WO2016190596A2 - Produit de polycétone industriel comprenant des fibres de polycétone et son procédé de fabrication - Google Patents

Produit de polycétone industriel comprenant des fibres de polycétone et son procédé de fabrication Download PDF

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WO2016190596A2
WO2016190596A2 PCT/KR2016/005248 KR2016005248W WO2016190596A2 WO 2016190596 A2 WO2016190596 A2 WO 2016190596A2 KR 2016005248 W KR2016005248 W KR 2016005248W WO 2016190596 A2 WO2016190596 A2 WO 2016190596A2
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Prior art keywords
polyketone
fiber
drying
fibers
stretching
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PCT/KR2016/005248
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English (en)
Korean (ko)
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WO2016190596A3 (fr
Inventor
이득진
최영민
황순동
구교성
차준호
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(주)효성
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Priority claimed from KR1020150074159A external-priority patent/KR101705638B1/ko
Priority claimed from KR1020150074176A external-priority patent/KR101664912B1/ko
Priority claimed from KR1020150074156A external-priority patent/KR101716225B1/ko
Priority claimed from KR1020150074174A external-priority patent/KR101716202B1/ko
Priority claimed from KR1020150074161A external-priority patent/KR101716228B1/ko
Priority claimed from KR1020150074162A external-priority patent/KR101716229B1/ko
Priority claimed from KR1020150074171A external-priority patent/KR101675288B1/ko
Priority claimed from KR1020150074167A external-priority patent/KR101716230B1/ko
Priority claimed from KR1020150074164A external-priority patent/KR101725825B1/ko
Priority claimed from KR1020150074158A external-priority patent/KR101716226B1/ko
Priority claimed from KR1020150074178A external-priority patent/KR101765791B1/ko
Priority claimed from KR1020150074173A external-priority patent/KR101716201B1/ko
Priority claimed from KR1020150074166A external-priority patent/KR101796978B1/ko
Priority claimed from KR1020150074168A external-priority patent/KR101716231B1/ko
Priority claimed from KR1020150074163A external-priority patent/KR101725824B1/ko
Priority claimed from KR1020150074172A external-priority patent/KR101716200B1/ko
Priority claimed from KR1020150074175A external-priority patent/KR101725827B1/ko
Priority claimed from KR1020150074160A external-priority patent/KR101716227B1/ko
Priority claimed from KR1020150074157A external-priority patent/KR101705650B1/ko
Priority claimed from KR1020150074165A external-priority patent/KR101725826B1/ko
Priority claimed from KR1020150074169A external-priority patent/KR101675289B1/ko
Application filed by (주)효성 filed Critical (주)효성
Publication of WO2016190596A2 publication Critical patent/WO2016190596A2/fr
Publication of WO2016190596A3 publication Critical patent/WO2016190596A3/fr

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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/015—Protective gloves
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B51/00—Stringing tennis, badminton or like rackets; Strings therefor; Maintenance of racket strings
    • A63B51/02—Strings; String substitutes; Products applied on strings, e.g. for protection against humidity or wear
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63C—SKATES; SKIS; ROLLER SKATES; DESIGN OR LAYOUT OF COURTS, RINKS OR THE LIKE
    • A63C5/00—Skis or snowboards
    • A63C5/03—Mono skis; Snowboards
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics

Definitions

  • 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.
  • 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.
  • 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.
  • high strength high elongation, vibration and high impact resistance
  • heat resistance not deterioration in dry and wet heat
  • bending resistance not deterioration in dry and wet heat
  • shape stability not deterioration in dry and wet heat
  • 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.
  • 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.
  • polyketone is a material useful as a high strength, high heat resistant resin, fiber, or film.
  • 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.
  • polyketone Since polyketone is easy to thermally crosslink when melted, it is preferable to use wet spinning when fiberizing.
  • polyketone poly (1-oxotrimethylene)
  • fibers containing substantially only carbon monoxide and ethylene, which have excellent physical properties, are susceptible to thermal crosslinking.
  • this fiber is very difficult to produce by melt spinning and can only be obtained substantially by wet spinning.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 °C
  • the stretching process is 230 It is characterized in that the heating chamber (heating chamber) stretching formula at 300 °C, 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 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.
  • 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).
  • V50 bulletproof performance
  • FSP 5.56mm fragmented coal
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • 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.
  • 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;
  • 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.
  • 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.
  • 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).
  • 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 °C.
  • moisture absorption rate (mass after absorption-mass before absorption) / (mass before absorption)
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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%.
  • the bicycle for racing made of polyketone fibers comprises the steps of laminating the polyketone fibers and a thermoplastic resin to form a laminate;
  • the manufacturing including the step of heating and pressing the laminate.
  • the heating is carried out at a temperature of 150 to 220 °C
  • 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.
  • 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.
  • 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;
  • 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.
  • 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.
  • 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.
  • the drying process is a hot roll dry type at 100 to 230 °C
  • the stretching process is characterized in that the heating chamber (heating chamber) stretching at 230 to 300 °C.
  • 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.
  • FIG. 1 is a view schematically showing a candle filter according to the prior art.
  • FIG. 2 is a view schematically showing a disk filter according to the present invention.
  • FIG. 3 is a view schematically showing the upper end of the candle filter and the disk filter.
  • FIG. 4 is a view schematically showing a role of a heat stabilizer according to the prior art.
  • FIG. 5 is a view of a schematic diagram of a hot air drying type dryer according to the prior art.
  • FIG. 6 is a schematic view of a hot roll drying method according to the present invention.
  • FIG. 7 is a cross-sectional view of the dry yarn according to the prior art hot air drying method.
  • FIG. 8 is a cross-sectional view of the dry yarn according to the hot roll drying method of the present invention.
  • FIG. 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.
  • 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.
  • 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.
  • drying process is a hot roll dry type at 100 to 230 °C
  • stretching process is preferably a heating chamber (heating chamber) stretching at 230 to 300 °C.
  • 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.
  • monomers can be added to the reactor during the polymerization if desired to maintain a constant pressure as well as temperature.
  • 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.
  • 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.
  • a mixed solvent of acetic acid and water is used as the liquid medium
  • the concentration of water is less than 10% by volume
  • the catalytic activity is less affected.
  • the concentration is more than 10% by volume
  • the catalytic activity rapidly increases.
  • the concentration of water exceeds 30% by volume
  • catalytic activity tends to decrease.
  • 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.
  • transition metal compounds (a) are nickel and copper compounds
  • 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)
  • 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.
  • 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.
  • 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) ((2,2-dimethyl) ((2,2-dimethyl) ((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.
  • 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.
  • DMSO dimethyl sulfoxide
  • 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.
  • 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.
  • 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.
  • reaction gas to be reacted with the polyketone production catalyst is preferably used by appropriately mixing carbon monoxide and ethylenically unsaturated compounds.
  • 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 ⁇ -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 olefin
  • ethylenically unsaturated compounds are used individually or in mixture of multiple types.
  • preferred ethylenically unsaturated compounds are ⁇ -olefins, more preferably ⁇ -olefins having 2 to 4 carbon atoms, and most preferably ethylene.
  • 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.
  • 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.
  • 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.
  • the polyketone copolymer used as the fiber may be composed of ethylene, propylene and carbon monoxide.
  • 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.
  • 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.
  • the molecular weight distribution of the most preferred polyketones is 2.5 to 3.5.
  • 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
  • HFIP Hexafluoroisopropylalcohol
  • the solution extruded from the spinning nozzle passes through the air gap in the vertical direction and solidifies in the coagulation bath.
  • 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.
  • the filament passed through the coagulation bath is passed through the washing tank.
  • the temperature of the coagulation bath and the washing tank is maintained at about 0 ⁇ 80 °C 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.
  • the coagulation bath is characterized in that the temperature is -10 to 40 °C and the metal salt concentration is 1 to 30% by weight, the water washing bath is preferably 0 to 40 °C temperature and metal salt concentration is 1 to 30% by weight.
  • aqueous metal salt solution recovered as described above may be reused as an aqueous metal salt solution for dissolving polyketone.
  • 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.
  • the filament yarn passing through the interlace nozzle is dried while passing through the drying apparatus.
  • the drying temperature and drying method have a great influence on the post process and the physical properties of the filament.
  • the filament which passed the drying apparatus is finally wound up by a winding machine via a secondary tanning apparatus.
  • 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.
  • hot air heating was more effective for producing high-strength polyketone fibers because the filament is easily damaged by contact with the roller surface.
  • 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.
  • 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 °C to 300 °C.
  • 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.
  • zinc salts include zinc bromide, zinc chloride, zinc iodide, and the like
  • calcium salts include calcium bromide, calcium chloride, calcium iodide, and the like
  • lithium salts such as lithium bromide, lithium chloride, and lithium iodide.
  • the iron salts include iron bromide and iron iodide.
  • 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.
  • 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.
  • an aqueous solution containing zinc bromide is preferable, and the composition ratio of zinc bromide in the metal salt is an important factor.
