EP1544330A1 - Vernetzte Polyvinylalkoholfaser und Verfahren zur Herstellung derselben - Google Patents

Vernetzte Polyvinylalkoholfaser und Verfahren zur Herstellung derselben Download PDF

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Publication number
EP1544330A1
EP1544330A1 EP04008282A EP04008282A EP1544330A1 EP 1544330 A1 EP1544330 A1 EP 1544330A1 EP 04008282 A EP04008282 A EP 04008282A EP 04008282 A EP04008282 A EP 04008282A EP 1544330 A1 EP1544330 A1 EP 1544330A1
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EP
European Patent Office
Prior art keywords
bobbin
raw cord
crosslinking
yarn
crosslinker
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Withdrawn
Application number
EP04008282A
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English (en)
French (fr)
Inventor
Ik-Hyeon Kwon
Soo-Myung Choi
Seong-Ho R & D Center for Fiber & Textile Park
Hak-Sung R & D Center for Fiber & Textile Kim
In-Seok R & D Center for Fiber & Textile Oh
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Hyosung Corp
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Hyosung Corp
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Publication date
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Publication of EP1544330A1 publication Critical patent/EP1544330A1/de
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/04—Carriers or supports for textile materials to be treated
    • D06B23/042—Perforated supports
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/123—Polyaldehydes; Polyketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the present invention relates to crosslinked polyvinyl alcohol fiber and method for producing the same, and more particularly, to crosslinked polyvinyl alcohol fiber, in which PVA resin having a degree of polymerization of more than 1,000 and a degree of saponification of more than 97.0 mol% is dissolved in dimethyl sulfoxide (hereinafter, referred to as DMSO), the solution is subjected to dry and wet gel spinning using methanol as a coagulation solution, drawn and thermally treated, the resulting polyvinyl alcohol drawn yarn with 500-3,000 deniers is twisted to produce a cabling yarn, the cabling yarn is plied into a 2-ply or 3-ply yarn to produce a raw cord, the raw cord is wound on a bobbin for crosslinking and crosslinked in an aqueous crosslinking solution containing an aromatic aldehyde compound and an acid catalyst. Moreover, the present invention relates to a crosslinker-introducing apparatus, which is used in the above method and can effectively induce the crosslinking reaction of
  • a polyvinyl alcohol fiber (hereinafter, referred to as PVA) shows superior strength and modulus to general purpose fibers, such as polyamide, polyester, and polyacrylonitrile fibers, and is very excellent in particularly adhesion, water dispersibility, alkaline resistance and chemical resistance. Thus, it is used as materials of various industrial fields.
  • PVA is also used as a reinforcement material for concrete, cement, rubber, plastic and the like, and studied and developed as a material with high applicability to new fields.
  • US Patent No. 4,440,711 discloses a method for preparing a high-strength PVA fiber using a gel spinning technique (US patent No. 4,698,194) in which high-molecular weight polyethylene as a raw material is drawn to high draw ratio to produce the high-strength fiber.
  • the gel spinning technique is a general method for producing the high-strength fiber, in which a polymer compound is mixed with solvent to prepare a uniform solution, and then, the solution is drawn to high draw ratio while suitably adjusting phase separation and gelling occurring in a spinning process.
  • Japanese patent laid-open publication No. Heisei 7-109616 discloses a method for producing a PVA multifilament fiber with a tensile strength of at least 22 g/denier, an initial modulus of at least 440 g/denier and a yarn CV of less than 5%, in which dry and wet spinning processes are performed using a spinneret with an orifice diameter of 0.1-1 mm and an orifice length-to-diameter (L/D) ratio of 3-20.
  • the PVA fiber produced by this method has excellent mechanical properties
  • the PVA resin is dissolved in hot water with a high temperature above 100 °C or has reduced mechanical properties, due to the hydrophilicity of PVA resin itself.
  • it has many limitations for use in applications, such as tire cords which have the biggest market among the industrial fibers.
  • a crosslinker is added to a spinning dope before a drawing process or during an extraction or oil-treating process.
  • Korean patent registration No. 210727 discloses a method for producing a polyvinyl alcohol fiber with excellent hot water resistance, in which a yarn containing an acetal compound of aliphatic dialdehyde as a crosslinker is prepared, subjected to dry heat drawing and crosslinked by an acid.
  • Korean patent laid-open publication No. 96-41438 discloses a method for producing a polyvinyl alcohol fiber with excellent hot water resistance, in which a yarn containing an ammonium sulfate crosslinker is subjected to dry heat drawing and then crosslinked.
  • the crosslinker is added to the spinning dope before the drawing process or in the extraction or oil-treating process.
