WO2016190596A2 - Industrial polyketone product comprising polyketone fibers and method for manufacturing same - Google Patents

Abstract

The purpose of the present invention is to provide polyketone fibers having excellent strength and water resistance, which are manufactured from a polyketone solution prepared from a copolymer of carbon monoxide, ethylene, and propylene, and a manufacturing method therefor. The industrial polyketone fibers manufactured according to the present invention have excellent strength, elongation, water resistance, heat resistance, and thermal conductivity, and thus are suitable for the use for marine ropes, hoses, protective products, Geotextile, fibers for enhancing FRP composite materials, cables, fishing nets, air bags, heat insulators, seat belts, safety nets, roung sling, flying film materials, non-woven fabrics, spun bonds, conveyor belts, flexible containers, fishing lines, sports cords, carbon fiber composite materials, longlines, carpets.

Description

Industrial polyketone industrial products containing polyketone fibers and manufacturing method thereof

The present invention provides a bulletproof garment, a bulletproof helmet, a debris protection material, a polyketone bulletproof material for an aircraft or a military aircraft, an aircraft wing tip device, a helicopter interior material, including a polyketone fiber having a markedly improved shock absorption performance and excellent mechanical properties and work performance. Automotive structural materials, marine platforms, submersible structural materials, fiber optic cable coverings, radar dome structural materials, bobbins of superconducting coils, cryogenic superconducting cables, skiboards, wires for tennis rackets, yacht structural materials, yacht sails, racing bicycles, parachute or paragliding poly It relates to a polyketone industrial product that can be used as ketone coated fabrics, safety gloves and the like.

Bulletproof clothing, bulletproof helmets, debris protection materials, polyketone bulletproof materials for aircraft or military aircraft, aircraft wingtip devices, helicopter interior materials, automotive structural materials, ship platforms, submersible structural materials, optical cable sheathing materials, radar dome structural materials, bobbins of superconducting coils, cryogenic superconductivity In various industries, such as cables, skiboards, wires for tennis rackets, yacht structures, yacht sails, racing bicycles, polyketone-coated fabrics for parachute or paragliding, safety gloves, etc. However, since each material does not satisfy all of the various functions to be equipped as a number of industrial fibers, it is used to determine the use according to the unique properties of each material. The basic performance of the reinforcing fiber required for the industry includes high strength, high elongation, vibration and high impact resistance, heat resistance, not deterioration in dry and wet heat, bending resistance, shape stability, and adhesion to rubber. There is a need for excellent, light weight, excellent mechanical properties, and the like, and there is an increasing demand for developing an industrial fiber having such performance and being widely used in various fields.

On the other hand, polyketones having a structure in which a repeating unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated compound are alternately connected are excellent in mechanical properties and thermal properties, have high wear resistance, chemical resistance, gas barrier property, and various fields. The development of is expected. For example, polyketone is a material useful as a high strength, high heat resistant resin, fiber, or film. In particular, when a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more is used as a raw material, fibers or films having very high strength and elastic modulus can be obtained. Such fibers and films are expected to be widely used for construction materials and industrial materials, such as rubber reinforcements such as belts, hoses and tire cords, protective articles, ropes and concrete reinforcements.

It is known that when carbon monoxide and olefins such as ethylene and propylene are polymerized using a transition metal complex such as palladium or nickel as a catalyst, an alternating polyketone of carbon monoxide and olefins is obtained.

Since polyketone is easy to thermally crosslink when melted, it is preferable to use wet spinning when fiberizing. In particular, polyketone (poly (1-oxotrimethylene)) fibers containing substantially only carbon monoxide and ethylene, which have excellent physical properties, are susceptible to thermal crosslinking. Thus, this fiber is very difficult to produce by melt spinning and can only be obtained substantially by wet spinning.

In the case of wet spinning polyketones, solvents used are hexafluoroisopropanol and m-cresol, phenolic solvents such as resorcinol / water, and organic solvents such as resorcinol / carbonate (Japanese Patent Laid-Open). (Japanese Patent Application Laid-Open No. 2-112413, Japanese Patent Application Laid-Open No. 4-228613, and Japanese Patent Application Laid-open No. Hei 7-508317). However, fibers obtained by wet spinning using such solvents are likely to be dispersed, and have insufficient fatigue resistance and processability for use as industrial materials. In addition, such solvents are highly toxic and flammable, and there is a problem in that extensive measures for the toxicity and flammability of the solvent are required to make industrial-scale spinning equipment.

A method of spinning using a polyketone solution prepared by dissolving polyketone in an aqueous solution containing zinc halides such as zinc chloride and zinc bromide or lithium salts such as lithium chloride, lithium iodide, lithium thiocyanate, etc. Is proposed (WO99 / 18143, USP5955019). These aqueous solutions are relatively inexpensive, less toxic and nonflammable and are excellent solvents for polyketones.

In order to solve the above problems, the present invention includes a polyketone copolymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, and before stretching in the manufacturing process of the multifilament, hot roll drying method and heat stabilizer It is an object of the present invention to provide a polyketone industrial product having excellent strength.

In order to achieve the above object, the present invention consists of a repeating unit represented by the following general formula (1) and (2), y / x is 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Bulletproof clothing, bulletproof helmets, debris protection material, polyketone bulletproof material for aircraft or military aircraft, aircraft wing tip, characterized in that the ketone copolymer comprising a polyketone fiber produced by spinning, washing, drying, and stretching processes Device, Helicopter Interior, Automobile Structural Materials, Ship Platform, Submersible Structural Materials, Optical Cable Cladding, Radar Dome Structural Materials, Bobbins of Superconducting Coils, Cryogenic Superconducting Cables, Skiboards, Wires for Tennis Rackets, Yacht Structural Materials, Yacht Sails, Racing Bikes, Parachuting Or it provides a polyketone fiber product selected from the group consisting of polyketone coating fabric, safety gloves for paraglide.

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

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

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

At this time, the stretching step is 1.0 times to 2.0 times the stretching process, the drying process is characterized in that the stretching is 1.0 times to 2.0 times, the drying process is hot roll dry type at 100 to 230 ℃, the stretching process is 230 It is characterized in that the heating chamber (heating chamber) stretching formula at 300 ℃, the heat stabilizer before the drying process and stretching process.

Polyketone bulletproof clothing is characterized in that it is produced by weaving the fabric in plain weave using polyketone fibers, and then treated with a surfactant, washed with water and dried.

The polyketone bulletproof clothing is 20 to 35 parts by weight of dipropylene glycol, 0.5 to 5.5 parts by weight of silicone oil, relative to 100 parts by weight of hardoxylated perfluoroalkylethyl acrylate copolymer. Isopropyl alcohol (isopropylalcohol) is characterized in that it is prepared through a manufacturing step further comprising the step of immersing in a water repellent consisting of 0.5 to 10 parts by weight.

In addition, the polyketone bulletproof clothing is characterized in that the bulletproof performance (V50) is 590 to 700m / s on the basis of 5.56mm fragmented coal (FSP).

In addition, the polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5,

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

The polyketone bulletproof helmet is manufactured by applying polyketone fibers to warp and weft yarns and weaving them in plain weave, and then applying a pressure in the chamber by adhering thermoplastic or thermosetting resins, and then laminating and curing the lower mold for helmet manufacturing. It is done.

At this time, the polyketone bulletproof helmet had an average speed (V50) of 590 to 700 kPa measured according to MIL-STD-662F regulation, and the average speed was completely penetrated using Cal. 22-caliber fragmentation bullet (FSP). It was measured from the average value of the speed at the time and the speed at the time of partial penetration.

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

The monofilament of the polyketone fiber is characterized in that the fineness of 0.5 to 8.0 denier.

Polyketone fragment protection material is characterized in that the polyketone multifilament is impregnated in the elastic matrix stock solution, to obtain an elastic sheet, laminated, heated and pressurized, bulletproof performance (V50) 5.56mm fragmentation bullet (FSP) is characterized in that the 590 to 700m / s.

In addition, the molar ratio of ethylene and propylene of the polyketone copolymer of polyketone fragment protection material is 100: 0 to 90:10, molecular weight distribution is 2.5 to 3.5,

The polyketone multifilament is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

Polyketone anti-ballistic material for aircraft or military aircraft is characterized by being produced by weaving polyketone fibers to cut the fabric mat and then laminated and put into a liquid resin molding apparatus to form a molded product and cut it in a predetermined length and width direction.

At this time, the aircraft or military aircraft polyketone bulletproof material is characterized in that the bulletproof performance (V50) is 590 to 700m / s based on 5.56mm fragmented coal (FSP), the molecular weight distribution of the polyketone copolymer is 2.5 to 3.5 ,

The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine).

At this time, the polyketone multifilament of the polyketone bulletproof material for aircraft or air conditioner has an initial modulus value of 200g / d or more, elongation of 2.5 to 3.5% at 10.0g / d, elongation of at least 0.5% at 19.0g / d or more ,

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

The polyketone aircraft wing tip device is manufactured by applying polyketone multifilament to warp and weft yarns to make plain weaves, impregnating them into an elastic matrix stock solution, and then laminating them on a wing tip manufacturing mold to bond them with thermoplastic or thermosetting resins to heat and press. Characterized in that,

The polyketone multifilament has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, and monofilament of 0.5 to 8.0 denier It is characterized by that.

The polyketone helicopter interior material is produced by applying the polyketone multifilament to the warp and weft yarn is made of plain weave, laminated to a mold and bonded with a thermoplastic or thermosetting resin, characterized in that it is produced by heating and pressing,

The molecular weight distribution of the polyketone copolymer of the polyketone helicopter interior material is 2.5 to 3.5,

The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine).

At this time, the polyketone multifilament has an initial modulus value of 200g / d or more, elongation of 2.5 to 3.5% at 10.0g / d, elongation of at least 0.5% at 19.0g / d or more,

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

Polyketone automotive structural material is characterized in that the polyketone filament is applied to warp and weft yarn and woven into a plain weave, then bonded by thermoplastic or thermosetting resin to apply pressure in the chamber, and then laminated to the mold and cured.

At this time, the polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5,

The polyketone multifilament is characterized in that the monofilament has a fineness of 1 to 10d, the cross-sectional variation rate index is 8 to 15%.

Polyketone ship platform is a frame installed on one side of the vessel to be movable in the outward direction from the inside of the vessel;

A body coupled to the frame; In the ship platform consisting of,

The body is composed of a repeating unit represented by the following general formula (1) and (2), spinning process, water washing a polyketone copolymer of y / x 0 to 0.1, intrinsic viscosity 4 to 8 dl / g It characterized in that it comprises a polyketone fiber produced through a process, drying process and stretching process.

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

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

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

At this time, the polyketone ship platform is characterized in that the strong maintenance rate of 70 to 90% immersion for 24 hours at room temperature in 15L of chlorine water of 3ppm active chlorine concentration, pH 7.5.

In addition, the monofilament of the polyketone fibers has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more,

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

The polyketone submersible structural material is manufactured by injecting polyketone multifilament together with a foam foam into a manufacturing mold, and heating and pressing to foam the foam.

The molecular weight distribution of the polyketone copolymer is 2.5 to 3.5,

The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine).

In addition, the polyketone multifilament has an initial modulus value of 200g / d or more, elongation of 2.5 to 3.5% at 10.0g / d, elongation of at least 0.5% at 19.0g / d or more,

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

Polyketone optical cable coating material is characterized in that the moisture absorption rate according to the following general formula (3) measured after drying for 30 minutes at 105 ℃.

General formula (3) moisture absorption rate = (mass after absorption-mass before absorption) / (mass before absorption)

At this time, the polyketone multifilament has an initial modulus value of 200g / d or more, elongation of 2.5 to 3.5% at 10.0g / d, elongation of at least 0.5% at 19.0g / d or more, the polyketone monofilament Is characterized in that the fineness of 0.5 to 8.0 denier.

The polyketone radar dome structure material is manufactured by applying the polyketone fibers to warp and weft yarns and weaving them in plain weave, then applying a pressure in a chamber by adhering a thermoplastic or thermosetting resin, and then laminating and curing the mold. do.

In this case, the polyketone multifilament is characterized in that the initial modulus value is more than 200g / d, elongation is 2.5 to 3.5% at 10.0g / d, elongation of at least 0.5% at 19.0g / d or more.

In addition, the stretch in the washing step 1.0 times to 2.0 times, the drying process is characterized in that stretching to 1.0 times to 2.0 times.

The bobbin of the polyketone superconducting coil is manufactured by applying polyketone fibers to warp and weft yarns and weaving them in plain weave, and then applying a pressure in the chamber by bonding thermoplastic or thermosetting resins, and then laminating them in the lower mold for manufacturing bobbins to manufacture them It is characterized by.

The polyketone copolymer of the bobbin of the polyketone superconducting coil has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5,

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

In addition, the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxy Phenyl) phosphine),

The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5,

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

The skiboard is manufactured by forming a curved surface by laminating polyketone fibers and thermoplastic resin or thermosetting resin by thermocompression, then pressing and warming and pressing through a press.

The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5,

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

The polyketone fiber multifilament of the wire for tennis rackets is characterized by consisting of 100 to 2200 individual filaments with a total denier range of 500 to 3,500 and a fineness of 5 to 16 deniers with a cutting load of 6.0 to 40.0 kg.

At this time, the initial modulus of the monofilament of the polyketone fiber is 200g / d or more, elongation is 2.5 to 3.5% at 10.0 g / d, characterized in that elongation of at least 0.5% or more at 19.0g / d or more. .

The yacht structural member is manufactured by laminating a polyketone fiber and a thermoplastic resin or a thermosetting resin, followed by thermocompression, then cutting and warming and pressing through a press to form a curved surface.

At this time, the molar ratio of ethylene and propylene constituting the polyketone copolymer of the polymethone fiber is 100: 0 to 90:10, the molecular weight distribution of the copolymer is 2.5 to 3.5,

The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine).

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

Polyketone yacht sails weaving the polyketone fibers into a fabric; And

It characterized in that it comprises a coating on the fabric using a coating agent.

The bicycle for racing made of polyketone fibers comprises the steps of laminating the polyketone fibers and a thermoplastic resin to form a laminate; And

It characterized in that the manufacturing including the step of heating and pressing the laminate.

At this time, the heating is carried out at a temperature of 150 to 220 ℃, the press is characterized in that carried out by applying a pressure of 5 to 20MPa for 10 to 20 minutes.

The monofilament of racing bicycle polyketone fibers has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more,

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

The polyketone coated fabric for parachute or paraglide comprises the steps of: weaving plain weave fabric using polyketone fibers as warp and weft yarns; And manufacturing a coating fabric by coating the thermoplastic polyurethane resin on both sides of the fabric.

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

The polyketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

Polyketone copolymer of polyketone safety gloves is made of ethylene, propylene, the molar ratio of the ethylene and propylene is from 100: 0 to 90:10,

The polyketone fiber is characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate is 8 to 15%.

The polyketone safety gloves are characterized in that the strength is more than 15g / d, the molecular weight distribution of the polyketone copolymer is characterized in that 2.5 to 3.5.