  • the weight ratio of zinc bromide and calcium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40.
  • 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.
  • the polyketone polymer After degassing the aqueous metal salt solution maintained at 20 to 40 °C at 200torr or less, the polyketone polymer is heated to 60 to 100 °C in a vacuum of 200torr or less and stirred for 0.5 to 10 hours to prepare a homogeneous dope sufficiently dissolved. .
  • 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.
  • 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.
  • the polyketone fibers claimed in the present invention are not limited by the following process.
  • an orifice having a diameter of 100 to 500 ⁇ m and a length of 100 to 1500 ⁇ m, wherein the ratio (L / D) of the diameter and the length is 1 to 3 to 8 times, and the orifice
  • 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.
  • 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.
  • peripheral devices such as a spinning pack and a nozzle are enlarged, which is disadvantageous to the installation surface.
  • the diameter of the nozzle orifice is less than 100 ⁇ m, a large number of trimmings occur during spinning, which adversely affects radioactivity. If the nozzle orifice exceeds 500 ⁇ m, 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.
  • the number of orifices is 100 to 2,200, more preferably 300 to 1,400.
  • 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.
  • 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.
  • 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.
  • the coagulation fluid shakes due to friction between the filament and the coagulation solution.
  • such a phenomenon is a factor that impairs process stability, it is necessary to minimize it.
  • the coagulation bath is characterized in that the temperature is -10 to 40 °C and the metal salt concentration is 1 to 30% by weight, the water washing bath is preferably 0 to 40 °C temperature and metal salt concentration is 1 to 30% by weight.
  • the dryer temperature is 100 °C or more, preferably 200 °C or more to impart an emulsion, heat-resistant agent, antioxidant or stabilizer to the fiber passed through the dryer.
  • the stretching process in the polyketone fibers of the present invention is very important for high strength and hot water resistance improvement.
  • the present invention provides a high-strength fiber through the heat-resistant stability and direct drying method during wet spinning of polyketone.
  • 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.
  • 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.
  • a radical oxidation mechanism polyketones emit carbon dioxide when exposed to oxygen above 90 ° C, resulting in oxidative degradation.
  • polyketones 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.
  • 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.
  • 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 °C. 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 °C 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).
  • 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.
  • the temperature-stretching at which the stretching temperature gradually increases as the draw ratio is increased.
  • the stretching process is carried out at a temperature of 240 to 270 °C, 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.
  • the polyketone fiber 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.
  • 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.
  • 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
  • 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 °C to 100 °C.
  • a surfactant such as NaOH or Na 2 CO 3 at 40 °C to 100 °C.
  • 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.
  • 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.
  • 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.
  • magnesium oxide magnesium hydroxide, zinc oxide, or the like may be used.
  • 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.
  • 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 dl / 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.
  • 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.
  • 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 dl / 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.
  • 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.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Production Example 4.
  • a polyketone powder with a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 dl / 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.
  • 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.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Production Example 8.
  • 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.
  • 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.
  • I.V. 1/4 ⁇ [(R.V.-1) / C] + 3/4 ⁇ (In R.V./C)
  • C represents the concentration of the sample in solution (g / 100ml).
  • 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.
  • the sample 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.
  • 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 (m ⁇ s) 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
  • 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.
  • 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.
  • 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.
  • 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.
  • Moisture absorption rate (%) (mass after absorption-mass before absorption) / (mass before absorption)
  • 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).
  • 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.
  • 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.
  • 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
  • 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, 255, 265, and 272 degreeC in extending
  • 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.
  • Example 4 It is the same as Example 4 except adjusting the intrinsic viscosity of polyketone polymer to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 4.
  • 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.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 7.
  • 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.
  • 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 Example 1 Comparative Example 2 Comparative Example 3 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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 °C.
  • Example 12 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
  • 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 °C.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 15.
  • the polyamide resin was bonded and coated by applying a pressure of 1.5 bar in an 80 ° C. chamber.
  • a bulletproof helmet was prepared by curing at a pressure of 160 bar and a temperature of 130 ° C. for 20 minutes.
  • Example 18 Same as Example 18, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 18.
  • 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 12 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 Example 4 Comparative Example 5 Comparative Example 6 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • Example 23 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 °C, it is the same as in Example 23.
  • Example 23 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 °C, it is the same as in Example 23.
  • Example 26 The same as in Example 26 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 26.
  • Example 29 Same as Example 29, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 29.
  • Example 23 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 23 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.
  • 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 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
  • Example 34 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 °C, the same as in Example 34.
  • Example 37 The same as in Example 37, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 37.
  • Example 40 Same as Example 40 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 40.
  • Example 34 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 34 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.
  • Example 34 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 (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • 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.
  • 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 45 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
  • Example 45 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 °C, it is the same as in Example 45.
  • 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.
  • 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 48 Same as Example 48 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 48.