  • the crosslinker contained in the PVA undrawn yarn cause crosslinking reaction to reduce drawability, or the crosslinker with low boiling point is volatilized to reduce crosslinking efficiency.
  • the crosslinker hardly has a hot water resistance above 130 °C.
  • the crosslinking treatment methods as described above have a problem in that, since crosslinking treatment is performed by simply dipping a bobbin wound with a undrawn yarn into the crosslinker, a portion of the undrawn yarn wound inside the bobbin is not impregnated with the crosslinker, and thus, incompletely crosslinked, or the outer side of the undrawn yarn wound on the bobbin is crosslinked at a significantly different level from the inside of the undrawn yarn.
  • An object of the present invention is to provide a crosslinked polyvinyl alcohol fiber, in which a polyvinyl alcohol drawn yarn with 500-3,000 deniers is twisted to form a cabling yarn, the cabling yarn is plied into a 2-ply or 3-ply yarn to prepare a raw cord, the raw cord wound on a bobbin for crosslinking reaction is crosslinked in an aqueous crosslinking solution containing an aromatic aldehyde compound and an acid catalyst.
  • Another object of the present invention is to provide a crosslinker-introducing apparatus, which is used in the above inventive method and allows the polyvinyl alcohol fiber to have excellent hot water resistance and high strength.
  • a crosslinked raw cord which is produced by a method comprising the steps of: (A) spinning polyvinyl alcohol having a degree of polymerization of 1,000-7,000 according to a dry and wet spinning technique or a wet spinning technique, drawing the undrawn yarn to high draw ratio, and thermally treating the drawn yarn; (B) twisting the polyvinyl alcohol drawn yarn to prepare a cabling yarn, and plying the cabling yarn into a 2-ply or 3-ply yarn to produce a raw cord; and (C) crosslinking the raw cord by dipping it into the crosslinker.
  • a crosslinker-introducing apparatus comprising a cylindrical bobbin which has a hollow formed therein, a plurality of through-holes formed on the circumferential surface and on which a raw cord is wound and a closed container which is charged with the crosslinker and provided in such a manner that the bobbin for crosslinking is dipped in the crosslinker.
  • a crosslinked raw cord which is produced by a method comprising the steps of: (A) dissolving polyvinyl alcohol having a degree of polymerization of 1,000-7,000 and a degree of saponification of more than 97.0 mol% in dimethyl sulfoxide, spinning the solution according to a dry and wet spinning technique or a wet spinning technique, drawing the undrawn yarn to high draw ratio, and thermally treating the drawn yarn; (B) twisting the polyvinyl alcohol drawn yarn to prepare a cabling yarn, and plying the cabling yarn into a 2-ply or 3-ply yarn to produce a raw cord; and (C) crosslinking the raw cord using the crosslinker-introducing apparatus described above in an aqueous crosslinking solution containing an aromatic aldehyde compound and an acid catalyst while adding alcohol to the aqueous crosslinker solution.
  • the alcohol added to the aqueous crosslinking solution in the step (C) is methanol.
  • the content of the alcohol added to the aqueous crosslinking solution in the step (C) is 1-30 wt%.
  • the content of the aromatic aldehyde compound crosslinked to the raw cord in the step (C) is 0.1-5.0 wt%.
  • the aromatic aldehyde crosslinked to the raw cord in the step (C) is terephthaldicarboxaldehyde (TDA).
  • the acid catalyst is used in the crosslinking of the raw cord in the step (C).
  • the acid catalyst used in the step (c) is acetic acid.
  • a treated cord for tire cords which is produced by treating the crosslinked raw cord described above with a dipping solution (RFL) and has the following physical properties: (1) a breaking load of 20.0-50.0 kgf; (2) a fineness of 1,000-6,000 deniers; (3) hot water resistance of at least 130 °C; and (4) a fatigue resistance of at least 80%.
  • RRL dipping solution
  • the crosslinker which is used in the present invention is preferably an aldehyde compound capable of crosslinking with the hydroxy group of PVA, and the aldehyde compound preferably has two or more aldehyde groups in order to increase crosslinking efficiency.
  • the aldehyde compound is more preferably an aromatic compound which infiltrates only into the non-crystalline region of the fiber.
  • this aromatic aldehyde compound examples include terephthaldicarboxaldehyde (TDA), isophthaldicarboxaldehyde (IDA) and naphthaldicarboxaldehyde (NDA), and a mixture of two or more thereof.
  • TDA terephthaldicarboxaldehyde
  • IDA isophthaldicarboxaldehyde
  • NDA naphthaldicarboxaldehyde
  • terephthaldicarboxaldehyde As the aromatic aldehyde compound, terephthaldicarboxaldehyde (TDA) is preferably used in the present invention.