Safety protective shoes are characterized in that the rubber sheet and the polyketone fibers are laminated and pressed to form a sole, and then put them in a mold together with the upper and molded at the same time in the mold.

In addition, the monofilament of the safety protective shoes polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, the poly Ketone monofilament is characterized in that the fineness of 0.5 to 8.0 denier.

Preparing a polyketone solution by injecting an aqueous metal salt solution and polyketone into an extruder to dissolve the polyketone solution;

Filtering the polyketone solution through a disk filter to remove impurities; And

It provides a method for producing a polyketone fiber using a disk filter comprising the step of producing a polyketone fiber through a spinning process, water washing process, drying process and stretching process.

In addition, the polyketone is a catalyst composition comprising a Group 9, Group 10 or 11 transition metal compound, a ligand comprising an element of Group 15 and an anion of an acid having a pKa of 4 or less; And polymerizing carbon monoxide and an ethylenically unsaturated compound in the presence of a mixed solvent.

In addition, the stretch in the water washing step is 1.0 times to 2.0 times, characterized in that the stretching process in the 1.0 times to 2.0 times.

At this time, the drying process is a hot roll dry type at 100 to 230 ℃, the stretching process is characterized in that the heating chamber (heating chamber) stretching at 230 to 300 ℃.

In addition, the heat-resistant stabilizer is characterized in that before the drying step and the stretching step.

The present invention is to prepare a polyketone solution from carbon monoxide, ethylene and propylene copolymers, and to provide a polyketone industrial product having excellent strength and water resistance from the polyketone solution.

1 is a view schematically showing a candle filter according to the prior art.

2 is a view schematically showing a disk filter according to the present invention.

3 is a view schematically showing the upper end of the candle filter and the disk filter.

4 is a view schematically showing a role of a heat stabilizer according to the prior art.

5 is a view of a schematic diagram of a hot air drying type dryer according to the prior art.

6 is a schematic view of a hot roll drying method according to the present invention.

7 is a cross-sectional view of the dry yarn according to the prior art hot air drying method.

8 is a cross-sectional view of the dry yarn according to the hot roll drying method of the present invention.

9 is a view schematically showing a disk filter according to the present invention.

The present invention comprises the steps of preparing a polyketone solution by dissolving a metal salt aqueous solution and polyketone in an extruder; Filtering the polyketone solution through a disk filter to remove impurities; And it provides a method for producing a polyketone fiber using a disk filter, characterized in that it comprises a step of producing a polyketone fiber through a spinning process, water washing process, drying process and stretching process.

At this time, the polyketone is a catalyst composition comprising a Group 9, Group 10 or 11 transition metal compound, a ligand containing an element of Group 15 and an anion of an acid having a pKa of 4 or less; And it is preferably prepared by polymerizing carbon monoxide and ethylenically unsaturated compounds in the presence of a mixed solvent, but is not limited thereto.

Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g It provides a polyketone industrial fiber comprising a polyketone fiber produced through a process and stretching process.

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

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

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

In addition, the stretch in the water washing step is 1.0 times to 2.0 times, the stretching process is characterized in that the stretching is 1.0 times to 2.0 times.

In addition, the drying process is a hot roll dry type at 100 to 230 ℃, the stretching process is preferably a heating chamber (heating chamber) stretching at 230 to 300 ℃.

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.

The monomer units are alternating, so that the polymer is composed of one or more olefinically unsaturated compounds (simplified as A), wherein the polymer consists of units of the formula-(CO) -A'- where A 'represents a monomeric unit derived from monomer A applied. High molecular weight linear polymer of carbon monoxide can be prepared by contacting a monomer with a palladium-containing catalyst composition solution in a diluent in which the polymer is insoluble or not actually dissolved. During the polymerization process, the polymer is obtained in the form of a suspension in diluent. Polymer preparation is mainly carried out batchwise.

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

In the present invention, as a liquid medium, not only methanol, dichloromethane or nitromethane, which have been mainly used in the production of polyketone, but also a mixed solvent of acetic acid and water, ethanol and propanol, and isopropanol can be used. In particular, when a mixed solvent of acetic acid and water is used as the liquid medium in the production of the polyketone, it is possible to improve the catalytic activity while reducing the production cost of the polyketone. In addition, since the use of methanol or dichloromethane solvents forms a mechanism for causing a stop reaction during the polymerization step, the use of acetic acid and water in the solvent except for methanol or dichloromethane does not have the effect of stopping the catalytic activity. Plays a huge role in improvement.

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

In the present invention, the organometallic complex catalyst contains (a) Group 9, Group 10 or Group 11 transition metal compound of the periodic table (IUPAC inorganic chemical nomenclature revision, 1989), and (b) Group 15 elements. Ligands, and (c) anions of acids with a pKa of 4 or less.

Examples of the Group 9 transition metal compound among Group 9, Group 10 or Group 11 transition metal compounds (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonic acid ruthenium.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, and palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.

Examples of the Group 11 transition metal compound include a complex of copper floating silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, Trifluoro silver acetate, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, and in terms of improving catalytic activity and intrinsic viscosity. Palladium acetate is most preferably used.

Examples of the ligand (b) having a group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2-bi-4-picolin, 2,2 Nitrogen ligands such as bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3 -Bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl) phosphino] propane , 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2-bis [[di ( 2-methoxy-4-sulfonic acid-phenyl) phosphino] methyl] benzene, 1,1-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) fo Phosphorus ligands, such as a spino] propane, are mentioned.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane.

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

[Formula 1]

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((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst, while maintaining the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in bulk.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding and stirring methanol 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 is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be carried out by obtaining a step.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used may be limited, since the appropriate value varies depending on the type of ethylenically unsaturated compound selected or other polymerization conditions. Although it is not possible, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase of the reactor.

Examples of the anion (c) of an acid having a pKa of 4 or less include anions of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethane sulfonic acid, p-toluene sulfonic acid, and m-toluene sulfonic 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 preferred anion (c) of an acid having a pKa of 4 or less in the present invention is p-toluene sulfonic acid, which has a high catalytic activity when used with a mixed solvent of acetic acid and water as a liquid medium, as well as a ship rope. It is possible to produce polyketones having a suitable high intrinsic viscosity.

The molar ratio of the ligands having the (a) Group 9, 10 or 11 transition metal compound and (b) Group 15 element is 0.1 to 20 moles of Group 15 element of ligand per mole of palladium element, preferably Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added less than 0.1 mole relative to the elemental palladium, the binding force between the ligand and the transition metal is lowered to accelerate the desorption of palladium during the reaction, and the reaction is terminated quickly, and the ligand exceeds 20 moles relative to the elemental palladium. When added, the ligand may cause a screening effect on the polymerization reaction by the organometallic complex catalyst, which may cause a disadvantage that the reaction rate is significantly lowered.

The molar ratio of (a) the Group 9, 10 or 11 transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 moles, preferably 0.1 to 10 moles of acid per mole of palladium element. Moles, more preferably from 0.1 to 5 moles are added. If the acid is added less than 0.1 mole relative to the elemental palladium, the effect of improving the intrinsic viscosity of the polyketone is not satisfactory, and if the acid is added more than 20 mole relative to the elemental palladium, the catalyst activity for polyketone production tends to be rather reduced, which is undesirable. not.

In the present invention, the reaction gas to be reacted with the polyketone production catalyst is preferably used by appropriately mixing carbon monoxide and ethylenically unsaturated compounds.

In the present invention, examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1 C2-C20 α-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; C2 to C20 alkenyl aromatic compound including styrene and (alpha) -methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra C4 to C40 cyclic olefins including cyclododecene; C2 to C10 vinyl halides including vinyl chloride; Any one or a mixture of two or more selected from C3 to C30 acrylic esters including ethyl acrylate and methyl acrylate may be selected and used. These ethylenically unsaturated compounds are used individually or in mixture of multiple types. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketone, the ratio of carbon monoxide to ethylenically unsaturated compound is generally 1: 1, but in the present invention, the ratio of carbon monoxide to ethylenically unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1. It is preferable. When the ethylenically unsaturated compound and carbon monoxide are mixed and used in an appropriate ratio as in the present invention, it is effective in terms of catalytic activity, and the effect of improving the intrinsic viscosity 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 may be lowered and the physical properties of the manufactured polyketone may be deteriorated.

On the other hand, the polyketone copolymer used as the fiber may be composed of ethylene, propylene and carbon monoxide. As the molar ratio of propylene increases, it is not suitable as a ship rope, and the molar ratio of ethylene and propylene is preferably 100: 0 to 90:10. Do.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 4.0, less than 1.5 has a problem of poor polymerization yield, 4.0 or more is poor workability. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of palladium catalyst and polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 or more, the molecular weight distribution is increased. The molecular weight distribution of the most preferred polyketones is 2.5 to 3.5.

Furthermore, polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography are particularly preferred. The physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present. Melting | fusing point of the conversion of the polymer used by this invention is 175-300 degreeC, and is 210-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more 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 during the manufacture of the fiber is lowered, if it exceeds 7.0, workability is poor.

The manufacturing method of the polyketone fiber of this invention is demonstrated.

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

Thereafter, the filament passed through the coagulation bath is passed through the washing tank. At this time, the temperature of the coagulation bath and the washing tank is maintained at about 0 ~ 80 ℃ in order to prevent the deterioration of physical properties due to the formation of pores (pore) in the fiber tissue due to the rapid desolvent.

The fiber passed through the washing tank is washed with acid in an aqueous solution containing acid, and then passed through a second washing bath to remove the acid, and then passed through a dryer to contain an oil and an additive in an emulsion treatment apparatus. do.

In the present invention, the coagulation bath is characterized in that the temperature is -10 to 40 ℃ and the metal salt concentration is 1 to 30% by weight, the water washing bath is preferably 0 to 40 ℃ temperature and metal salt concentration is 1 to 30% by weight.

At this time, by recovering the aqueous metal salt solution used in the coagulation bath and washing tank, and passed through the reverse osmosis membrane, it is possible to recover a high concentration of the metal salt solution. The aqueous metal salt solution recovered as described above may be reused as an aqueous metal salt solution for dissolving polyketone.

In addition, it passed through an interlace nozzle to improve flatness and improve focusing. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm 2 and the number of entanglements per meter of filament was 2 to 40 times.

Thereafter, the filament yarn passing through the interlace nozzle is dried while passing through the drying apparatus. At this time, the drying temperature and drying method have a great influence on the post process and the physical properties of the filament.

And the filament which passed the drying apparatus is finally wound up by a winding machine via a secondary tanning apparatus.

In addition, the stretching process in the polyketone fibers of the present invention is very important for high strength and hot water resistance improvement. The heating method of the stretching process includes hot air heating and roller heating. However, in the hot air heating, hot air heating was more effective for producing high-strength polyketone fibers because the filament is easily damaged by contact with the roller surface. However, the inventors of the present invention apply a heat stabilizer using a roller heating type, especially a hot roll drying method, and stretch the process 1.0 to 2.0 times, preferably 1.2 to 1.6 times, and more preferably 1.4 times during the cleaning of the fibers. Through high strength multifilament could be obtained. At this time, the strength of the fiber at the time of stretching below 1.0 times decreases, and the workability at the time of stretching above 2.0 times falls.

That is, the present invention is characterized in that the stretching process is performed using a method of passing through a heating chamber (heating chamber) of 230 ℃ to 300 ℃.

On the other hand, 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 as a solvent for dissolving the polyketone. Specifically, zinc salts include zinc bromide, zinc chloride, zinc iodide, and the like, and calcium salts include calcium bromide, calcium chloride, calcium iodide, and the like, and lithium salts such as lithium bromide, lithium chloride, and lithium iodide. The iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one member selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in view of solubility of the raw polyketone and homogeneity of the polyketone solution.

Moreover, it is preferable that the density | concentration of metal salt in the metal salt aqueous solution of this invention is 30-80 weight. If the concentration of the metal salt is less than 30% by weight solubility is lowered, if the concentration of the metal salt is more than 80% by weight the cost of concentration increases disadvantageous economically. Water, methanol, ethanol and the like may be used as a solvent for dissolving the metal salt, but in particular, water is used in the present invention because it is advantageous in terms of economics and solvent recovery.

In order to obtain a polyketone fiber having high strength and excellent fatigue resistance and dimensional stability as a key 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 and 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 weight ratio of the sum 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 and lithium bromide at the time is 40/60 to 90/10, preferably 60/40 to 85/15.

Although it does not restrict | limit especially as a manufacturing method of a polyketone solution, The example of a preferable manufacturing method is demonstrated below.

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

At this time, it is preferable to remove impurities by filtering the polyketone polymer through a disk filter as shown in FIG.

In the case of using a disk filter to remove impurities, there is no low flow or dead area, and the flowability of the spinning solution is enhanced by uniform pressure distribution, thereby improving filter life. In the case of using a conventional candle filter (FIG. 1), the life of the filter is up to 9 days, whereas in the case of the disk filter can be improved to more than 45 days due to the optimization of the melting process. In addition, a stable continuous operation may be possible due to the improvement of the life of the filter.

In addition, in the present invention, the polyketone polymer may be used by mixing other polymer materials or additives. Polymeric materials include polyvinyl alcohol, carboxymethyl polyketone, polyethylene glycol, and the like, and additives include viscosity enhancing agents, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method for producing polyketone fibers, including the steps of spinning, washing, drying and stretching the prepared 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.

In more detail the spinning process of the method according to the present invention, an orifice having a diameter of 100 to 500 μm and a length of 100 to 1500 μm, wherein the ratio (L / D) of the diameter and the length is 1 to 3 to 8 times, and the orifice The spacing between the extrusion and spinning of the spinning stock solution through a spinning nozzle including a plurality of orifices of 1.0 to 5.0mm, allowing the fibrous spinning stock to pass through the air layer to reach the coagulation bath, and then solidify it to obtain a multifilament. .

The spinning nozzle used is usually circular in shape and has a nozzle diameter of 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 adhesion may occur before the discharged solution is solidified. If the nozzle diameter is too large, peripheral devices such as a spinning pack and a nozzle are enlarged, which is disadvantageous to the installation surface. In addition, if the diameter of the nozzle orifice is less than 100 μm, a large number of trimmings occur during spinning, which adversely affects radioactivity. If the nozzle orifice exceeds 500 μm, the solidification rate of the solution in the coagulation bath after spinning is slow, and the solvent is removed from the metal salt solution. And washing with water becomes difficult.

Considering that it is an industrial fiber in terms of use, in consideration of the orifice spacing for uniform cooling of the solution, the number of orifices is 100 to 2,200, more preferably 300 to 1,400.

If the number of orifices is less than 100, the fineness of each filament becomes thick, so that the solvent cannot be sufficiently released within a short time, so that solidification and washing with water are not completed. In addition, if the number of orifices exceeds 2,200, the filament and affixes close to the filament are likely to occur in the air layer section, and the stability of each filament decreases after spinning, which leads to the deterioration of physical properties. Can cause.

