the samples were measured by the average of the remaining eight values, excluding the maximum and minimum values, respectively, of the ten values measured from the ten samples. The initial modulus represents the slope of the graph before the yield point.

(4) The strength (g / d), elongation (%) and modulus (g / d)

24 monofilaments were extracted from the yarn (multifilament) which was allowed to stand for 24 hours at a temperature of 25 ° C. and a relative humidity of 55 RH%. The monofilament tensile tester Vibrojet 2000 manufactured by Lenzing Corporation was used to measure the dewar load in the Vibrojet (Mono-denier x50 (mg)) is added, and the sample is measured at a length of 20 mm and a tensile strength of 20 / min. The monofilament properties were measured by the average of the 22 values obtained by excluding the maximum value and the minimum value, respectively, out of the 24 values measured. The initial modulus represents the slope of the graph before the yield point.

A kite Multi-filament properties Monofilament properties Strength (g / d) Shinto (%) Toughness Initial modulus (g / d) 10.0g / d Elongation (%) when stressed 19.0g / d ~ Elongation (%) when stressed to cut Example 1 20.75 5.9 53.54 220 2.4 1.8 Example 2 21.00 5.6 54.02 280 2.5 2.1 Example 3 20.84 5.7 53.65 205 2.3 1.7 Example 4 19.95 6.3 52.95 250 2.9 2.0 Example 5 20.55 6.0 53.55 290 3.1 1.0 Example 6 20.13 6.1 53.13 212 2.8 1.4 Example 7 19.74 6.3 52.74 210 2.7 1.2 Example 8 20.87 5.7 53.87 230 3.2 1.3 Example 9 20.14 6.1 53.14 220 3.1 1.3 Example 10 20.20 6.0 53.20 260 3.4 1.4 Example 11 21.04 5.6 54.04 230 2.8 1.2 Comparative Example 1 6.8 4.9 41.18 210 3.1 0 Comparative Example 2 7.2 4.7 40.13 200 3.2 0 Comparative Example 3 6.6 5.0 40.19 215 3.0 0

As shown in Table 2, the geotextile including the polyketone fibers manufactured by the embodiments of the present invention has excellent elongation and strength and is excellent in toughness, and thus is suitable for use in a geotextile style.

Claims

A polyketone copolymer composed of the repeating units represented by the following general formulas (1) and (2) and having an y / x of more than 0 and not more than 0.1 and an intrinsic viscosity of 5 to 7 dl / g is subjected to a spinning process, Wherein the monofilament has an initial modulus value of at least 200 g / d, an elongation at 2.5 to 3.5% at 10.0 g / d and a polyketone length of at least 0.5% at 19.0 g / d or more, A polyketone geotextile characterized by containing fibers.
- [- CH2CH2-CO-] x- (1)
- [- CH2 --CH (CH3) - CO--] y- (2)
(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

The method according to claim 1,
Wherein the polyketone geotextile comprises forming a web with the polyketone fibers; And combining the formed web with the polyketone geotextile.

delete

The method according to claim 1,
Wherein the polyketone fiber monofilament has a fineness of 0.5 to 8.0 denier.

The method according to claim 1,
Wherein the stretching is 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step.

The method according to claim 1,
Wherein the drying step is hot-rolled at 100 to 230 ° C, and the stretching step is a heating chamber stretching method at 230 to 300 ° C.

The method according to claim 1,
Characterized in that the heat stabilizer is treated before the drying step and the stretching step.

The method according to claim 1,
Wherein said polyketone fibers have a strength of at least 15 g / d.