  • 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.
  • 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 51 Same as Example 51 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 51.
  • 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 45 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 Example 13 Comparative Example 14 Comparative Example 15 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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 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
  • Example 56 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 °C, it is the same as in Example 56.
  • Example 59 Same as Example 59 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 59.
  • 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 62 Same as Example 62 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 62.
  • Example 56 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 56 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 Example 16 Comparative Example 17 Comparative Example 18 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • 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.
  • 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 °C to prepare an automobile structural material.
  • 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.
  • 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 °C to prepare an automobile structural material.
  • Example 70 The same as in Example 70, except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 70.
  • 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.
  • 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 °C to prepare an automobile structural material.
  • Example 73 Same as Example 73, except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 73.
  • Example 67 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 67 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.
  • 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 (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • thermoplastic or thermosetting resin 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 78 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 °C, it is the same as in Example 78.
  • Example 78 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 °C, it is the same as in Example 78.
  • An airbag was manufactured using the polyketone fibers obtained through the preparation example 4 above.
  • Example 81 Same as Example 81 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 81.
  • 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 84 Same as Example 84 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 84.
  • Example 78 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 78 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 Example 22 Comparative Example 23 Comparative Example 24 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • 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 89 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 89 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.
  • 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 92 Same as Example 92 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 92.
  • 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 95 Same as Example 95 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 95.
  • Example 89 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 89 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 Example 25 Comparative Example 26 Comparative Example 27 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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 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
  • Example 100 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 °C, it is the same as in Example 100.
  • Example 103 The same as in Example 103 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 103.
  • Example 106 Same as Example 106 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 106.
  • Example 100 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 100 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.
  • 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 (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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
  • 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.
  • 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 111 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 °C, it is the same as Example 111.
  • Example 111 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 °C, it is the same as in Example 111.
  • Example 114 Same as Example 114 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 114.
  • Example 117 Same as Example 117 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 117.
  • Example 111 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 111 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 Example 31 Comparative Example 32 Comparative Example 33 Hot Air Dryer Temperature (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • 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 122 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 °C, it is the same as Example 122.
  • Example 122 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 °C, it is the same as Example 122.
  • 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 125 It is the same as Example 125 except the intrinsic viscosity of polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 125.
  • thermoplastic or thermosetting resin 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 128 Same as Example 128 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 128.
  • Example 122 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 122 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.
  • Example 122 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 (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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.
  • it has been found to be suitable for use as a coating material for superconducting coils instead of bobbins for superconducting coils.
  • the cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 1.
  • Example 133 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
  • Example 133 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 °C, it is the same as in Example 133.
  • the cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 4.
  • Example 136 Same as Example 136 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 136.
  • the cryogenic insulation material was manufactured using the polyketone fiber obtained through the process of Preparation Example 7.
  • Example 139 Same as Example 139 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 141.
  • Example 133 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 133 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.
  • 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.
  • 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.
  • 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 144 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 °C, it is the same as in Example 144.
  • Example 144 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 °C, it is the same as in Example 144.
  • 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 147 Same as Example 147 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 147.
  • 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 150 It is the same as Example 150 except the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • 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 153 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.
  • 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 (°C) 240 °C 260 °C 280 °C Drawing ratio in water washing process (times) 1.0x 1.0x 1.0x
  • 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 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
  • Example 155 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
  • Example 158 Same as Example 158 except that the inherent viscosity of the polyketone polymer was adjusted to 6.1 dl / g.
  • the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 dl / g as in Example 158.
  • Example 161 It is the same as Example 161 except the molecular weight distribution of the polyketone polymer was adjusted to 2.8.
  • the molecular weight distribution of the polyketone polymer was adjusted to 3.5, which is the same as in Example 161.
  • Example 155 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 155 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.
  • 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.
  • 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.
  • 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 166 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Woven Fabrics (AREA)
  • Polyethers (AREA)
  • Artificial Filaments (AREA)