When the fibrous spinning stock solution passed through the spinning nozzle is solidified in the upper coagulating solution, the larger the diameter of the fluid, the greater the difference in the coagulation rate between the surface and the inside, thus making it difficult to obtain a dense and uniform fiber. Therefore, when spinning the polyketone solution, even the same discharge amount can be obtained into the coagulating liquid with a smaller diameter while maintaining the appropriate air layer.

The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. Too short air gap distances increase the rate of micropores generated during rapid surface layer solidification and desolvation, which hinders the increase in elongation ratio, while too long air gap distances are associated with filament adhesion, atmospheric temperature, and humidity. It is difficult to maintain process stability by receiving a lot.

The composition of the coagulation bath used in the present invention is such that the concentration of the aqueous metal salt solution is 1 to 20% by weight. The coagulation bath temperature is maintained at -10 to 60 ° C, more preferably -5 to 20 ° C. In the coagulation bath, when the filament passes through the coagulation bath, if the spinning speed increases more than 500m / min, the coagulation fluid shakes due to friction between the filament and the coagulation solution. In order to improve productivity by extending the excellent physical properties and spinning speed through the stretching orientation, such a phenomenon is a factor that impairs process stability, it is necessary to minimize it.

In the present invention, the coagulation bath is characterized in that the temperature is -10 to 40 ℃ and the metal salt concentration is 1 to 30% by weight, the water washing bath is preferably 0 to 40 ℃ temperature and metal salt concentration is 1 to 30% by weight.

In the present invention, the dryer temperature is 100 ℃ or more, preferably 200 ℃ or more to impart an emulsion, heat-resistant agent, antioxidant or stabilizer to the fiber passed through the dryer.

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

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

The present invention provides a high-strength fiber through the heat-resistant stability and direct drying method during wet spinning of polyketone. In the existing spinning process, even when the optimal drying and stretching temperature is optimized, the maximum strength is 13g / d, but the present invention optimizes the heating method and the temperature profile of the drying method to form a dense structure by fusion of the cross section of the dry yarn, This improves the draw ratio and strength. In addition, the stretching ratio and the strength is improved through a process including a heat stabilizer during drying and stretching to prevent thermal degradation of the polyketone during heating.

Polyketone fibers have an oxidation or deterioration mechanism at high temperatures. As a radical oxidation mechanism, polyketones emit carbon dioxide when exposed to oxygen above 90 ° C, resulting in oxidative degradation. In addition, due to radical deterioration mechanisms, polyketones emit carbon monoxide and ethylene when exposed to high temperatures of 200 ° C. or higher, and thermal degradation occurs. Heat stabilizers are used to prevent oxidation and degradation of polyketones at these high temperatures. As the heat stabilizer, both antioxidants which can prevent radical oxidation and deterioration may be used.

Preferably, a phenolic heat stabilizer is used, and one or more kinds of heat stabilizers may be used alone or in combination. The oxidation and deterioration prevention mechanism prevents the chain reaction by radicals by trapping an alkyl radical generated by heat or ultraviolet rays with a heat stabilizer as a heat stabilizer (see FIG. 1). The heat stabilizer may be used before drying or stretching, and the method may be a dipping method or a coating method alone or one or more. Specifically, 0.1% of the solution of the phenolic heat stabilizer in which the phenolic heat stabilizer is mixed with a methanol solvent in the pre-drying and stretching steps is applied in the pre-drying and stretching steps, and is present on the fiber in the pre-drying step. The heat stabilizer was 250 ppm, but after the drying and stretching step, 25 ppm remain. The heat stabilizer should be used in an appropriate amount depending on the process, but the workability is low in many, and the heat stability is not sufficient in a small amount. Heat stabilizers can be used in one or two dips or more.

On the other hand, the present invention is to use the direct drying method of hot roller drying method instead of the indirect drying method of the conventional hot air drying method to increase the strength of the fiber. The conventional hot air drying method used the hot air drying method as shown in Figure 2 for a residence time of about 3 minutes 30 seconds at a temperature of 180 ℃. It is possible to dry uniformly and has the effect of improving affix, but tangling, loops, static electricity generated a lot of fusion (fusion) structure is difficult to generate a tissue (see Fig. 4). The present invention uses a hot roll drying method as shown in Figure 3 for a residence time of about 1 minute 30 seconds at a temperature of 220 to 230 ℃ by hot roll drying method. When the drying method is used, there is no tangling, little static electricity is generated, and the tissue is dense due to the formation of a fusion structure, and it is easy to apply to commercialization (see FIG. 5).

In addition, the present invention is subjected to the stretching process, the fiber is stretched by 15 to 18 times because of the stretching. The stretching is carried out in one or two or more stages of multistage for stretching the polyketone fibers. In addition, when performing multistage stretching, it is preferable that the temperature-stretching at which the stretching temperature gradually increases as the draw ratio is increased. Specifically, the stretching process is carried out at a temperature of 240 to 270 ℃, the residence time is within about 1 minute 30 seconds, and undergoes the first and second stages. Stretching is performed 7 times in the 1st stage and 2.5 times in the 2nd stage, and stretching is performed step by step in the 2nd stage. After the first stage, the polyketone fiber has 10% elongation and 8g / d strength, but after the second stage, the elongation is about 5.2% and 20g / d polyketone fiber is obtained.

In addition, as a result of the drying and stretching process as described above, heat deterioration of polyketone occurs at a high temperature, and thus a heat stabilizer is added. The heat stabilizer may be applied before drying or stretching, and in the present invention, either one dip or two dip may be used. In general, when the two-dip or more is performed, the elongation of the fiber is lowered apart from the increase in strength, but in the case of the hot roll drying method according to the present invention, there is almost no elongation.

The multifilaments produced by the process according to the invention are polyketone multifilaments with a total denier range of 500 to 3,500 and a cutting load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2200 individual filaments having a fineness of 0.5 to 8.0 denier.

The fiber density of the monofilament is 1.295-1.310 g / cm3 by the process of adding the hot roll drying method and the heat stabilizer of the present invention, and the structure shows a dense structure as shown in FIG. As a result, the initial modulus of the polyketone monofilament produced by the above process is 200 g / d or more, elongation is 2.5 to 3.5% at 10.0 g / d, and elongates at least 0.5% or more at 19.0 g / d or more.

The polyketone body armor of the present invention is manufactured through a process of weaving a fabric, a process of refining the fabric, and a water repellent treatment of the fabric using the polyketone fibers produced by the above method as warp and weft yarns.

The process of weaving the fabric may include a process of weaving the polyketone multifilament with warp and weft yarns and weaving with plain or basket weaving. The inclined density and weft density may be 10 to 25 bone / cm respectively.

The process of refining the fabric is to remove the oil or foreign matter adhering to the polyketone multifilament constituting the fabric, in order to improve the flexibility of the fabric.

The process of refining the fabric may be carried out using a surfactant such as NaOH or Na 2 CO 3 at 40 ℃ to 100 ℃.

The process of water repellent treatment of the fabric is a process of treating the fabric so as not to absorb moisture, and to prevent property degradation due to moisture absorption during long-term use, after removing the foreign matter attached to the surface of the fabric through the refining process, This is done by dipping the fabric in a water repellent and drying.

The water repellent is 20 to 35 parts by weight of dipropylene glycol, 0.5 to 5.5 parts by weight of silicone oil and isopropyl alcohol, relative to 100 parts by weight of hardoxylated perfluoroalkylethyl acrylate copolymer. (isopropylalcohol) is prepared to contain 0.5 to 10 parts by weight.

Polyketone fibers produced by the present invention can be produced by a bulletproof helmet.

For example, a bulletproof helmet can be manufactured by coating a thermoplastic resin on a polyketone fiber as described above, laminating a polyketone fiber coated with a thermosetting resin or thermoplastic resin on an outer layer in a helmet-shaped mold, and then pressing it. have.

The thermosetting resin is not particularly limited, but a phenol resin, urea resin, melamine resin, silicone resin, epoxy resin, polyurethane resin, or the like may be used.

The thermoplastic resin is preferably an acrylic resin, vinyl chloride resin, vinylacetyl resin, polymethacrylic resin, polystyrene resin, polyethylene resin, nylon, or the like. However, it is not necessarily limited thereto.

Polyketone fibers produced by the present invention may be made of a polyketone bulletproof material for aircraft or military aircraft.

The polyketone multifilament prepared by the above method is applied to warp and weft yarns to make plain weave, and then impregnated in the elastic matrix stock solution, then laminated on a wing tip manufacturing mold, bonded with a thermoplastic or thermosetting resin, and heated and pressurized to polyketone Manufacture aircraft wing tip devices.

The elastic matrix stock solution is prepared by mixing 5 to 15 parts by weight of anti-aging agent, 3 to 8 parts by weight of carbon black and 20 to 30 parts by weight of inorganic fillers relative to 100 parts by weight of rubber chloride.

The rubber chloride is made of chloroprene rubber, acrylonitrile butadiene rubber, acrylic rubber, or a mixture of two or more thereof.

The anti-aging agent is a phenol-based, phosphorus-based, thio-based antioxidant.

As the inorganic filler, magnesium oxide, magnesium hydroxide, zinc oxide, or the like may be used.

The thermosetting resin is not particularly limited, but a phenol resin, urea resin, melamine resin, silicone resin, epoxy resin, polyurethane resin, or the like may be used.

The thermoplastic resin is preferably an acrylic resin, vinyl chloride resin, vinylacetyl resin, polymethacrylic resin, polystyrene resin, polyethylene resin, nylon, or the like. However, it is not necessarily limited thereto.

The polyketone multifilament prepared above is applied to warp and weft yarns, and then manufactured in plain weave, and then laminated on a mold to be bonded with a thermoplastic or thermosetting resin to heat and pressurize to prepare a polyketone helicopter interior.

The polyketone fibers produced by the present invention are polyketone automotive structural materials, marine platforms, submersible structural materials, optical cable sheathing materials, radar dome structural materials, bobbins of superconducting coils, cryogenic insulation materials, wires for tennis rackets, yacht structural materials, yacht sails, competition It can be made of bicycles, coated fabrics for paraglides, safety gloves.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Preparation Example 1

A 60% by weight zinc bromide solution was injected into the extruder maintained at an injection temperature of 25 ° C. and 30 ° C. at a speed of 13000 g / hour with a gear pump, and had a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 ㎗ / g. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55-60 ° C. and the screw was operated at 110 rpm to produce polyketone fibers by wet and dry spinning.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃. Final monofilament fineness was adjusted to 1.5 denier.

Preparation Example 2

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber system was adjusted to 240, 250, 260 and 268 ℃, it is the same as in Preparation Example 1.

Preparation Example 3

It is the same as the manufacture example 1 except the temperature of each step of 1st and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Preparation Example 4

A polyketone powder with a zinc bromide solution having a concentration of 60% by weight was injected at an injection temperature of 25 ° C. at an internal temperature of 30 ° C. with a gear pump at a speed of 13000 g / hour, having a molecular weight distribution of 3.0 and an intrinsic viscosity of 5.7 ㎗ / g. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55-60 ° C. and the screw was operated at 110 rpm to produce polyketone fibers by wet and dry spinning.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃.

Preparation Example 5

It is the same as Preparation Example 4, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Preparation Example 6

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Production Example 4.

Preparation Example 7

A polyketone powder with a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 ㎗ / g is injected into the extruder with a concentration of 60% by weight of a zinc bromide solution at an injection temperature of 25 ° C. at a speed of 13000 g / hour using a gear pump. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55-60 ° C. and the screw was operated at 110 rpm to produce polyketone fibers by wet and dry spinning.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃.

Preparation Example 8

Except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8 it is the same as in Preparation Example 7.

Preparation Example 9

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Production Example 8.

Preparation Example 10

A phenolic heat stabilizer was prepared in the same manner as in Preparation Example 1 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Preparation Example 11

A phenolic heat stabilizer was prepared in the same manner as in Preparation Example 1, except that a 0.1% solution of Adeka's AO80 and methanol was subjected to two dips before drying and before stretching.

Property evaluation

(1) intrinsic viscosity

After dissolving 0.1 g of the sample in a reagent (90 ° C.) mixed with phenol and 1,1,2,2-tetrachloroethanol 6: 4 (weight ratio) for 90 minutes, transfer to a Ubbelohde viscometer and place it in a 30 ° C. thermostat. The solution is held for 10 minutes at, and the drop seconds of the solution are obtained by using a viscometer and an aspirator. The number of seconds of falling of the solvent can also be obtained by the following equations obtained from the above equations. The value was calculated

R.V. = Number of drops of solvent / number of drops of solvent

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

Where C represents the concentration of the sample in solution (g / 100ml).

(2) molecular weight distribution

The polyketone was dissolved in a hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate so that the polyketone concentration was 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).

Shoga GPCHFIP-G

(B): Shodex HFIP-606M

(C): Shodex HFIP-606M

Column temperature: 40 ℃

Mobile phase: Hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate

Flow rate: 0.5 ml / min

Detector: parallax refractometer

Injection volume: 30 μl

The weight of the PMMA conversion of polyketone measured from the calibration curve of PMMA obtained under the same conditions as the above measurement conditions using polymethyl methacrylate (PMMA) having a monodisperse molecular weight distribution as a standard sample (concentration 0.01% by weight). Average molecular weight (Mw) and number average molecular weight (Mn) were calculated | required, and Mw / Mn was made into molecular weight distribution.

(3) Measuring Modulus and Elongation

After leaving the yarn in a standard condition, that is, a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 65% for 24 hours, the sample is measured by a tensile tester using the ASTM 2256 method. The physical properties of the samples were measured with the remaining eight average values except one of the maximum and the minimum of 10 values measured from the 10 samples. Initial modulus represents the slope of the graph before the yield point.

(4) Method of measuring ballistic performance

The average speed (V50) indirectly indicating the degree of bulletproof performance of the bulletproof helmet was measured according to MIL-STD-662F specification, and the average speed (㎧) was completely penetrated using a Cal. 22-caliber fragmented bullet (FSP). The speed at the time of carrying out and the speed at the time of partial penetration were calculated | required from the average value.

(5) Measuring method of section variation (CV%)

The cross-sectional variation rate (CV%) of the multifilament manufactured in Examples and Comparative Examples was obtained by measuring the cross-sectional state of the fiber manufactured by using a cross-section cutting copper plate and a microscope, and then the relative filaments corresponding to 90% or more of the filaments. The area was quantified. In this case, the area of each filament need not be an absolute area, and relative units such as pixels obtained from image analysis software may be used. In the present invention, three points were specified at the interface of each circular filament, and the relative area of the filament was calculated using the circumscribed circle of the triangle. This operation is preferably performed using as large a magnification and image magnification as possible to reduce errors in the selection of interface points. The section variation rate was calculated as follows.

×100(%)

× 100 (%)

(6) strength (g / d), elongation (%) and modulus (g / d) of monofilament

After extracting 24 monofilaments from a yarn (multifilament) that was left for 24 hours at a temperature of 25 ° C. and a relative humidity of 55 RH%, the dendritic load was defined by the denier in Vibrojet using Vibrojet 2000's monofilament tensile tester. About monodenier x 50 (mg)) was added, and the sample length was measured at 20 mm and tensile strength 20 mm / min. The monofilament properties were measured with the remaining 22 average values except one of the maximum and the minimum of 24 measured values. Initial modulus represents the slope of the graph before the yield point.

