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WO2006060523A1 - Procedes continus de fabrication de fibres composites - Google Patents

Procedes continus de fabrication de fibres composites Download PDF

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Publication number
WO2006060523A1
WO2006060523A1 PCT/US2005/043392 US2005043392W WO2006060523A1 WO 2006060523 A1 WO2006060523 A1 WO 2006060523A1 US 2005043392 W US2005043392 W US 2005043392W WO 2006060523 A1 WO2006060523 A1 WO 2006060523A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
polymer
aramid
anisotropic
isotropic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2005/043392
Other languages
English (en)
Inventor
Jon David Hartzler
Bhatnagar Chitrangad
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to BRPI0517126-1A priority Critical patent/BRPI0517126A/pt
Priority to MX2007006390A priority patent/MX2007006390A/es
Priority to JP2007544487A priority patent/JP2008522055A/ja
Priority to CA2586635A priority patent/CA2586635C/fr
Priority to CN2005800414171A priority patent/CN101076622B/zh
Priority to EP05852581A priority patent/EP1825037B1/fr
Publication of WO2006060523A1 publication Critical patent/WO2006060523A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides

Definitions

  • This invention relates to continuous processes for making composite fibers.
  • the invention relates to continuous processes for making composite fibers from aramid polymers.
  • U.S. Patent 5,135,687 discloses a batch process for making a polyvinyl pyrroldione) [PVP]/p-phenylene terephthalamide [PPD-T] composite fiber.
  • the process includes agitating an anisotropic mixture of acid solvent, aramid, and PVP; heating the agitated mixture to above its melting point; extruding the mixture through a spinneret, into and through a non-coagulating layer; and passing the extruded mixture into and through an aqueous coagulating bath.
  • the mixture is heated with stirring for two hours at 85°C.
  • Composite fibers made using aramids in conventional processes have desirable properties including tenacity, dyeability, thermal resistance and adhesion to elastomeric matrices.
  • new and/or improved continuous processes for making composite fibers, particularly composite fibers made from aramid polymers, are desirable.
  • the present invention is directed to these and other important ends.
  • One aspect of the present invention is a process for making a composite fiber.
  • the process includes: continuously combining an anisotropic polymer solution of an aramid polymer and an isotropic solution of a second polymer to form a combined polymer solution; passing the combined polymer solution through at least one static mixer to form a spin dope; and extruding the spin dope through a spinneret to form a composite fiber.
  • the process further includes: passing the composite fiber through an air gap; contacting the composite dope fiber with a quench solution to form a coagulated composite fiber; contacting the coagulated composite fiber with a wash solution; contacting the washed composite fiber with a neutralization solution to form a neutralized and washed composite fiber; drying the neutralized and washed composite fiber; and winding up the dried composite fiber.
  • the dried composite fiber can be wound onto a bobbin on a windup device.
  • Figure 1 is a schematic illustration of one embodiment of a process for making composite yarn in accordance with the present invention.
  • the present invention provides composite fibers of aramids and processes for the preparation of such fibers.
  • the invention further relates to yarns, cords, fabrics, and articles incorporating the fibers, and processes for making such yarns, cords, fabrics, and articles.
  • fiber is used herein interchangeably with "filament”, and means a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length.
  • the fiber cross section can be any shape, but is often somewhat circular.
  • Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floe. Multifilament yarns can be combined to form cords. Yarn can be intertwined and/or twisted.
  • spin refers to the extrusion of a polymer solution through a spinneret.
  • anisotropic solutions of polymers utilize anisotropic solutions of polymers.
  • "Anisotropic" means having microscopic regions that are birefringent; that is, a bulk sample of an anistropic solution depolarizes plane polarized light because the light transmission properties of the microscopic regions of the solution (or polymer spin dope) vary with direction.
  • Anisotropy in the polymer solutions and dopes used in the processes disclosed herein is due to the existence of at least part of the solution or dope in a liquid crystalline state.
  • aramid is meant a polyamide wherein at least 85% of the amide (- CO-NH-) linkages are attached directly to two aromatic rings. Suitable aramid fibers are described in Man-Made Fibers-Science and Technology, Volume 2, Section titled Fiber-Forming Aromatic Polyamides, page 297, W. Black et al., lnterscience Publishers, 1968. Aramid fibers are, also, disclosed in U.S. Patent Nos. 4,172,938; 3,869,429; 3,819,587; 3,673,143; 3,354,127; and 3,094,511.
  • Para-aramids are the primary polymers in aramid yarn fibers of this invention and poly(p-phenylene terephthalamide)(PPD-T) is the preferred para-aramid.