Abstract

L'objectif de la présente invention est de fournir des fibres de polycétone présentant d'excellentes propriétés en termes de résistance et de résistance à l'eau, qui sont fabriquées à partir d'une solution de polycétone préparée à partir d'un copolymère de monoxyde de carbone, d'éthylène et de propylène ; ainsi qu'un procédé de fabrication associé. Les fibres de polycétone industrielles fabriquées selon la présente invention présentes d'excellentes propriétés en termes de résistance, d'allongement, de résistance à l'eau, de résistance à la chaleur, et de conductivité thermique, et sont par conséquent appropriées pour être utilisées dans des cordes marines, des tuyaux, des produits de protection, des fibres géotextiles pour renforcer des matériaux composites FRP, des câbles, des filets de pêche, des coussins de sécurité gonflables, des isolants thermiques, des ceintures de sécurité, des filets de sécurité, des élingues rondes, des matériaux de film à utiliser dans le domaine de l'aviation, des non-tissés, des non-tissés par filage direct, des courroies de transport, des contenants souples, des lignes de pêche, des cordes de sport, des matériaux composites de fibres de carbone, des lignes de fond, des tapis.
PCT/KR2016/005248 2015-05-27 2016-05-18 Produit de polycétone industriel comprenant des fibres de polycétone et son procédé de fabrication WO2016190596A2 (fr)

Applications Claiming Priority (42)

Application Number Priority Date Filing Date Title
KR1020150074174A KR101716202B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유로 이루어진 경기용 자전거
KR1020150074161A KR101716228B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 헬리콥터 내장재
KR10-2015-0074174 2015-05-27
KR1020150074162A KR101716229B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 자동차 구조재
KR10-2015-0074166 2015-05-27
KR1020150074171A KR101675288B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유로 이루어진 테니스 라켓용 와이어
KR1020150074167A KR101716230B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 초전도 코일의 보빈
KR1020150074164A KR101725825B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 잠수정 구조재
KR10-2015-0074167 2015-05-27
KR1020150074158A KR101716226B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 파편방호 소재
KR1020150074156A KR101716225B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 방탄의류
KR1020150074163A KR101725824B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 선박 플랫폼
KR10-2015-0074176 2015-05-27
KR10-2015-0074168 2015-05-27
KR1020150074159A KR101705638B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 항공기 또는 군항기용 폴리케톤 방탄재
KR10-2015-0074160 2015-05-27
KR1020150074168A KR101716231B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 극저온성 초전도 케이블
KR10-2015-0074159 2015-05-27
KR10-2015-0074173 2015-05-27
KR1020150074166A KR101796978B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 레이더돔 구조재
KR10-2015-0074171 2015-05-27
KR10-2015-0074156 2015-05-27
KR10-2015-0074161 2015-05-27
KR10-2015-0074164 2015-05-27
KR1020150074172A KR101716200B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 요트 구조재
KR1020150074175A KR101725827B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유로 이루어진 낙하산 또는 페러글라이드용 폴리케톤 코팅 직물
KR1020150074160A KR101716227B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 항공기 윙팁장치
KR10-2015-0074175 2015-05-27
KR10-2015-0074163 2015-05-27
KR10-2015-0074172 2015-05-27
KR1020150074157A KR101705650B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 방탄헬멧
KR10-2015-0074158 2015-05-27
KR10-2015-0074169 2015-05-27
KR1020150074165A KR101725826B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 폴리케톤 광케이블 피복재
KR10-2015-0074157 2015-05-27
KR1020150074169A KR101675289B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유를 포함하는 스키보드
KR1020150074176A KR101664912B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유로 이루어진 안전장갑
KR10-2015-0074162 2015-05-27
KR1020150074173A KR101716201B1 (ko) 2015-05-27 2015-05-27 폴리케톤 섬유로 이루어진 요트 돛
KR1020150074178A KR101765791B1 (ko) 2015-05-27 2015-05-27 디스크 필터를 이용한 폴리케톤 섬유의 제조방법
KR10-2015-0074178 2015-05-27
KR10-2015-0074165 2015-05-27