     (5) Water resistance and chlorine resistance test

Water resistance experiment

15 laminated yarns prepared according to the examples and comparative examples were laminated and pressed, and then a specimen was prepared and cut to 100 mm and the weight (W1) was measured. After adjusting the temperature of the water in the water bath to 21 ℃, pour water so that the top of the sample is submerged in water about 3 inches (75mm), press it with a screen so that the sample does not float on the water, and then put the sample on the bottom of the water bath. It was kept for 24 hours with at least 2 inches from.

Then, after 24 hours, the product was taken out, and one side was clamped and held vertically for 30 minutes to allow the absorbed water to fall naturally. The weight (W2) was measured to take an average value, and the absorption rate was calculated according to the following equation. The results are shown in Table 3.

% Absorption = (W2-W1) / W1 × 100%

Chlorine Resistance Test

The stretched yarns prepared according to the above Examples and Comparative Examples were measured to measure the strength before and after deposition for 24 hours at room temperature in 15 L of chlorine water with an active chlorine concentration of 3 ppm and pH 7.5, respectively. Retention rate was calculated. Instron 4301 (Instron, USA) was used for the strength measurement. The sample length was 5 centimeters, and the cell was measured at a cross head speed of 300 mm / min using 1 Kg. The results are shown in Table 3.

Strong retention rate = S / So% (So: strong before treatment; S: strong after treatment)

(6) measurement of moisture absorption rate

Specimens (100 mm) were prepared, and each of the specimens was dried at 105 ° C. for 30 minutes, and then the respective masses were measured. Subsequently, the specimens were immersed in distilled water at room temperature for 24 hours, taken out, wiped off the moisture on the surface of each specimen, and the respective masses were measured, which was referred to as 'mass after absorption'. Thereafter, the moisture absorption rate was obtained from Equation 1 below.

[Equation 1]

Moisture absorption rate (%) = (mass after absorption-mass before absorption) / (mass before absorption)

(7) flame retardancy test

The burned length (cm) of the specimens was measured by evaluating flame retardancy according to the IEC 332-3C flame retardant test (combustion length 240 cm or less).

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Property retention rate after moisture absorption (%) Heat resistance (%) Toughness Dry Heat Shrinkage (%) Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Preparation Example 1 20.75 5.9 94.3 94.3 53.54 1.25 220 2.4 1.8 Preparation Example 2 21.00 5.6 93.1 93.1 54.02 1.14 280 2.5 2.1 Preparation Example 3 20.84 5.7 92.3 92.3 53.65 1.15 205 2.3 1.7 Preparation Example 4 19.95 6.3 94.0 94.0 52.95 1.35 250 2.9 2.0 Preparation Example 5 20.55 6.0 92.4 92.4 53.55 1.26 290 3.1 1.0 Preparation Example 6 20.13 6.1 92.3 92.3 53.13 1.06 212 2.8 1.4 Preparation Example 7 19.74 6.3 91.1 91.1 52.74 1.37 210 2.7 1.2 Preparation Example 8 20.87 5.7 90.7 90.7 53.87 1.15 230 3.2 1.3 Preparation Example 9 20.14 6.1 93.1 93.1 53.14 1.27 220 3.1 1.3 Preparation Example 10 20.20 6.0 91.5 91.5 53.20 1.29 260 3.4 1.4 Preparation Example 11 21.04 5.6 91.3 91.3 54.04 1.11 230 2.8 1.2

As shown in Table 1, the polyketone fibers produced by the examples of the present invention were excellent in elongation and strength, and excellent in water resistance, heat resistance, toughness, dry heat shrinkage ratio, and the like.

Example 1

Using the polyketone fibers obtained through the above Preparation Example 1, the fabric was woven into a plain weave with a polyketone multifilament inclined density and weft density of 1,000 pieces each having a fineness of 1.5 deniers of 10 bones / cm. Subsequently, the fabric was treated with a surfactant, washed with water and dried, and then 20 to 35 parts by weight of dipropylene glycol, relative to 100 parts by weight of hardoxylated perfluoroalkylethyl acrylate copolymer. , 0.5 to 5.5 parts by weight of silicone oil and 0.5 to 10 parts by weight of isopropyl alcohol (isopropylalcohol) was prepared, the fabric was immersed by impregnating the water repellent, and then dried through a padding process to manufacture bulletproof clothing.

Example 2

It is the same as Example 1 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 3

It is the same as Example 1 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Example 4

Using the polyketone fibers obtained through the above Preparation Example 4, the fabric was woven into a plain weave with a polyketone multifilament inclination density and weft density of 1,000 pieces of 1.5 deniers of 10 bone / cm, respectively. Subsequently, the fabric was treated with a surfactant, washed with water, and dried, and then 20 to 35 parts by weight of dipropylene glycol relative to 100 parts by weight of the hardoxylated perfluoroalkylethyl acrylate copolymer. , 0.5 to 5.5 parts by weight of silicone oil and 0.5 to 10 parts by weight of isopropyl alcohol (isopropylalcohol) was prepared, the fabric was immersed by impregnating the water repellent, and then dried through a padding process to manufacture bulletproof clothing.

Example 5

It is the same as Example 4 except adjusting the intrinsic viscosity of polyketone polymer to 6.1 dl / g.

Example 6

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 4.

Example 7

Using the polyketone fibers obtained through the above Preparation Example 7, the fabric was woven into a plain weave of 1,500 polyketone multifilament of denier 8.0 with a warp density and a weft density of 10 bones / cm, respectively. Subsequently, the fabric was treated with a surfactant, washed with water and dried, and then 20 to 35 parts by weight of dipropylene glycol, relative to 100 parts by weight of hardoxylated perfluoroalkylethyl acrylate copolymer. , 0.5 to 5.5 parts by weight of silicone oil and 0.5 to 10 parts by weight of isopropyl alcohol (isopropylalcohol) was prepared, the fabric was immersed by impregnating the water repellent, and then dried through a padding process to manufacture bulletproof clothing.

Example 8

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

Example 9

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 7.

Example 10

A phenolic heat stabilizer was the same as in Example 1 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 11

A phenolic heat stabilizer was the same as in Example 1 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 1 to 3

Except for using aramid fibers in the production of bulletproof clothing, the draw ratio is 1.0 times in the washing process and hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 1, the spinning conditions of Table 1 Was performed.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Bulletproof performance (V50 FSP) Cross Section% Change Example 1 20.75 5.9 590 9 Example 2 21.00 5.6 610 8 Example 3 20.84 5.7 590 7 Example 4 19.95 6.3 610 11 Example 5 20.55 6.0 700 12 Example 6 20.13 6.1 550 10 Example 7 19.74 6.3 600 8 Example 8 20.87 5.7 570 13 Example 9 20.14 6.1 590 12 Example 10 20.20 6.0 600 8 Example 11 21.04 5.6 580 9 Comparative Example 1 10.8 1.9 470 22 Comparative Example 2 11.2 2.1 510 21 Comparative Example 3 9.6 1.7 560 18

Polyketone filaments produced by the embodiment of the present invention as shown in Table 3

It has been found that the strength, elongation and cross-sectional variation is excellent, the bulletproof clothing containing the polyketone filament is excellent in ballistic performance.

Example 12

After applying 1,000 denier polyketone filaments obtained through the process of Preparation Example 1 to warp and weft yarns and weaving them in a plain weave, the epoxy resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber, followed by a helmet After lamination to the lower mold for production, a bulletproof helmet was prepared by curing for 20 minutes at a pressure of 160 bar and a temperature of 130 ℃.

Example 13

It is the same as Example 12 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 14

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber system is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 12.

Example 15

1,000 denier polyketone filaments obtained through the process of Preparation Example 4 were applied to warp and weft yarns and weaved in plain weave, and then coated with acrylic resin by applying a pressure of 1.5 bar in an 80 ° C. chamber, followed by a helmet After lamination to the lower mold for production, a bulletproof helmet was prepared by curing for 20 minutes at a pressure of 160 bar and a temperature of 130 ℃.

Example 16

Except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g is the same as in Example 15.

Example 17

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 15.

Example 18

After applying 1,000 denier polyketone filaments obtained through the process of Preparation Example 7 to warp and weft yarns and weaving them in plain weave, the polyamide resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber. After lamination to the lower mold for helmet production, a bulletproof helmet was prepared by curing at a pressure of 160 bar and a temperature of 130 ° C. for 20 minutes.

Example 19

Same as Example 18, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 20

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 18.

Example 21

A phenolic heat stabilizer was the same as in Example 12 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 22

As a phenolic heat stabilizer, the same procedure as in Example 12 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 4 to 6

Except for using the aramid fibers in the production of bulletproof helmet, the draw ratio of 1.0 times in the washing process and hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 12, the spinning conditions of Table 4 Was performed.

Comparative Example 4 Comparative Example 5 Comparative Example 6 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Bulletproof Helmet Properties Monofilament Property Strength (g / d) Elongation (%) Bulletproof performance (V50 FSP) Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Example 12 20.75 5.9 590 220 2.4 1.8 Example 13 21.00 5.6 610 280 2.5 2.1 Example 14 20.84 5.7 590 205 2.3 1.7 Example 15 19.95 6.3 610 250 2.9 2.0 Example 16 20.55 6.0 700 290 3.1 1.0 Example 17 20.13 6.1 550 212 2.8 1.4 Example 18 19.74 6.3 600 210 2.7 1.2 Example 19 20.87 5.7 570 230 3.2 1.3 Example 20 20.14 6.1 590 220 3.1 1.3 Example 21 20.20 6.0 600 260 3.4 1.4 Example 22 21.04 5.6 580 230 2.8 1.2 Comparative Example 4 10.8 1.9 470 210 3.1 0 Comparative Example 5 11.2 2.1 510 200 3.2 0 Comparative Example 6 9.6 1.7 560 215 3.0 0

Polyketone filaments produced by the embodiment of the present invention as shown in Table 5

It has been found that the strength, elongation and cross-sectional variation is excellent, the bulletproof helmet containing the polyketone filament was excellent in ballistic performance.

Example 23

After impregnating the polyketone multifilament obtained through the process of Preparation Example 1 in an elastic matrix stock solution containing 10 parts by weight of a phenolic anti-aging agent, 5 parts by weight of carbon black and 30 parts by weight of magnesium oxide compared to 100 parts by weight of the chloroprene rubber And drying to obtain an elastic sheet, which was laminated in 20 layers, and heated and pressurized at a temperature of 155 ° C. and a pressure of 150 kgf / cm 2 to prepare a bulletproof test piece.

Example 24

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber system was adjusted to 240, 250, 260 and 268 ℃, it is the same as in Example 23.

Example 25

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system was adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 23.

Example 26

After impregnating the polyketone multifilament obtained through the process of Preparation Example 4 in an elastic matrix stock solution containing 10 parts by weight of a phenolic anti-aging agent, 5 parts by weight of carbon black and 30 parts by weight of magnesium oxide compared to 100 parts by weight of the chloroprene rubber And drying to obtain an elastic sheet, which was laminated in 20 layers, and heated and pressurized at a temperature of 155 ° C. and a pressure of 150 kgf / cm 2 to prepare a bulletproof test piece.

Example 27

The same as in Example 26 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 28

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 26.

Example 29

After impregnating the polyketone multifilament obtained through the process of Preparation Example 7 with an elastic matrix stock solution containing 10 parts by weight of a phenolic anti-aging agent, 5 parts by weight of carbon black and 30 parts by weight of magnesium oxide compared to 100 parts by weight of the chloroprene rubber And drying to obtain an elastic sheet, which was laminated in 20 layers, and heated and pressurized at a temperature of 155 ° C. and a pressure of 150 kgf / cm 2 to prepare a bulletproof test piece.

Example 30

Same as Example 29, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 31

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 29.

Example 32

As a phenolic heat stabilizer, the same procedure as in Example 23 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 33

As a phenolic heat stabilizer, the same procedure as in Example 23 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 7 to 9

Except for using the aramid fibers in the production of fragment protection material, the draw ratio in the washing step to 1.0 times and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 23, the spinning of Table 6 Carried out under conditions.

Comparative Example 7 Comparative Example 8 Comparative Example 9 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Bulletproof performance (V50 FSP) Cross Section% Change Example 23 20.75 5.9 590 9 Example 24 21.00 5.6 610 8 Example 25 20.84 5.7 590 7 Example 26 19.95 6.3 610 11 Example 27 20.55 6.0 700 12 Example 28 20.13 6.1 550 10 Example 29 19.74 6.3 600 8 Example 30 20.87 5.7 570 13 Example 31 20.14 6.1 590 12 Example 32 20.20 6.0 600 8 Example 33 21.04 5.6 580 9 Comparative Example 7 10.8 1.9 470 22 Comparative Example 8 11.2 2.1 510 21 Comparative Example 9 9.6 1.7 560 18

As shown in Table 7, the polyketone filaments produced by the examples of the present invention were found to have excellent strength, elongation and cross-sectional variation, and the fragment protection material including the polyketone filaments was found to have excellent ballistic performance.

Example 34

After weaving the polyketone filament obtained through the process of Preparation Example 1 to cut the fabric mat, 15 sheets of the fabric mat is laminated and placed in a molding apparatus to form a molded article and cut it in a predetermined length and width direction to aircraft or Polyketone bulletproof material for military aircraft was prepared.

Example 35

It is the same as Example 34 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 36

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system was adjusted to 240, 255, 265 and 272 ℃, the same as in Example 34.

Example 37

After weaving the polyketone filament obtained through the process of Preparation Example 4 to cut the fabric mat, 15 sheets of the fabric mat is laminated and put into a molding apparatus to form a molded article and cut it in a predetermined length and width direction to aircraft or Polyketone bulletproof material for military aircraft was prepared.

Example 38

The same as in Example 37, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 39

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 37.

Example 40

After weaving the polyketone filament obtained through the process of Preparation Example 7 and cutting the fabric mat, 15 sheets of the fabric mat are laminated and placed in a molding apparatus to form a molded article, which is cut in a predetermined length and width direction, or by aircraft or Polyketone bulletproof material for military aircraft was prepared.

Example 41

Same as Example 40 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 42

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 40.

Example 43

As a phenolic heat stabilizer, the same procedure as in Example 34 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 44

As a phenolic heat stabilizer, the same procedure as in Example 34 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 10 to 12

In the manufacture of bulletproof materials for aircraft or military aircraft, it was carried out in the same manner as in Example 34 except that aramid fibers were used, the draw ratio was 1.0 times in the washing process, and the hot air drying method was performed instead of the hot roll drying method. It was carried out under the spinning condition of.