  • PPD-T is meant the homopolymer resulting from mole-for- mole polymerization of p-phenylene diamine and terephthaloyl chloride and, also, copolymers resulting from incorporation of small amounts of other diamines with the p-phenylene diamine and of small amounts of other diacid chlorides with the terephthaloyl chloride.
  • PPD-T means copolymers resulting from incorporation of other aromatic diamines and other aromatic diacid chlorides such as, for example, 2,6-naphthaloyl chloride or chloro- or dichloroterephthaloyl chloride or 3,4'-diaminodiphenylether. Preparation of PPD-T is described in U.S. Patent Nos. 3,869,429; 4,308,374; and 4,698,414.
  • the isotropic solution of polymer can be made using any polymer selected from known flexible chain polymers, but preferred polymers are those that form isotropic solutions in mineral acids, including chlorosulfonic acid and fluorosulfonic acid, particularly sulfuric acid.
  • a highly preferred polymer for use in the isotropic solution is PVP.
  • suitable polymers include aliphatic polyamides (e.g., 6-nylon, 6,6-nylon, and 6,12- nylon), polyaniline, polyether ketone ketone (PEKK), aromatic polyamides (MPD-I, MPD-I/T), and copolymers of PVP, such as PVP/VA(Vinyl Acetate).
  • the formation, during mixing, of droplets of sufficiently small size e.g., having average diameters of about 10 percent or less the magnitude of the diameter desired in a filament formed from the combined polymers, aids in the mixing of the anisotropic aramid solution and the isotropic polymer solution.
  • the droplet size formed during mixing is less than about 5 percent of the desired filament diameter, more preferably less than about 2 percent of the desired filament diameter.
  • a composite fiber can be prepared from PPD-T and a flexible chain polymer.
  • a static mixer comprises a pipe having therein an arrangement of elements (plates) at varying angles with respect to the wall of the pipe.
  • the plates provide shear and mixing as a material flows through the pipe.
  • the number of plates can vary.
  • An example of a suitable static mixer is a Sulzer type SMX, manufactured by Sulzer Chemtech, Tulsa, OK.
  • Conditions and parameters for mixing can be determined by one skilled in the art. For purposes of example only, the following is provided.
  • Homogeneity can be measured by a compositional uniformity coefficient of variation (CoV) with values between 5% and 0.1 %.
  • CoV compositional uniformity coefficient of variation
  • Lower CoVs are obtained by increasing mixer length.
  • An anisotropic solution of an aramid polymer and an isotropic solution of a flexible chain polymer are not fully miscible and form a microscopically inhomogeneous system comprising small droplets that are generally not visible to the naked eye.
  • a measurable parameter is drop size, also called particle size.
  • the drop size can be set by a stress criterion and a strength parameter characteristic of the two polymer solutions, such as interfacial tension.
  • An interfacial tension of about 10 dynes/cm is typical of organics in water, and can be used as a guideline or starting point.
  • the static mixer can be designed to produce dispersed droplets of the isotropic solution within the anisotropic solution with an average diameter that can be as small as about 1/60 of the diameter of the composite fiber or smaller. It is generally desirable to minimize drop size.
  • An equilibrium drop size is preferably obtained by the time the combined polymers have passed through a length in the mixer that is less than about 10 mixer diameters.
  • the optimal dimensions of a static mixer can vary, depending upon the polymer solutions to be mixed, and in particular, on the viscosity and interfacial tension of the solutions. For example, for a pipe size of 0.815 inch (2.07 cm) inner diameter (ID) containing 18 mixer elements, a droplet size of about 0.45-1.3 microns has been estimated with a pressure drop of 407-141 psi (28.6-9.9 kg/cm 2 ).
  • the droplet size is further reduced to an estimated diameter of 0.18-0.55 micron with a pressure drop of 594-205 psi (41.8-14.4 kg/cm 2 ).
  • the pressure drop increases as the number of plates in the mixer increases, and as the diameter of the pipe decreases.
  • One skilled in the art can adjust the diameter and/or number of plates to result in a desired droplet size at a given pressure drop.
  • an aramid polymer 2 is dissolved in an acid solvent, such as sulfuric acid 4, to form an anisotropic solution of aramid polymer.
  • the acid solvent is preferably concentrated, e.g., about 98-101%, typically 98-100.2%, sulfuric acid.
  • Other acids that can be used include chlorosulfonic acid and fluorosulfonic acid.
  • the anisotropic solution of aramid polymer preferably contains a high enough concentration of aramid polymer to form an acceptable filament after extrusion and coagulation.
  • a practical minimum concentration of aramid polymer is that concentration that provides anisotropy in the solution. For example, a concentration of at least about 18 weight percent can be used.