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017002839U1 (de) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketonfasern, deren Herstellung und Verwendung
WO2019171194A1 (fr) 2018-03-06 2019-09-12 Sapa S.P.A. Élément pour compartiment moteur en couches co-moulées pour véhicules
IT201900008217A1 (it) 2019-06-06 2020-12-06 Agotex S R L Substrato composito termoisolante ininfiammabile per autoveicoli e metodo di produzione
IT202100001727A1 (it) 2021-01-28 2022-07-28 Sapa S P A Sistema di isolamento termico di un vano motore mediante l’utilizzo di materiali compositi
IT202100002696A1 (it) 2021-02-08 2022-08-08 Agotex S R L Metodo ottimizzato per la produzione di un termoisolante composito
WO2022198102A1 (fr) * 2021-03-19 2022-09-22 Safari Belting Systems, Inc. Module transporteur dont de petits fragments sont détectables magnétiquement et aux rayons x

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JP4330741B2 (ja) * 1999-12-20 2009-09-16 旭化成せんい株式会社 ポリケトン繊維よりなる防弾防刃チョッキ
JP2004292992A (ja) * 2003-03-27 2004-10-21 Ichimura Sangyo Co Ltd 扁平織物、その積層体、それらを用いたプリプレグ、繊維強化プラスチック並びに複合成型物、及びこれらを用いた防護製品
KR100595990B1 (ko) * 2004-10-22 2006-07-03 주식회사 효성 폴리케톤 섬유 및 그의 제조 방법
KR100960049B1 (ko) * 2007-12-28 2010-05-31 주식회사 효성 폴리케톤 섬유의 제조방법
KR101154703B1 (ko) * 2008-08-22 2012-06-08 코오롱인더스트리 주식회사 방탄용 직물 및 그 제조방법, 및 그를 이용한 방탄복

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017002839U1 (de) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketonfasern, deren Herstellung und Verwendung
WO2018219494A1 (fr) 2017-05-30 2018-12-06 Perlon Gmbh Fibres de polycétone, leur fabrication et leur utilisation
WO2018219495A1 (fr) 2017-05-30 2018-12-06 Perlon Gmbh Soie en filament synthétique, brosse munie de telles soies et procédé pour fabriquer de telles soies
WO2019171194A1 (fr) 2018-03-06 2019-09-12 Sapa S.P.A. Élément pour compartiment moteur en couches co-moulées pour véhicules
IT201900008217A1 (it) 2019-06-06 2020-12-06 Agotex S R L Substrato composito termoisolante ininfiammabile per autoveicoli e metodo di produzione
WO2020245735A1 (fr) 2019-06-06 2020-12-10 Agotex S.R.L. Substrat composite ininflammable et isolant thermique destiné à des véhicules motorisés et procédé de production
IT202100001727A1 (it) 2021-01-28 2022-07-28 Sapa S P A Sistema di isolamento termico di un vano motore mediante l’utilizzo di materiali compositi
EP4035889A1 (fr) 2021-01-28 2022-08-03 Sapa S.p.A. Système d'isolation thermique dans un compartiment moteur au moyen de l'utilisation de matériaux composites
IT202100002696A1 (it) 2021-02-08 2022-08-08 Agotex S R L Metodo ottimizzato per la produzione di un termoisolante composito
WO2022167931A1 (fr) 2021-02-08 2022-08-11 Agotex S.R.L. Procédé optimisé de production d'une isolation thermique composite
WO2022198102A1 (fr) * 2021-03-19 2022-09-22 Safari Belting Systems, Inc. Module transporteur dont de petits fragments sont détectables magnétiquement et aux rayons x

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