Comparative Example 10 Comparative Example 11 Comparative Example 12 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Bulletproof material properties Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Bulletproof performance (V50 FSP) Example 34 20.75 5.9 220 2.4 1.8 590 Example 35 21.00 5.6 280 2.5 2.1 610 Example 36 20.84 5.7 205 2.3 1.7 590 Example 37 19.95 6.3 250 2.9 2.0 610 Example 38 20.55 6.0 290 3.1 1.0 700 Example 39 20.13 6.1 212 2.8 1.4 550 Example 40 19.74 6.3 210 2.7 1.2 600 Example 41 20.87 5.7 230 3.2 1.3 570 Example 42 20.14 6.1 220 3.1 1.3 590 Example 43 20.20 6.0 260 3.4 1.4 600 Example 44 21.04 5.6 230 2.8 1.2 580 Comparative Example 10 10.8 1.9 210 3.1 0 470 Comparative Example 11 11.2 2.1 200 3.2 0 510 Comparative Example 12 9.6 1.7 215 3.0 0 560

As shown in Table 9, the polyketone multifilament prepared by the embodiments of the present invention is excellent in strength and elongation, and the polyketone bulletproof material including the same has excellent antiballistic performance and is suitable for use as a bulletproof material for aircraft or military aircraft. appear.

Example 45

The polyketone multifilament obtained through the process of Preparation Example 1 was impregnated with an elastic matrix solution mixed with 100 parts by weight of chloroprene rubber, 10 parts by weight of phenolic antioxidant, 5 parts by weight of carbon black, and 20 parts by weight of magnesium oxide. After taking out and laminating the mold for wingtip manufacturing, the aircraft wingtip device was manufactured by heating and pressing at a temperature of 100 to 150 ° C. and a pressure of 15 to 25 bar.

Example 46

It is the same as Example 45 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 47

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method was adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 45.

Example 48

The polyketone multifilament obtained through the process of Preparation Example 4 was impregnated in an elastic matrix solution mixed with 100 parts by weight of chloroprene rubber, 10 parts by weight of a phenolic antioxidant, 5 parts by weight of carbon black, and 20 parts by weight of magnesium oxide. After taking out and laminating the mold for wingtip manufacturing, the aircraft wingtip device was manufactured by heating and pressing at a temperature of 100 to 150 ° C. and a pressure of 15 to 25 bar.

Example 49

Same as Example 48 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 50

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 48.

Example 51

The polyketone multifilament obtained through the process of Preparation Example 7 was impregnated with an elastic matrix solution mixed with 100 parts by weight of chloroprene rubber, 10 parts by weight of a phenolic antioxidant, 5 parts by weight of carbon black, and 20 parts by weight of magnesium oxide. After taking out and laminating the mold for wingtip manufacturing, the aircraft wingtip device was manufactured by heating and pressing at a temperature of 100 to 150 ° C. and a pressure of 15 to 25 bar.

Example 52

Same as Example 51 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 53

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 51.

Example 54

A phenolic heat stabilizer was the same as in Example 45 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 55

As a phenolic heat stabilizer, the same procedure as in Example 45 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 13 to 15

In the manufacture of aircraft wingtip device was carried out in the same manner as in Example 45 except for using aramid fibers, the draw ratio in the water washing process to 1.0 times and performing a hot air drying method instead of hot roll drying method, spinning of Table 10 Carried out under conditions.

Comparative Example 13 Comparative Example 14 Comparative Example 15 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 45 20.75 5.9 220 2.4 1.8 Example 46 21.00 5.6 280 2.5 2.1 Example 47 20.84 5.7 205 2.3 1.7 Example 48 19.95 6.3 250 2.9 2.0 Example 49 20.55 6.0 290 3.1 1.0 Example 50 20.13 6.1 212 2.8 1.4 Example 51 19.74 6.3 210 2.7 1.2 Example 52 20.87 5.7 230 3.2 1.3 Example 53 20.14 6.1 220 3.1 1.3 Example 54 20.20 6.0 260 3.4 1.4 Example 55 21.04 5.6 230 2.8 1.2 Comparative Example 13 10.8 1.9 210 3.1 0 Comparative Example 14 11.2 2.1 200 3.2 0 Comparative Example 15 9.6 1.7 215 3.0 0

As shown in Table 11, the polyketone multifilament manufactured according to the embodiment of the present invention is excellent in strength and elongation, and the aircraft wing tip device to which the same is applied has been found to have excellent flexibility.

Example 56

After applying the polyketone multifilament obtained in the manufacturing example 1 to the warp and weft yarn to make a plain weave, laminated to a mold and bonded with an acrylic resin through a heat treatment for 30 minutes with a heat press roll of 150 ℃, 2.5bar Polyketone Helicopter Interior

Example 57

It is the same as Example 56 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 58

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber system was adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 56.

Example 59

After applying the polyketone multifilament obtained through the manufacturing example 4 to the warp and weft yarn to produce a plain weave, laminated to a mold and bonded with an acrylic resin through a heat treatment process for 30 minutes with a heat press roll of 150 ℃, 2.5bar Polyketone helicopter interiors were prepared.

Example 60

Same as Example 59 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 61

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 59.

Example 62

The polyketone multifilament prepared above is applied to warp and weft yarns, and then manufactured in plain weave, laminated to a mold, bonded to an acrylic resin, and then heat treated with a heat press roll at 150 ° C. and 2.5 bar for 30 minutes. Prepared.

Example 63

Same as Example 62 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 64

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 62.

Example 65

As a phenolic heat stabilizer, the same procedure as in Example 56 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 66

As a phenolic heat stabilizer, the same procedure as in Example 56 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 16 to 18

Except for using aramid fiber in the manufacture of helicopter interior materials, the draw ratio in the water washing process to 1.0 times and performing the hot air drying method instead of hot roll drying method, was carried out in the same manner as in Example 56, the spinning conditions of Table 12 Was performed.

Comparative Example 16 Comparative Example 17 Comparative Example 18 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 56 20.75 5.9 220 2.4 1.8 Example 57 21.00 5.6 280 2.5 2.1 Example 58 20.84 5.7 205 2.3 1.7 Example 59 19.95 6.3 250 2.9 2.0 Example 60 20.55 6.0 290 3.1 1.0 Example 61 20.13 6.1 212 2.8 1.4 Example 62 19.74 6.3 210 2.7 1.2 Example 63 20.87 5.7 230 3.2 1.3 Example 64 20.14 6.1 220 3.1 1.3 Example 65 20.20 6.0 260 3.4 1.4 Example 66 21.04 5.6 230 2.8 1.2 Comparative Example 16 10.8 1.9 210 3.1 0 Comparative Example 17 11.2 2.1 200 3.2 0 Comparative Example 18 9.6 1.7 215 3.0 0

As shown in Table 13, the polyketone fibers produced by the examples of the present invention were found to be excellent in strength and elongation, and were suitable for use as helicopter interior materials.

Example  67

The polyketone fiber obtained through the above Preparation Example 1 process was adjusted to 1.5 denier final monofilament fineness. 1,000 denier polyketone filaments obtained through the above process were applied to warp and weft yarns, and then woven into plain weave. Then, epoxy resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber, and then laminated on a mold. , Cured for 20 minutes at a pressure of 160 bar and a temperature of 130 ℃ to prepare an automobile structural material.

Example 68

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system is adjusted to 240, 250, 260 and 268 ℃, it is the same as in Example 67.

Example 69

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 67.

Example 70

The polyketone fiber obtained through the above Preparation Example 4 process was adjusted to 1.5 denier final monofilament fineness. 1,000 denier polyketone filaments obtained through the above process were applied to warp and weft yarns, and then woven into plain weave. Then, epoxy resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber, and then laminated on a mold. , Cured for 20 minutes at a pressure of 160 bar and a temperature of 130 ℃ to prepare an automobile structural material.

Example 71

The same as in Example 70, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 72

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 70.

Example 73

The polyketone fibers obtained through the above Preparation Example 7 were adjusted to 1.5 denier final monofilament fineness. 1,000 denier polyketone filaments obtained through the above process were applied to warp and weft yarns, and then woven into plain weave. Then, epoxy resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber, and then laminated on a mold. , Cured for 20 minutes at a pressure of 160 bar and a temperature of 130 ℃ to prepare an automobile structural material.

Example 74

Same as Example 73, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 75

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 73.

Example 76

As a phenolic heat stabilizer, the same procedure as in Example 67 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 77

As a phenolic heat stabilizer, the same procedure as in Example 67 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 19 to 21

Except for using the aramid fiber in the manufacture of automotive structural materials, the draw ratio is 1.0 times in the washing process and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 67, the spinning conditions of Table 1 Was performed.

Comparative Example 19 Comparative Example 20 Comparative Example 21 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Cross Section% Change Example 67 20.75 5.9 9 Example 68 21.00 5.6 8 Example 69 20.84 5.7 7 Example 70 19.95 6.3 11 Example 71 20.55 6.0 12 Example 72 20.13 6.1 10 Example 73 19.74 6.3 8 Example 74 20.87 5.7 13 Example 75 20.14 6.1 12 Example 76 20.20 6.0 8 Example 77 21.04 5.6 9 Comparative Example 19 10.8 1.9 22 Comparative Example 20 11.2 2.1 21 Comparative Example 21 9.6 1.7 18

As shown in Table 15, the automobile structural member including the polyketone multifilament manufactured by the embodiment of the present invention was found to be suitable for use as an automobile structural member due to its excellent strength and elongation.

Example 78

After applying the polyketone multifilament obtained through the manufacturing example 1 to the warp and weft yarn, and woven into plain weave, the thermoplastic or thermosetting resin is bonded to apply pressure in the chamber, and then laminated to the mold to cure the ship platform Was prepared.

Example 79

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system was adjusted to 240, 250, 260 and 268 ℃, it is the same as in Example 78.

Example 80

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 78.

Example 81

An airbag was manufactured using the polyketone fibers obtained through the preparation example 4 above.

Example 82

Same as Example 81 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 83

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 81.

Example 84

The polyketone multifilament obtained through the process of Preparation Example 7 was applied to warp and weft yarns, and then woven into plain weave. Was prepared.

Example 85

Same as Example 84 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 86

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 84.

Example 87

As a phenolic heat stabilizer, the same procedure as in Example 78 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 88

As a phenolic heat stabilizer, the same procedure as in Example 78 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 22 to 24

Except for using aramid fiber in the manufacture of the ship platform, the draw ratio in the water washing process to 1.0 times and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 78, the spinning conditions of Table 16 Was performed.

Comparative Example 22 Comparative Example 23 Comparative Example 24 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Drawing company Strength (g / d) Elongation (%) Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Absorption rate (%) Strong retention rate after 24 hours Example 78 20.75 5.9 220 2.4 1.8 158 88 Example 79 21.00 5.6 280 2.5 2.1 162 86 Example 80 20.84 5.7 205 2.3 1.7 144 84 Example 81 19.95 6.3 250 2.9 2.0 154 87 Example 82 20.55 6.0 290 3.1 1.0 138 85 Example 83 20.13 6.1 212 2.8 1.4 150 82 Example 84 19.74 6.3 210 2.7 1.2 155 84 Example 85 20.87 5.7 230 3.2 1.3 162 80 Example 86 20.14 6.1 220 3.1 1.3 168 88 Example 87 20.20 6.0 260 3.4 1.4 154 82 Example 88 21.04 5.6 230 2.8 1.2 167 78 Comparative Example 22 10.8 1.9 210 3.1 0 425 55 Comparative Example 23 11.2 2.1 200 3.2 0 408 48 Comparative Example 24 9.6 1.7 215 3.0 0 398 52

As shown in Table 17, the polyketone multifilament prepared by the examples of the present invention was found to be suitable for use as a ship platform because of its excellent strength, water resistance and chlorine resistance.

Example 89

The polyketone multifilament obtained through the process of Preparation Example 1 was injected into a manufacturing mold together with a polyurethane resin, and heated and pressurized at 50 ° C. and 3.5 bar for 1 hour to prepare a submersible structure.

Example 90

The same procedure as in Example 89 was carried out except that the temperature of each step of the first and second stages was adjusted to 240, 250, 260 and 268 ° C in the stretching of the heating chamber method.

Example 91

The same procedure as in Example 89 was carried out except that the temperature of each step of the first and second stages was adjusted to 240, 255, 265, and 272 ° C in the stretching of the heating chamber method.

Example 92

The polyketone multifilament obtained through the process of Preparation Example 4 was injected into a production mold together with a polyurethane resin, and heated and pressurized at 50 ° C. and 3.5 bar for 1 hour to prepare a submersible structure.

Example 93

Same as Example 92 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 94

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 92.

Example 95

The polyketone multifilament obtained through the process of Preparation Example 7 was injected into a production mold together with a polyurethane resin, and heated and pressurized at 50 ° C. and 3.5 bar for 1 hour to prepare a submersible structure.

Example 96

Same as Example 95 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 97

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 95.

Example 98

As a phenolic heat stabilizer, the same procedure as in Example 89 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 99

As a phenolic heat stabilizer, the same procedure as in Example 89 was carried out except that a 0.1% solution of Adeka's AO80 and methanol was subjected to two dips before drying and before stretching.

Comparative Examples 25 to 27

Except for using aramid fiber in the manufacture of the submersible structural material, the draw ratio in the water washing process to 1.0 times and the hot air drying method, not hot roll drying method was carried out in the same manner as in Example 89, the spinning conditions of Was performed.

Comparative Example 25 Comparative Example 26 Comparative Example 27 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 89 20.75 5.9 220 2.4 1.8 Example 90 21.00 5.6 280 2.5 2.1 Example 91 20.84 5.7 205 2.3 1.7 Example 92 19.95 6.3 250 2.9 2.0 Example 93 20.55 6.0 290 3.1 1.0 Example 94 20.13 6.1 212 2.8 1.4 Example 95 19.74 6.3 210 2.7 1.2 Example 96 20.87 5.7 230 3.2 1.3 Example 97 20.14 6.1 220 3.1 1.3 Example 98 20.20 6.0 260 3.4 1.4 Example 99 21.04 5.6 230 2.8 1.2 Comparative Example 25 10.8 1.9 210 3.1 0 Comparative Example 26 11.2 2.1 200 3.2 0 Comparative Example 27 9.6 1.7 215 3.0 0

As shown in Table 19, the submersible structural material including the polyketone fiber prepared by the examples of the present invention was found to be suitable for use as a submersible structural material because of its excellent strength.

Example 100

Using the polyketone fibers obtained through the procedure of Preparation Example 1 to prepare an optical cable covering.

Example 101

It is the same as Example 100 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 102

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 100.

Example 103

Using the polyketone fibers obtained through the process of Preparation Example 4 to prepare an optical cable covering.

Example 104

The same as in Example 103 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 105

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 103.

Example 106

Using the polyketone fibers obtained through the process of Preparation Example 7 to prepare an optical cable coating material.

Example 107

Same as Example 106 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 108

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 106.

Example 109

As a phenolic heat stabilizer, the same procedure as in Example 100 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 110

As a phenolic heat stabilizer, the same procedure as in Example 100 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 28 to 30

Except for using the aramid fiber in the manufacture of the optical cable coating material, the draw ratio is 1.0 times in the washing process and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 100, the spinning conditions of Table 20 Was performed.