  • Yarn properties such as tenacity and modulus are affected in part by the polymer concentration of the anisotropic solution of aramid polymer, and the concentration can be adjusted to enhance desired properties. Generally, lowering the concentration below about 18 weight percent can cause a decrease in such properties.
  • the polymer and acid for the anisotropic solution are mixed in a mixer 6 such as a twin-screw mixer, while being heated to an elevated temperature, e.g., 80 to 100 0 C for p-phenylene terephthalamide (PPD-T), to provide a solution 58 of the polymer in acid.
  • a mixer 6 such as a twin-screw mixer
  • an elevated temperature e.g. 80 to 100 0 C for p-phenylene terephthalamide (PPD-T)
  • PPD-T p-phenylene terephthalamide
  • the polymer solution is then transferred via transfer pump 8, to vessel 10, where it is deaerated under reduced pressure. Deaeration can be facilitated, e.g., by agitation.
  • the solution 58 is then transferred via pump 12 through filter 14.
  • an isotropic solution 60 is prepared by dissolving a flexible- chain polymer in acid, preferably the same acid as used in making the anisotropic solution.
  • the isotropic solution preferably has a viscosity less than that of the anisotropic solution.
  • the acid is first cooled to a frozen slurry before the flexible chain polymer is added in powder form.
  • the anisotropic solution and the isotropic solution are maintained at about the same temperature after they are made and before they are combined. For example, for an anisotropic solution of poly p-phenyleneterephthalamide combined with an isotropic solution of PVP, the solutions are preferably maintained at a temperature of about 80 0 C prior to mixing.
  • the isotropic solution 60 is prepared in mixer 18, then transferred using jacketed transfer lines via transfer pump 20 through filter 22 and into optional hold tank 24 and through stuffing pump 26 to injection pump 28 and injection valve 16.
  • the isotropic solution 60 is injected into the anisotropic solution 58 to form a combined polymer solution 62.
  • the combined polymer solution 62 is biphasic, due to immiscibility of the anisotropic solution of aramid polymer and the isotropic solution of flexible chain polymer.
  • the combined polymer solution 62 is passed through at least one static mixer 30 and optional additional static mixer(s) 32 to form a mixed, combined polymer solution 64. In preferred embodiments, two mixers are used.
  • the mixers are placed as to minimize the residence time (time between the initial combining of the solutions and extrusion from the spinneret) of the combined solutions.
  • the residence time after mixing is less than 20 minutes, preferably less than 15 minutes, more preferably less than 10 minutes. More than two static mixers can be used, for example, to form smaller size droplets and/or to redisperse any agglomerated droplets.
  • the mixed, combined polymer solution is then pumped via meter pump 34 to optional heat exchanger 36, to help control the temperature of the combined polymer solution.
  • the concentration of aramid polymer in the mixed, combined polymer solution 64 is preferably high enough to provide a liquid-crystalline dope, preferably at least about 15 weight percent, more preferably at least about 16 weight percent.
  • the maximum total concentration of polymers in the dope is limited primarily by practical factors, such as polymer solubility and dope viscosity.
  • the concentration of total solids in the dope is preferably no more than about 22 weight percent, and more preferably no more than about 20 weight percent.
  • Each polymer solution and/or the combined stream can contain additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
  • the mixed, combined polymer solution 64 is extruded through spinneret 38 to form filament(s) 42.
  • the spinneret 38 preferably contains a plurality of holes. The number of holes in the spinneret and their arrangement is not critical to the invention, but it is desirable to maximize the number of holes for economic reasons.
  • the spinneret 38 can contain as many as 100 or 1000 or more, and they may be arranged in circles, grids, or in any other desired arrangement.
  • the spinneret 38 can be constructed out of any materials that are resistant to the acids used in the process. Materials suitable for use in the spinnerets of the present process are disclosed, for example, in US Patents 4,137,032 and 4,054,468.
  • Filaments 42 exiting the spinneret 38 enter gap 40 between the spinneret 38 and a coagulation bath (quench bath) 44 containing water, where the acid solvent is removed.
  • the gap 40 is typically called an "air gap” although it need not contain air.
  • the gap 40 can contain any fluid that does not induce coagulation or react adversely with the stream, such as air, nitrogen, argon, helium or carbon dioxide.
  • spin stretch factor is the ratio of the velocity of a fiber as it exits the coagulating bath to the jet velocity. Jet velocity is the average velocity of the spinning dope exiting the spinneret as calculated from the volume of material passing through an orifice per unit time and the cross- sectional area of the orifice.
  • the minimum spin stretch factor for use with a particular composition and orifice is that which allows the formation of a filament of relatively uniform denier and having desired physical properties.