Comparative Example 28 Comparative Example 29 Comparative Example 30 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Hygroscopicity (%) Flame retardant (cm) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 100 20.75 5.9 0.01 45 220 2.4 1.8 Example 101 21.00 5.6 0.01 48 280 2.5 2.1 Example 102 20.84 5.7 0.02 43 205 2.3 1.7 Example 103 19.95 6.3 0.01 42 250 2.9 2.0 Example 104 20.55 6.0 0.03 50 290 3.1 1.0 Example 105 20.13 6.1 0.01 52 212 2.8 1.4 Example 106 19.74 6.3 0.02 44 210 2.7 1.2 Example 107 20.87 5.7 0.01 46 230 3.2 1.3 Example 108 20.14 6.1 0.02 50 220 3.1 1.3 Example 109 20.20 6.0 0.01 44 260 3.4 1.4 Example 110 21.04 5.6 0.01 46 230 2.8 1.2 Comparative Example 28 10.8 1.9 0.30 120 210 3.1 0 Comparative Example 29 11.2 2.1 0.32 138 200 3.2 0 Comparative Example 30 9.6 1.7 0.31 132 215 3.0 0

As shown in Table 21, the optical cable covering material including the polyketone multifilament prepared according to the embodiment of the present invention was excellent in strength, elongation, low hygroscopicity, and was excellent in flame retardancy and thus suitable for use as an optical cable covering material.

Example 111

After applying the polyketone fibers obtained through the process of Preparation Example 1 to the warp and weft yarn and woven into a plain weave, the acrylic resin is bonded and coated by applying pressure in a chamber, and then laminated to the mold to harden A polyketone radar dome structure was fabricated.

Example 112

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method was adjusted to 240, 250, 260 and 268 ℃, it is the same as Example 111.

Example 113

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 111.

Example 114

After applying the polyketone fibers obtained through the process of Preparation Example 4 to the warp and weft yarn and woven into a plain weave, the acrylic resin is bonded and coated by applying pressure in a chamber, and then laminated on the mold to cure A polyketone radar dome structure was fabricated.

Example 115

Same as Example 114 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 116

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 114.

Example 117

After applying the polyketone fibers obtained through the process of Preparation Example 7 to the warp and weft yarn and woven into a plain weave, the acrylic resin is bonded to the coating by applying pressure in the chamber, and then laminated to the mold to cure A polyketone radar dome structure was fabricated.

Example  118

Same as Example 117 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 119

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 117.

Example 120

As a phenolic heat stabilizer, the same procedure as in Example 111 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 121

As a phenolic heat stabilizer, the same procedure as in Example 111 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 31 to 33

Except for using aramid fiber in the manufacture of the radar dome structural material, the draw ratio in the water washing process to 1.0 times and performing the hot air drying method instead of hot roll drying method, it was carried out in the same manner as in Example 111, spinning of Table 22 Carried out under conditions.

Comparative Example 31 Comparative Example 32 Comparative Example 33 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 111 20.75 5.9 220 2.4 1.8 Example 112 21.00 5.6 280 2.5 2.1 Example 113 20.84 5.7 205 2.3 1.7 Example 114 19.95 6.3 250 2.9 2.0 Example 115 20.55 6.0 290 3.1 1.0 Example 116 20.13 6.1 212 2.8 1.4 Example 117 19.74 6.3 210 2.7 1.2 Example 118 20.87 5.7 230 3.2 1.3 Example 119 20.14 6.1 220 3.1 1.3 Example 120 20.20 6.0 260 3.4 1.4 Example 121 21.04 5.6 230 2.8 1.2 Comparative Example 31 10.8 1.9 210 3.1 0 Comparative Example 32 11.2 2.1 200 3.2 0 Comparative Example 33 9.6 1.7 215 3.0 0

As shown in Table 23, the polyketone multifilament manufactured by the embodiments of the present invention was excellent in strength, elongation, and initial modulus, and the radar dome structural material including the same was found to be suitable for use as a radar dome structural material.

Example 122

After applying the polyketone fibers obtained through the process of Preparation Example 1 to the warp and weft yarn, and woven into plain weave, the thermoplastic or thermosetting resin was bonded to apply pressure in the chamber, and then laminated to the lower mold for bobbin manufacturing and injection molding To prepare a bobbin of the polyketone superconducting coil.

Example 123

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber system was adjusted to 240, 250, 260 and 268 ℃, it is the same as Example 122.

Example 124

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method was adjusted to 240, 255, 265 and 272 ℃, it is the same as Example 122.

Example 125

After applying the polyketone fibers obtained through the process of Preparation Example 4 to the warp and weft yarn, and woven into a plain weave, the thermoplastic or thermosetting resin was bonded to apply pressure in the chamber, and then laminated to the lower mold for bobbin injection molding To prepare a bobbin of the polyketone superconducting coil.

Example 126

It is the same as Example 125 except the intrinsic viscosity of polyketone polymer was adjusted to 6.1 dl / g.

Example 127

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 125.

Example 128

After applying the polyketone fibers obtained through the process of Preparation Example 7 to the warp and weft yarn, and woven into plain weave, the thermoplastic or thermosetting resin is bonded to apply pressure in the chamber, and then laminated to the lower mold for bobbin injection molding To prepare a bobbin of the polyketone superconducting coil.

Example 129

Same as Example 128 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 130

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 128.

Example 131

As a phenolic heat stabilizer, the same procedure as in Example 122 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 132

As a phenolic heat stabilizer, the same procedure as in Example 122 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 34 to 36

In the preparation of the bobbin of the superconducting coil, it was carried out in the same manner as in Example 122 except that the aramid fibers were used, the draw ratio was 1.0 times in the washing step and the hot air drying method, not the hot roll drying method, was performed. It was performed under spinning conditions.

Comparative Example 34 Comparative Example 35 Comparative Example 36 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Strength (g / d) Elongation (%) Cross Section% Change Example 122 20.75 5.9 9 Example 123 21.00 5.6 8 Example 124 20.84 5.7 7 Example 125 19.95 6.3 11 Example 126 20.55 6.0 12 Example 127 20.13 6.1 10 Example 128 19.74 6.3 8 Example 129 20.87 5.7 13 Example 130 20.14 6.1 12 Example 131 20.20 6.0 8 Example 132 21.04 5.6 9 Comparative Example 34 10.8 1.9 22 Comparative Example 35 11.2 2.1 21 Comparative Example 36 9.6 1.7 18

As shown in Table 25, the bobbin of the superconducting coil including the polyketone fiber prepared according to the embodiment of the present invention was found to be suitable for use as a bobbin of the superconducting coil due to its excellent strength. In addition, it has been found to be suitable for use as a coating material for superconducting coils instead of bobbins for superconducting coils.

Example 133

The cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 1.

Example 134

It is the same as Example 133 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 135

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 133.

Example 136

The cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 4.

Example 137

Same as Example 136 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 138

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 136.

Example 139

The cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 7.

Example 140

Same as Example 139 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 141

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 141.

Example 142

As a phenolic heat stabilizer, the same procedure as in Example 133 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 143

As a phenolic heat stabilizer, the same solution as in Example 133 was carried out except that a 0.1% solution of Adeka AO80 and methanol solution was applied before drying and stretching.

Comparative Examples 37 to 39

In the manufacture of cryogenic insulation material was carried out in the same manner as in Example 133, except that aramid fibers were used, the draw ratio was 1.0 times in the water washing process and the hot air drying method is carried out instead of the hot roll drying method, spinning of Table 26 Carried out under conditions.

Comparative Example 37 Comparative Example 38 Comparative Example 39 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Strength (g / d) Elongation (%) Insulation test Cross Section% Change Example 133 20.75 5.9 OK 9 Example 134 21.00 5.6 OK 8 Example 135 20.84 5.7 OK 7 Example 136 19.95 6.3 OK 11 Example 137 20.55 6.0 OK 12 Example 138 20.13 6.1 OK 10 Example 139 19.74 6.3 OK 8 Example 140 20.87 5.7 OK 13 Example 141 20.14 6.1 OK 12 Example 142 20.20 6.0 OK 8 Example 143 21.04 5.6 OK 9 Comparative Example 37 10.8 1.9 OK 22 Comparative Example 38 11.2 2.1 OK 21 Comparative Example 39 9.6 1.7 OK 18

As shown in Table 27, the cryogenic insulation material including the polyketone fiber manufactured according to the embodiment of the present invention was found to be suitable for use as a cryogenic insulation material due to its excellent strength.

Example 144

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 1, followed by thermocompression, followed by cutting and warming and pressing through a press to form a curved surface to manufacture a ski board including polyketone fibers.

Example 145

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method is adjusted to 240, 250, 260 and 268 ℃, it is the same as in Example 144.

Example 146

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 144.

Example 147

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 4, followed by thermocompression, followed by cutting and warming and pressing through a press to form a curved surface to manufacture a ski board including polyketone fibers.

Example 148

Same as Example 147 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 149

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 147.

Example 150

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 7, followed by thermocompression, followed by cutting and warming and pressing through a press to form a curved surface to manufacture a ski board including polyketone fibers.

Example 151

It is the same as Example 150 except the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 152

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 150.

Example 153

As a phenolic heat stabilizer, the same procedure as in Example 153 was performed except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 154

As a phenolic heat stabilizer, the same procedure as in Example 153 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 40 to 42

Aramid fiber was used in the manufacture of the ski board, the draw ratio in the washing process was carried out in the same manner as in Example 144, except that the draw ratio is 1.0 times and the hot air drying method, not hot roll drying method, the spinning conditions of Table 28 Was performed.

Comparative Example 40 Comparative Example 41 Comparative Example 42 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Cross Section% Change Example 144 20.75 5.9 9 Example 145 21.00 5.6 8 Example 146 20.84 5.7 7 Example 147 19.95 6.3 11 Example 148 20.55 6.0 12 Example 149 20.13 6.1 10 Example 150 19.74 6.3 8 Example 151 20.87 5.7 13 Example 152 20.14 6.1 12 Example 153 20.20 6.0 8 Example 154 21.04 5.6 9 Comparative Example 40 10.8 1.9 22 Comparative Example 41 11.2 2.1 21 Comparative Example 42 9.6 1.7 18

As shown in Table 29, the skiboard including the polyketone fiber prepared according to the embodiment of the present invention was found to be suitable for use as a skiboard because of excellent strength of the polyketone fiber.

Example 155

Using a polyketone fiber obtained through the process of Preparation Example 1 was prepared a tennis racket wire.

Example 156

It is the same as Example 155 except for adjusting the temperature of each step of 1st stage and 2nd stage to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 157

It is the same as Example 155 except the temperature of each step of 1st and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Example 158

Using a polyketone fiber obtained through the process of Preparation Example 4 was prepared for the tennis racket wire.

Example 159

Same as Example 158 except that the inherent viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 160

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 158.

Example 161

Using a polyketone fiber obtained through the process of Preparation Example 7 was prepared for the tennis racket wire.

Example 162

It is the same as Example 161 except the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 163

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 161.

Example 164

As a phenolic heat stabilizer, the same procedure as in Example 155 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 165

As a phenolic heat stabilizer, the same procedure as in Example 155 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 43 to 45

Aramid fiber was used in the manufacture of the tennis racket wire, the draw ratio in the washing process was carried out in the same manner as in Example 155, except that the draw ratio is 1.0 times and the hot air drying method instead of the hot roll drying method, It was performed under spinning conditions.

Comparative Example 43 Comparative Example 44 Comparative Example 45 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) 10g / d Stress Elongation (%) Elongation (%) when stressed from 19.0 g / d to cutting Example 155 20.75 5.9 220 2.4 1.8 Example 156 21.00 5.6 280 2.5 2.1 Example 157 20.84 5.7 205 2.3 1.7 Example 158 19.95 6.3 250 2.9 2.0 Example 159 20.55 6.0 290 3.1 1.0 Example 160 20.13 6.1 212 2.8 1.4 Example 161 19.74 6.3 210 2.7 1.2 Example 162 20.87 5.7 230 3.2 1.3 Example 163 20.14 6.1 220 3.1 1.3 Example 164 20.20 6.0 260 3.4 1.4 Example 165 21.04 5.6 230 2.8 1.2 Comparative Example 43 10.8 1.9 210 3.1 0 Comparative Example 44 11.2 2.1 200 3.2 0 Comparative Example 45 9.6 1.7 215 3.0 0

As shown in Table 31, the skiboard including the polyketone fiber prepared according to the embodiment of the present invention was found to be suitable for use as a wire for tennis rackets due to the excellent strength of the polyketone fiber.

Example 166

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 1, followed by thermocompression, followed by heating and pressing through a press to prepare a yacht structural material including the polyketone fibers.

Example 167

It is the same as Example 166 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 168

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method was adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 166.

Example 169

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 4, followed by thermocompression, followed by heating and pressing through a press to prepare a yacht structural material including the polyketone fibers.

Example 170

Same as Example 169, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 171

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 169.

Example 172

Melamine resin was laminated on the polyketone fibers obtained through the process of Preparation Example 7, followed by thermocompression, followed by cutting and warming and pressing through a press to prepare a yacht structural material including the polyketone fibers.

Example 173

Same as Example 172 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 174

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 172.

Example 175

As a phenolic heat stabilizer, the same procedure as in Example 166 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 176

As a phenolic heat stabilizer, the same procedure as in Example 16 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 46 to 48

Except for using aramid fiber in the manufacture of yacht structural materials, the draw ratio is 1.0 times in the water washing process and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 166, the spinning conditions of Table 32 Was performed.

Comparative Example 46 Comparative Example 47 Comparative Example 48 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Cross Section% Change Example 166 20.75 5.9 9 Example 167 21.00 5.6 8 Example 168 20.84 5.7 7 Example 169 19.95 6.3 11 Example 170 20.55 6.0 12 Example 171 20.13 6.1 10 Example 172 19.74 6.3 8 Example 173 20.87 5.7 13 Example 174 20.14 6.1 12 Example 175 20.20 6.0 8 Example 176 21.04 5.6 9 Comparative Example 46 10.8 1.9 22 Comparative Example 47 11.2 2.1 21 Comparative Example 48 9.6 1.7 18

As shown in Table 33, the yacht structural member including the polyketone fiber prepared according to the embodiment of the present invention was found to be suitable for use as a yacht structural member due to its excellent strength.

Example 177

The yacht sail was manufactured using the polyketone fiber obtained through the process of Preparation Example 1.

Example 178

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method was adjusted to 240, 250, 260 and 268 ℃, it is the same as in Example 177.

Example 179

Except that the temperature of each step of the first stage and the second stage in the stretching of the heating chamber method is adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 177.

Example 180

A yacht sail was manufactured using the polyketone fiber obtained through the process of Preparation Example 4.

Example 181

It is the same as Example 180 except the intrinsic viscosity of polyketone polymer was adjusted to 6.1 dl / g.

Example 182

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g, the same as in Example 180.

Example 183

The fiber obtained through the manufacturing example 7 was wound up to prepare a fiber for manufacturing a flexible container.