  • the practical upper limit of the spin stretch factor is preferably that at which breakage is eliminated.
  • the filament then is passed via feed rolls 46 to wash station 48 and neutralization station 50. Then the filament is dried in dryer 52 to remove water.
  • the temperature of the filament as it exits the dryer is typically 120°C to 220 0 C.
  • the dryer residence time of the filament is typically several seconds. Finish is applied at finish applicator 54.
  • the filament can be wound up onto a bobbin at windup device 56.
  • the coagulated filament is washed in one or more wash steps to remove acid solvent from the filament.
  • the washing and neutralization of the filament is preferably carried out in a continuous process by running the filament through a series of baths and/or through one or more washing cabinets.
  • Washing cabinets typically comprise an enclosed cabinet containing one or more rolls which the filament travels around a number of times, and across, prior to exiting the cabinet. As the filament travels around the roll, it is sprayed with a washing fluid. The washing fluid is continuously collected in the bottom of the cabinet and drained therefrom.
  • the temperature of the washing fluid(s) is preferably at least about 5°C, and preferably no greater than about 65°C, more preferably no greater than about 50 0 C. In a continuous process, the duration of the entire washing process which includes the time in the coagulation bath and in the washing bath(s) and/or cabinet(s) is sufficient to remove acid solvent from the spun filaments.
  • Fibers made according to the processes disclosed herein can be used in any applications where fibers are used.
  • composite fibers containing aramids made according to the processes disclosed herein can be used in yarn, cord (twisted yarn) or fabric form to provide reinforcement for a variety of matrices, including elastomers.
  • the composite fibers, and yarns, cords and fabrics made therefrom, can be used in the manufacture of shaped articles, such as, for example, tires, belts and hoses.
  • Denier is determined according to ASTM D 1577 and is the linear density of a yarn as expressed as weight in grams of 9000 meters of yarn. Denier times (10/9) is equal to decitex (dtex).
  • the fibers to be tested are conditioned and then tested based on the procedures described in ASTM D885-98.
  • Tenacity (breaking tenacity), elongation to break, and modulus of elasticity are determined by breaking test yarns on an lnstron tester. Tenacity is reported as breaking stress divided by linear density. Modulus is reported as the slope of the initial stress/strain curve converted to the same units as tenacity. Elongation is the percent increase in length at break. Both tenacity and modulus are first computed in g/denier units which, when multiplied by 0.8838, yield dN/tex units. Each reported measurement is the average of six breaks.
  • Tensile properties for yarns are measured at 24° C and 55% relative humidity after conditioning under the test conditions for a minimum of 14 hours. Before testing, each yarn is twisted to a 1.1 twist multiplier. Each twisted specimen has a test length of 50 cm and is elongated at a rate of 50%/minute in an lnstron tester.
  • HASR is a test to determine how much of its initial strength a yarn retains after heat aging. HASR is reported in percent of the breaking strength retained after exposure to controlled heat.
  • a fresh yarn sample is conditioned at 24 0 C and 55% relative humidity for 14 hours.
  • a portion of the sample is subjected to dry heat at a temperature of 24O 0 C for 3 hours and is then tested for tensile strength (Heat aged tenacity).
  • a portion of the sample that has not been heated is also tested for tensile strength (As is tenacity).
  • HASR 100 X [Heat aged tenacity]/[As is tenacity]
  • An isotropic, 20 wt % solids solution of polyvinylpyrrolidone (PVP) in 100.1 % sulfuric acid was injected, by means of a diaphragm pump, into an anisotropic, 19.5 wt % solids solution of poly(p-phenyleneterephthalamide) in 100.1% sulfuric acid at a volumetric solution ratio (isotropic/anisotropic) of 'x ⁇ listed in Table 1.
  • the resulting mixture was passed through a series of motionless Sulzer SMX mixers to intimately mix the two solutions.
  • the first mixer had a pipe ID of 0.815 inch (2.07 cm) and was fitted with eighteen (18) removable mixing elements.
  • the second mixer had an ID of 0.612 inch (1.55 cm) and was fitted with ten (10) mixing elements. Within about seven (7) minutes of passing through the second mixer, the resulting solution was extruded through a 667-hole spinneret having orifice diameters of 0.063 mm and spun using a conventional air gap-wet spinning process. The extruded solution was drawn through a 0.8 cm length air gap into an aqueous coagulating bath at 5 degrees C containing about 5% sulfuric acid. The resulting fiber was washed, neutralized and dried.
  • Fibers of varying PVP content were produced depending on the volumetric ratio (isotropic/anisotropic) 'x 1 of the two polymer solutions. Yarn tensile properties are shown for several compositions in Table 1 derived from isotropic and anisotropic polymer solutions with solids concentrations of 20% and 19.5%, respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