Example 184

Same as Example 183, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 185

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 183.

Example 186

As a phenolic heat stabilizer, the same procedure as in Example 177 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 187

As a phenolic heat stabilizer, the same procedure as in Example 177 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 49 to 51

Except for using aramid fiber in the manufacture of yacht sails, the draw ratio in the water washing process to 1.0 times and the hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 177, the spinning conditions of Table 34 Was performed.

Comparative Example 49 Comparative Example 50 Comparative Example 51 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Example 177 20.75 5.9 Example 178 21.00 5.6 Example 179 20.84 5.7 Example 180 19.95 6.3 Example 181 20.55 6.0 Example 182 20.13 6.1 Example 183 19.74 6.3 Example 184 20.87 5.7 Example 185 20.14 6.1 Example 186 20.20 6.0 Example 187 21.04 5.6 Comparative Example 49 10.8 1.9 Comparative Example 50 11.2 2.1 Comparative Example 51 9.6 1.7

Yacht sail comprising a polyketone fiber prepared according to an embodiment of the present invention as shown in Table 35 is excellent in strength and appeared to be suitable for use as a sail sail.

Example 188

The polyketone fibers obtained through the process of Preparation Example 1 were laminated with an acrylic resin, put into a mold, and heated and pressurized at 150 ° C. and 5 bar to prepare a racing bicycle frame.

Example 189

It is the same as Example 188 except that the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 190

It is the same as Example 188 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Example 191

The polyketone fibers obtained through the process of Preparation Example 4 were laminated with an acrylic resin, put into a mold, and heated and pressurized at 150 ° C. and 5 bar to manufacture a racing bicycle frame.

Example 192

Same as Example 191, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 193

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 191.

Example 194

The polyketone fibers obtained through the process of Preparation Example 7 were laminated with an acrylic resin, put into a mold, and heated and pressurized at 150 ° C. and 5 bar to prepare a racing bicycle frame.

Example 195

Same as Example 194, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 196

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 194.

Example 197

As a phenolic heat stabilizer, the same procedure as in Example 188 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to one dip before drying.

Example 198

As a phenolic heat stabilizer, the same procedure as in Example 188 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 52 to 54

Except for using aramid fiber in the manufacture of racing bicycles, the draw ratio in the water washing process to 1.0 times and hot air drying method instead of hot roll drying method was carried out in the same manner as in Example 188, the spinning of Table 36 Carried out under conditions.

Comparative Example 52 Comparative Example 53 Comparative Example 54 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Example 188 20.75 5.9 220 2.4 1.8 Example 189 21.00 5.6 280 2.5 2.1 Example 190 20.84 5.7 205 2.3 1.7 Example 191 19.95 6.3 250 2.9 2.0 Example 192 20.55 6.0 290 3.1 1.0 Example 193 20.13 6.1 212 2.8 1.4 Example 194 19.74 6.3 210 2.7 1.2 Example 195 20.87 5.7 230 3.2 1.3 Example 196 20.14 6.1 220 3.1 1.3 Example 197 20.20 6.0 260 3.4 1.4 Example 198 21.04 5.6 230 2.8 1.2 Comparative Example 52 10.8 1.9 210 3.1 0 Comparative Example 53 11.2 2.1 200 3.2 0 Comparative Example 54 9.6 1.7 215 3.0 0

As shown in Table 37, the racing bicycle including the polyketone fiber prepared by the examples of the present invention was found to be suitable for use as a racing bicycle due to its excellent strength.

Example 199

Using the fibers obtained in the manufacturing example 1 process as the warp and weft yarn, weaving plain weave fabric of both the warp density and weft density of 70 / inch. Coating fabric was prepared by coating a thermoplastic polyurethane resin added with titanium oxide on both sides of the woven fabric.

Example 200

A polyketone coated fabric for parachute or peraglide was prepared in the same manner as in Example 1 except that the polyketone fiber was prepared by performing 1.2 times stretching in the washing process.

Example 201

A polyketone coated fabric for parachute or peraglide was prepared in the same manner as in Example 1 except that the polyketone fiber was prepared by performing 1.6-fold stretching in the washing process.

Comparative Example 55

Using 1000 denier polyester fibers as warp and weft yarns, weaving plain weave fabrics with both warp and weft density of 22 bones / inch. Coating fabric was prepared by coating a thermoplastic polyurethane resin on both sides of the woven fabric. Subsequently, a polyester film was laminated on one side of the coating fabric using a urethane adhesive to prepare a parachute membrane material.

Experimental Example 1

Tensile strength and helium leakage of the airship membrane material prepared in Examples 199 to 201 and Comparative Example 55, respectively, were evaluated, and the results are shown in Table 1 below.

Multifilament Property Monofilament Property Tensile strength (kg / cm) Weight (g / m2) Helium leak (l / m2 hours Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Example 199 108 187 1.8 220 2.4 1.8 Example 200 157 192 1.1 280 2.5 2.1 Example 201 171 195 1.3 205 2.3 1.7 Comparative Example 55 78 238 3.8 210 3.1 0

As shown in Table 38, the parachute including the polyketone fiber prepared according to the embodiment of the present invention was found to be suitable for use as a parachute due to its excellent strength.

Example 202

Safety gloves were prepared using the polyketone fibers obtained through the Preparation Example 1.

Example 203

It is the same as Example 202 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 204

It is the same as Example 202 except the temperature of each step of 1st and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Example 205

Safety gloves were prepared using the polyketone fibers obtained through the Preparation Example 4 process.

Example 206

It was the same as Example 205 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 207

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 205.

Example 208

Safety gloves were prepared using the polyketone fibers obtained through the Preparation Example 7 process.

Example 209

Same as Example 208 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 210

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 208.

Example 211

As a phenolic heat stabilizer, the same procedure as in Example 202 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 212

As a phenolic heat stabilizer, the same procedure as in Example 202 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 56 to 58

Except for using aramid fiber in the manufacture of safety gloves, the draw ratio in the washing process to 1.0 times and hot air drying method, not hot roll drying method was carried out in the same manner as in Example 202, the spinning conditions of Table 39 Was performed.

Comparative Example 56 Comparative Example 57 Comparative Example 58 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Drawing company Strength (g / d) Elongation (%) Cross Section% Change Example 202 20.75 5.9 9 Example 203 21.00 5.6 8 Example 204 20.84 5.7 7 Example 205 19.95 6.3 11 Example 206 20.55 6.0 12 Example 207 20.13 6.1 10 Example 208 19.74 6.3 8 Example 209 20.87 5.7 13 Example 210 20.14 6.1 12 Example 211 20.20 6.0 8 Example 212 21.04 5.6 9 Comparative Example 56 10.8 1.9 22 Comparative Example 57 11.2 2.1 21 Comparative Example 58 9.6 1.7 18

As shown in Table 40, the safety gloves including the polyketone fibers prepared by the examples of the present invention were found to be suitable for use as safety gloves due to their excellent strength.

Example 213

The polyketone fibers obtained through the above Preparation Example 1 were laminated with a rubber sheet and pressed to form a sole, and then put into a mold together with the upper to simultaneously form a shoe for safety protection.

Example 214

It is the same as Example 213 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 215

It is the same as Example 213 except the temperature of each step of 1st and 2nd stage was adjusted to 240, 255, 265, and 272 degreeC in extending | stretching of a heating chamber system.

Example 216

The polyketone fibers obtained through the manufacturing example 4 were laminated with a rubber sheet and pressed to form an outsole, and then put into a mold together with the upper to form a shoe for safety at the same time.

Example 217

The same as in Example 216 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.

Example 218

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 216.

Example 219

The polyketone fibers obtained through the manufacturing example 7 were laminated with a rubber sheet and pressed to form an outsole, and then put into a mold together with the upper to form a shoe for safety at the same time.

Example 220

Same as Example 219 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 221

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 219.

Example 222

As a phenolic heat stabilizer, the same procedure as in Example 213 was carried out except that a 0.1% solution of the mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 223

A phenolic heat stabilizer was the same as in Example 213 except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Examples 59 to 61

In the preparation of the composite material was carried out in the same manner as in Example 205 except for using a polypropylene film and a PAN-based carbon fabric, the draw ratio in the water washing process to 1.0 times and performing a hot air drying method instead of hot roll drying method. , The spinning conditions of Table 41 were carried out.

Comparative Example 59 Comparative Example 60 Comparative Example 61 Hot Air Dryer Temperature (℃) 240 ℃ 260 ℃ 280 ℃ Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x

Multifilament Property Monofilament Property Strength (g / d) Elongation (%) Initial modulus (g / d) % Elongation at 10.0 g / d stress Elongation (%) when stressed from 19.0 g / d to cutting Example 213 20.75 5.9 220 2.4 1.8 Example 214 21.00 5.6 280 2.5 2.1 Example 215 20.84 5.7 205 2.3 1.7 Example 216 19.95 6.3 250 2.9 2.0 Example 217 20.55 6.0 290 3.1 1.0 Example 218 20.13 6.1 212 2.8 1.4 Example 219 19.74 6.3 210 2.7 1.2 Example 220 20.87 5.7 230 3.2 1.3 Example 221 20.14 6.1 220 3.1 1.3 Example 222 20.20 6.0 260 3.4 1.4 Example 223 21.04 5.6 230 2.8 1.2 Comparative Example 59 10.8 1.9 210 3.1 0 Comparative Example 60 11.2 2.1 200 3.2 0 Comparative Example 61 9.6 1.7 215 3.0 0

As shown in Table 42, the shoe including the polyketone fiber manufactured according to the embodiment of the present invention was excellent in strength and was found to be suitable for use as an industrial safety shoe.

Example 224

A 60% by weight zinc bromide solution was injected into the extruder maintained at an injection temperature of 25 ° C. and 30 ° C. at a speed of 13000 g / hour with a gear pump, and had a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 ㎗ / g. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55 to 60 ° C., degassed, and the polyketone solution was filtered through a disk filter to remove impurities, and then polyketone fibers were produced by wet spinning through G / P.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃.

Example 225

It is the same as Example 224 except the temperature of each step of 1st stage and 2nd stage was adjusted to 240, 250, 260, and 268 degreeC in extending | stretching of a heating chamber system.

Example 226

Except that the temperature of each step of the first and second stages in the stretching of the heating chamber method was adjusted to 240, 255, 265 and 272 ℃, it is the same as in Example 224.

Example 227

A polyketone powder with a zinc bromide solution having a concentration of 60% by weight was injected at an injection temperature of 25 ° C. at an internal temperature of 30 ° C. with a gear pump at a speed of 13000 g / hour, having a molecular weight distribution of 3.0 and an intrinsic viscosity of 5.7 ㎗ / g. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55 to 60 ° C., degassed, and the polyketone solution was filtered through a disk filter to remove impurities, and then polyketone fibers were produced by wet spinning through G / P.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃.

Example 228

Except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g is the same as in Example 7.

Example 229

The intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 227.

Example 230

A polyketone powder with a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 ㎗ / g is injected into the extruder with a concentration of 60% by weight of a zinc bromide solution at an injection temperature of 25 ° C. at a speed of 13000 g / hour using a gear pump. The extruder was injected at 1160g / hour with a silver screw type feeder, so that the residence time in the extruder swelling zone was 0.8 minutes and the temperature was raised to 40 ° C, so that the polyketone powder was sufficiently dissolved in the metal salt solution. The temperature was maintained at 55 to 60 ° C., degassed, and the polyketone solution was filtered through a disk filter to remove impurities, and then polyketone fibers were produced by wet spinning through G / P.

The nozzle odd number and hole diameter were 667 and 0.18 mm, respectively, and a circular nozzle having an L / D of 1 was used and the air gap was 10 mm. The concentration of polyketone in the discharged solution was 8.2% by weight and homogeneous without undissolved polyketone particles.

The obtained fiber was stretched 1.2 times in the washing process, and before drying, the heat stabilizer was immersed in a 0.1% solution of a mixed solution of Adeka's AO80 and methanol with a phenolic heat stabilizer. In the drying process, after stretching 1.2 times by hot roll drying method, fibers were produced by heating chamber method with total draw ratio of 16.8 times, 1 to 7 times stretching, 2 to 2.4 times stretching, and 2 stages respectively. 3 step stretching of 1.5, 1.3, 1.23 times, each step is carried out at a temperature of 240, 255, 265 and 268 ℃.

Example 231

It is the same as Example 230 except the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 232

The molecular weight distribution of the polyketone polymer was adjusted to 3.5, the same as in Example 230.

Example 233

As a phenolic heat stabilizer, the same procedure as in Example 224 was carried out except that a 0.1% solution of a mixed solution of Adeka AO80 and methanol was subjected to one dip before drying.

Example 234

As a phenolic heat stabilizer, the same solution as in Example 224 was carried out except that a 0.1% solution of Adeka's AO80 and methanol solution was subjected to two dips before drying and before stretching.

Comparative Example 62

In removing impurities, polyketone fibers were prepared in the same manner as in Example 224, except that a candle filter was used instead of the disk filter used in Example 224.

Property evaluation

The replacement cycle of the filter is determined by the differential pressure values at the front and rear of the filter. In the case of the Disk Filter, the replacement is performed when the limit differential pressure reaches 40 bar.

Filter replacement cycle Continuous operation Example 224 45 days or more 45 days or more Example 225 45 days or more 45 days or more Example 226 45 days or more 45 days or more Example 227 45 days or more 45 days or more Example 228 45 days or more 45 days or more Example 229 45 days or more 45 days or more Example 230 45 days or more 45 days or more Example 231 45 days or more 45 days or more Example 232 45 days or more 45 days or more Example 233 45 days or more 45 days or more Example 234 45 days or more 45 days or more Comparative Example 62 Within 9 days Within 9 days

As shown in Table 43, in the case of the embodiment, the life of the filter was improved to 45 days or more, and continuous operation was possible for 45 days or more.

Claims (85)

Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Bulletproof clothing, bulletproof helmets, debris protection materials, polyketone bulletproof materials for aircraft or military aircraft, aircraft wingtip devices, helicopter interior materials, automobile structural materials, ship platforms, Submersible Structural Materials, Fiber Optic Cable Covers, Radar Dome Structural Materials, Bobbins of Superconducting Coils, Cryogenic Superconducting Cables, Skiboards, Wires for Tennis Rackets, Yacht Structural Materials, Yacht Sails, Cycling Bikes, Parachute Polyketone Coating Fabrics, Polyketone Coatings for Paragliding One polyketone fiber product selected from the group consisting of fabrics and safety gloves. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 1, Stretching 1.0 times to 2.0 times during the washing step, and stretches 1.0 times to 2.0 times during the drying process polyketone fiber product. The method of claim 1, The drying process is a hot roll dry type at 100 to 230 ℃, the stretching process is a heating chamber (heating chamber) stretching at 230 to 300 ℃ polyketone fiber product. The method of claim 1, A polyketone fiber product, characterized in that the heat stabilizer is treated before the drying step and the stretching step. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone bulletproof clothing comprising a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 5, The polyketone bulletproof clothing is a polyketone bulletproof clothing, characterized in that manufactured by weaving the fabric in plain weave using polyketone fibers, and then treated with a surfactant, washed with water and dried. The method of claim 5, The polyketone bulletproof clothing is 20 to 35 parts by weight of dipropylene glycol, 0.5 to 5.5 parts by weight of silicone oil, relative to 100 parts by weight of hardoxylated perfluoroalkylethyl acrylate copolymer. Polyketone bulletproof clothing, characterized in that is manufactured through a manufacturing step further comprising the step of immersing in a water repellent consisting of 0.5 to 10 parts by weight of isopropyl alcohol (isopropylalcohol) The method according to any one of claims 5 to 7, The polyketone bulletproof clothing has a bulletproof performance (V50) of polyketone bulletproof clothing, characterized in that 590 to 700m / s on the basis of 5.56mm fragmented coal (FSP). The method of claim 5, The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone fibers are polyketone bulletproof clothing, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation index is 8 to 15%. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone bulletproof helmet characterized in that it comprises a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 10, The polyketone bulletproof helmet is manufactured by applying polyketone fibers to warp and weft yarns and weaving them in plain weave, then applying a pressure in the chamber by adhering thermoplastic or thermosetting resins, and then laminating and curing the lower mold for helmet manufacturing. Featured polyketone bulletproof helmet The method according to any one of claims 10 or 11, The polyketone bulletproof helmet has an average speed (V50) of 590 to 700 kPa measured according to MIL-STD-662F specification, The average speed is measured by averaging the speed at the time of full penetration and the speed at the time of partial penetration using Cal.22 diameter fragment fragment bomb (FSP). The method of claim 10, The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, Polyketone bulletproof helmet, characterized in that the monofilament of the polyketone fiber has a fineness of 0.5 to 8.0 denier Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone fragment protection material comprising a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 14, The polyketone fragment protection material is produced by impregnating polyketone multifilament in an elastic matrix stock solution, and then obtaining an elastic sheet, laminating it, heating and pressurizing the polyketone fragment protection material. The method of claim 14, The polyketone fragment protection material, polyketone fragment protection material, characterized in that the bulletproof performance (V50) is 590 to 700m / s based on 5.56mm fragmented coal (FSP). The method of claim 14, The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone multifilament polyketone fragment protection material, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation index is 8 to 15% Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone bulletproof material for a polyketone aircraft or military aircraft characterized in that it comprises a polyketone fiber produced through a process and stretching process -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 18, The polyketone bulletproof material for aircraft or military aircraft is manufactured by weaving polyketone fibers, cutting and then laminating fabric mats, placing them in a liquid resin molding apparatus to form molded articles, and cutting them in a predetermined length and width direction. Or polyketone bulletproof materials for military aircraft. The method of claim 18, The polyketone anti-ballistic material for aircraft or military aircraft is characterized in that the bulletproof performance (V50) is 590 to 700m / s on the basis of 5.56mm fragmented coal (FSP). The method of claim 18, The molecular weight distribution of the polyketone copolymer is 2.5 to 3.5, The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine) polyketone bulletproof material for aircraft or military aircraft. The method of claim 18, The polyketone multifilament has an initial modulus of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament polyketone bulletproof material for aircraft or military aircraft characterized in that the fineness of 0.5 to 8.0 denier. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone aircraft wingtip device characterized in that it comprises a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 23, The polyketone aircraft wing tip device is manufactured by applying a polyketone multifilament to warp and weft yarn to make a plain weave, impregnated in an elastic matrix stock solution, laminated to a wing tip manufacturing mold, bonded to a thermoplastic or thermosetting resin, and heated and pressurized. Polyketone aircraft wing tip device characterized in that it is. The method of claim 23, The polyketone multifilament is characterized in that the initial modulus value is more than 200g / d, elongation of 2.5 to 3.5% at 10.0g / d, polyketone monofilament extending at least 0.5% at 19.0g / d or more Polyketone aircraft wing tip device. The method of claim 23, The polyketone monofilament polyketone aircraft wing tip device, characterized in that the fineness of 0.5 to 8.0 denier. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone helicopter interior material characterized in that it comprises a polyketone fiber produced through a process and stretching process -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 27, The polyketone helicopter interior material is prepared by applying the polyketone multifilament to the warp and weft yarn to make a plain weave, laminated to a mold and bonded with a thermoplastic or thermosetting resin to heat and pressurized polyketone helicopter interior material The method of claim 27, The molecular weight distribution of the polyketone copolymer is 2.5 to 3.5, The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine) polyketone helicopter interior material The method of claim 27, The polyketone multifilament has an initial modulus of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament is polyketone helicopter interior material, characterized in that the fineness of 0.5 to 8.0 denier Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone automotive structural material comprising a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 31, wherein The polyketone automotive structural member is manufactured by applying polyketone filament to warp and weft yarns and weaving them in plain weave, then applying a pressure in a chamber by bonding a thermoplastic or thermosetting resin, and then laminating and curing the mold. Polyketone Bulletproof Helmet Polyketone Automobile Structural Material The method of claim 31, wherein The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone multifilament is a polyketone automotive structural material, characterized in that the monofilament has a fineness of 1 to 10d, the cross-sectional variation index is 8 to 15% A frame installed on one side of the ship to be movable outward from the inside of the ship; A body coupled to the frame; In the ship platform consisting of, The body is composed of a repeating unit represented by the following general formula (1) and (2), spinning process, water washing a polyketone copolymer of y / x 0 to 0.1, intrinsic viscosity 4 to 8 dl / g A polyketone ship platform comprising a polyketone fiber produced through a process, drying process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 34, wherein The polyketone ship platform is a polyketone ship platform, characterized in that 70 ~ 90% of the strong retention rate deposited at room temperature in 15L chlorine water 15L of chlorine chlorine concentration of 3ppm, pH 7.5 for 24 hours. The method of claim 34, wherein The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament is a polyketone ship platform, characterized in that the fineness of 0.5 to 8.0 denier Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone submersible structural material comprising a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 37, The polyketone submersible structural material is a polyketone submersible structural material, characterized in that the polyketone multi-filament is prepared by injecting the foam with a foam and heated, pressurized and foamed. The method of claim 37, The molecular weight distribution of the polyketone copolymer is 2.5 to 3.5, The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine) polyketone submersible structural material. The method of claim 37, The polyketone multifilament has an initial modulus of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament is polyketone anti-submersible structural material, characterized in that the fineness of 0.5 to 8.0 denier. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone optical cable sheath comprising polyketone fiber manufactured by process and drawing process General formula (1)-[-CH2CH2-CO-] x- General formula (2)-[-CH2-CH (CH3) -CO-] y- (x, y are mole% of each of the general formulas (1) and (2) in the polymer) 42. The method of claim 41 wherein The polyketone optical cable coating material is a polyketone optical cable coating material, characterized in that the moisture absorption rate of 0.01 to 0.03 by the following general formula (3) measured after drying for 30 minutes at 105 ℃. General formula (3) moisture absorption rate = (mass after absorption-mass before absorption) / (mass before absorption) 42. The method of claim 41 wherein The polyketone multifilament is characterized in that the initial modulus value is more than 200g / d, elongation of 2.5 to 3.5% at 10.0g / d, polyketone monofilament extending at least 0.5% at 19.0g / d or more Polyketone optical cable sheathing The method of claim 43, The polyketone monofilament is polyketone optical cable sheathing material characterized in that the fineness of 0.5 to 8.0 denier Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Polyketone radar dome structural material comprising a polyketone fiber produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 45, The polyketone radar dome structure material is manufactured by applying the polyketone fibers to warp and weft yarns and weaving them in plain weave, then applying a pressure in a chamber by adhering thermoplastic or thermosetting resins, and then laminating and curing the mold. Polyketone radar dome structural material. The method of claim 45, The polyketone multifilament is characterized in that the initial modulus value is more than 200g / d, elongation of 2.5 to 3.5% at 10.0g / d, polyketone monofilament extending at least 0.5% at 19.0g / d or more Polyketone radar dome structural material. The method of claim 45, A polyketone radar dome structural material, characterized in that stretched 1.0 times to 2.0 times during the washing step, stretched 1.0 times to 2.0 times during the drying process. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Bobbin of a polyketone superconducting coil comprising polyketone fibers produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 49, The bobbin of the polyketone superconducting coil is applied to warp and weft yarns of polyketone fibers, and then woven into plain weave, and then bonded by thermoplastic or thermosetting resin under pressure in a chamber, and then laminated by injection molding into a lower mold for bobbin manufacturing. Bobbin of polyketone superconducting coils, characterized in that manufactured The method of claim 49, The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone fiber bobbin of the polyketone superconducting coil, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation index is 8 to 15% Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Cryogenic superconducting cable containing polyketone fibers, characterized in that the manufacturing process and stretching process -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 52, wherein The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Cryogenic superconducting cable comprising polyketone fibers, characterized in that The method of claim 52, wherein The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone fiber is a cryogenic superconducting cable containing polyketone fibers, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation index is 8 to 15% Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Ski board comprising a polyketone fiber produced by a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 55, The skiboard comprises a polyketone fiber and a polyketone fiber, characterized in that the polyketone fibers and thermoplastic resins or thermosetting resins are laminated by thermo-compression, and then pressed and warmed and pressed through a press to form a curved surface. The method of claim 55, The polyketone copolymer has a molar ratio of ethylene and propylene of 100: 0 to 90:10, molecular weight distribution of 2.5 to 3.5, The polyketone fiber is a skid comprising a polyketone fiber, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation rate index is 8 to 15%. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 5 to 7 dl / g Tennis racket wire made of polyketone fibers, characterized in that the manufacturing process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 58, The multi-filament of the polyketone fiber is made of polyketone fibers, characterized in that the total denier range of 500 to 3,500, consisting of 100 to 2200 individual filaments, 5 to 16 denier fineness of the cutting load is 6.0 to 40.0kg Wire for tennis rackets. The method of claim 58, The initial modulus of the monofilament of the polyketone fibers is at least 200 g / d, elongation of 2.5 to 3.5% at 10.0 g / d, polyketone fibers characterized in elongation of at least 0.5% at 19.0 g / d or more Tennis racket wire. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Yacht structural material comprising a polyketone fiber, characterized in that is produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) 62. The method of claim 61, The yacht structural material is a yacht structural material comprising a polyketone fiber, characterized in that the polyketone fiber and a thermoplastic resin or thermosetting resin is laminated by thermocompression, and then pressed and heated and pressed through a press to form a curved surface. 62. The method of claim 61, The mole ratio% of ethylene and propylene constituting the polyketone copolymer is 100: 0 to 90:10, Said polyketone fiber has a fineness of 1 to 10d monofilament, the cross-sectional variation index is 8 to 15% yacht structural material comprising a polyketone fiber, characterized in that. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 5 to 7 dl / g Yacht sails made of polyketone fibers, characterized in that the process is produced through a stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 64, wherein The molecular weight distribution of the polyketone copolymer is 2.5 to 3.5, The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine) yacht sails made of polyketone fibers. The method of claim 64, wherein Weaving the polyketone fibers into a fabric; And Polyketone yacht sails, characterized in that it comprises the step of coating the fabric using a coating agent. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 5 to 7 dl / g Competition bicycle made of polyketone fibers, characterized in that the manufacturing process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 67, The composite material including the polyketone fibers may include forming a laminate by laminating the polyketone fibers and a thermoplastic resin; And a polyketone fiber, comprising: heating and pressurizing the laminate. The method of claim 67, The heating is carried out at a temperature of 150 to 220 ℃, the pressurization racing bicycle made of polyketone fibers, characterized in that performed by applying a pressure of 5 to 20MPa for 10 to 20 minutes. The method of claim 67, The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament race bike made of polyketone fibers, characterized in that the fineness of 0.5 to 8.0 denier. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 5 to 7 dl / g Polyketone coating fabric for parachutes or peraglides made of polyketone fibers, characterized in that it is produced through a process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 71, wherein The polyketone coating fabric weaving a plain weave fabric using the polyketone fibers as warp and weft; And coating a thermoplastic polyurethane resin on both sides of the fabric to produce a coating fabric. The method of claim 71 wherein The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, The polyketone monofilament is a polyketone coating fabric for parachute or paraglide made of polyketone fibers, characterized in that the fineness of 0.5 to 8.0 denier. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 4 to 8 dl / g Safety gloves made of polyketone fibers, characterized in that the manufacturing process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 74, wherein The polyketone copolymer is composed of ethylene, propylene, the molar ratio of the ethylene and propylene is from 100: 0 to 90:10, The polyketone fiber is a safety glove made of polyketone fiber, characterized in that the fineness of the monofilament is 1 to 10d, the cross-sectional variation index is 8 to 15%. The method of claim 74, wherein The polyketone safety gloves safety gloves made of polyketone fibers, characterized in that the strength is more than 15g / d. The method of claim 74, wherein Safety gloves made of polyketone fibers, characterized in that the molecular weight distribution of the polyketone copolymer is 2.5 to 3.5. Spinning process, washing process, drying a polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2), y / x of 0 to 0.1, intrinsic viscosity of 5 to 7 dl / g Safety protective shoes comprising a polyketone fiber, characterized in that the manufacturing process and stretching process. -[-CH2CH2-CO-] x- (1) -[-CH2-CH (CH3) -CO-] y- (2) (x, y are mole% of each of the general formulas (1) and (2) in the polymer) The method of claim 78, The shoe is a safety protection shoe comprising a polyketone fiber, characterized in that the rubber sheet and the polyketone fiber laminated by pressing to form a sole, and then put it in the mold with the upper and molded at the same time in the mold. The method of claim 78, The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, elongation of 2.5 to 3.5% at 10.0 g / d, elongation of at least 0.5% at 19.0 g / d or more, and the polyketone monofilament is Safety protection shoes comprising polyketone fibers, characterized in that the fineness of 0.5 to 8.0 denier. Preparing a polyketone solution by injecting an aqueous metal salt solution and polyketone into an extruder to dissolve the polyketone solution; Filtering the polyketone solution through a disk filter to remove impurities; And Method for producing a polyketone fiber using a disk filter comprising the step of producing a polyketone fiber through a spinning process, water washing process, drying process and stretching process. 82. The method of claim 81 wherein The polyketone comprises a catalyst composition comprising a Group 9, Group 10 or Group 11 transition metal compound, a ligand comprising an element of Group 15 and an anion of an acid having a pKa of 4 or less; And polymerizing carbon monoxide and an ethylenically unsaturated compound in the presence of a mixed solvent. 82. The method of claim 81 wherein A method of producing a polyketone fiber using a disk filter, characterized in that the stretching step of 1.0 times to 2.0 times during the washing step, and 1.0 times to 2.0 times during the drying process. 82. The method of claim 81 wherein The drying process is a hot roll dry type at 100 to 230 ℃, the stretching process is a method of producing a polyketone fiber using a disk filter, characterized in that the heating chamber (heating chamber) stretching at 230 to 300 ℃. 82. The method of claim 81 wherein Method of producing a polyketone fiber using a disk filter, characterized in that the heat stabilizer is treated before the drying step and the stretching step.

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