L'invention concerne des procédés continus de fabrication de fibres composites à partir de polymères aramides. Ces procédés sont destinés à produire des fibres utiles dans diverses applications, notamment dans le renforcement de matériaux élastomères.
PCT/US2005/043392 2004-12-01 2005-11-30 Procedes continus de fabrication de fibres composites Ceased WO2006060523A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI0517126-1A BRPI0517126A (pt) 2004-12-01 2005-11-30 processos para a fabricação de uma fibra compósita
MX2007006390A MX2007006390A (es) 2004-12-01 2005-11-30 Procesos continuos para elaborar fibras compuestas.
JP2007544487A JP2008522055A (ja) 2004-12-01 2005-11-30 複合繊維を作製するための連続方法
CA2586635A CA2586635C (fr) 2004-12-01 2005-11-30 Procedes continus de fabrication de fibres composites
CN2005800414171A CN101076622B (zh) 2004-12-01 2005-11-30 制造复合纤维的连续方法
EP05852581A EP1825037B1 (fr) 2004-12-01 2005-11-30 Procedes continus de fabrication de fibres composites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/001,432 US20060113700A1 (en) 2004-12-01 2004-12-01 Continuous processes for making composite fibers
US11/001,432 2004-12-01

Publications (1)

Publication Number Publication Date
WO2006060523A1 true WO2006060523A1 (fr) 2006-06-08

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PCT/US2005/043392 Ceased WO2006060523A1 (fr) 2004-12-01 2005-11-30 Procedes continus de fabrication de fibres composites

Country Status (9)

Country Link
US (1) US20060113700A1 (fr)
EP (1) EP1825037B1 (fr)
JP (1) JP2008522055A (fr)
KR (1) KR20070086810A (fr)
CN (1) CN101076622B (fr)
BR (1) BRPI0517126A (fr)
CA (1) CA2586635C (fr)
MX (1) MX2007006390A (fr)
WO (1) WO2006060523A1 (fr)

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EP4077506A1 (fr) * 2019-12-20 2022-10-26 Teijin Aramid B.V. Procédé continu de recyclage

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US8100285B2 (en) * 2007-03-09 2012-01-24 Danielle Aseff Food cooking, serving and storage device
JP7030805B2 (ja) * 2016-11-08 2022-03-07 テイジン・アラミド・ビー．ブイ． ポリエーテルケトンケトン繊維の製造方法
US11078627B2 (en) 2018-08-14 2021-08-03 Dupont Safety & Construction, Inc. High tensile strength paper suitable for use in electrochemical cells
US11578461B2 (en) 2020-03-17 2023-02-14 Dupont Safety & Construction, Inc. Papers comprising aerogel powder and aramid polymer fibrils
US20210296685A1 (en) 2020-03-17 2021-09-23 Dupont Safety & Construction, Inc. Solid-state composite electrolytes comprising aramid polymer fibrils
WO2022031302A1 (fr) 2020-08-04 2022-02-10 Dupont Safety & Construction, Inc. Papier comprenant de la pâte d'aramide adaptée pour cellules électrochimiques, et cellules électrochimiques fabriquées à partir de celui-ci
WO2023038346A1 (fr) * 2021-09-08 2023-03-16 코오롱인더스트리 주식회사 Fibre discontinue de para-aramide, fils filés d'aramide et procédé de fabrication associé
KR20240072178A (ko) 2021-10-07 2024-05-23 듀폰 세이프티 앤드 컨스트럭션, 인크. 기재 및 도포된 피브릴 커버링을 포함하는 부직포 시트 재료

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CA2586635C (fr) 2012-05-22
CN101076622B (zh) 2010-05-26
MX2007006390A (es) 2007-06-20
BRPI0517126A (pt) 2008-09-30
CA2586635A1 (fr) 2006-06-08
EP1825037A1 (fr) 2007-08-29
CN101076622A (zh) 2007-11-21
US20060113700A1 (en) 2006-06-01

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