  • the aromatic aldehyde capable of infiltrating only into the non-crystalline region of the drawn yarn is used as the crosslinker. Since the aromatic aldehyde is mainly infiltrated only into the non-crystalline region of the yarn, the tenacity of the drawn yarn can be prevented from being reduced due to the crosslinker.
  • the most important characteristic of the present invention is a crosslinking process.
  • crosslinking there is used a method wherein the crosslinker is dissolved in an organic solvent in an extraction process in order to infiltrate the crosslinker into the inside of the fiber.
  • this crosslinker within the undrawn fiber causes a reduction in drawability in a thermal drawing step at high temperature above 200 °C, so that the drawn yarn does not have sufficient hot water resistance and fatigue resistance.
  • the crosslinker used in the extraction process makes organic solvent recovery difficult and thus an entire process difficult.
  • the twisted PVA raw cord is crosslinked after it is infiltrated with the crosslinker.
  • a key technical point in the present invention is that the raw cord is crosslinked in a crosslinking solution containing an aromatic aldehyde compound and an acid catalyst while adding alcohol to the aqueous crosslinking solution.
  • the addition of alcohol to the crosslinking solution allows significant prevention of reduction in tenacity.
  • PVA has a degree of polymerization of about 1,000-7,000, and preferably 1,500-4,000. At a degree of polymerization lower than 1,000, it is difficult to form it into fibers, and at a degree of polymerization higher than 7,000, it has so high viscosity to reduce spinning processability. Since the high-strength PVA fibers which are mostly used in the industrial material field need to have hot water resistance, PVA with a saponification degree of more than 97.0 mol% is used.
  • the organic solvent ethylene glycol, glycerin, and DMSO may be used, but DMSO is suitable for its highest solubility for PVA. This DMSO is preferably purified to a water content of less than several tens ppm before use.
  • the concentration of the PVA dope is adjusted such that its viscosity is preferably in a range of 50-4,000 poise, and more preferably 500-3,000 poise in order to obtain excellent physical properties. At a viscosity below 50 poise, it is difficult to form the PVA dope into a fiber, and at a viscosity above 4,000 poise, fiber spinnability is reduced.
  • a coagulation bath has a temperature of -30 to 30 °C for possible spinning, and preferably -10 to 10 °C for the formation of uniform gel. If the temperature of the coagulation bath is below -30 °C, PVA spinning dope may be frozen. If the temperature of the coagulation bath is higher than 30 °C, gel formation becomes impossible so that spinnability will be reduced.
  • a method for producing a PVA fiber is performed by a dry spinning technique, a wet spinning technique, and a dry and wet spinning technique, but in a method for producing a high-strength PVA fiber where a drawing process with high draw ratio is required, the dry and wet spinning technique is preferred.
  • the air-gap in the dry and wet spinning technique may be 5-200 mm, but for thermal drawing to high draw ratio, a narrow air-gap of 5-50 mm is preferred. At an air-gap below 5 mm, workability will be reduced.
  • crystallinity is greater than gelling to make the thermal drawing at high draw ratio impossible, and also the fusion between fibers on a nozzle section occurs to reduce productivity.
  • the drawing process is very important for high strength and improved hot water resistance.
  • a heating manner in the drawing process include a hot air heating manner and a roller heating manner.
  • a filament is in contact with the roller surface such that the fiber surface is liable to be damaged.
  • the hot air heating manner is more effective for the production of the high-strength PVA fiber.
  • the heating temperature may be 140-250 °C, and preferably 160-230 °C. At a heating temperature below 140 °C, molecular chains will not sufficiently move to make the thermal drawing at high draw ratio impossible, and above 250 °C, PVA is liable to be decomposed to cause a reduction in physical properties.
  • a PVA drawn yarn is twisted to produce a raw cord.
  • an increase in twist number will result in a reduction in tenacity but an increase in fatigue resistance.
  • selecting suitable twist number according to the purpose of use is very important. For example, a tire cord used for carcass of a tire with 1500 d/2p is twisted to 300-500 TPM (turns per meter) before use.
  • the twisted PVA raw cord is crosslinked by the addition of a crosslinker.
  • the aromatic aldehyde is used as the crosslinker as described above.
  • the aromatic aldehyde compound which is used in the present invention, is preferably terephthaldicarboxaldehyde (TDA).
  • TDA terephthaldicarboxaldehyde
  • the crosslinking compound is used at the amount of 0.1-5 wt% relative to a fiber, and preferably 0.5-2.0 wt%. If it is used at the amount of less than 0.1 wt%, an insufficient heat water resistance below 130 °C will be caused, and if it is used at the amount of more than 5.0 wt%, a great reduction in tenacity will be caused to make the use of the high-tenacity tire cord difficult.
  • an acid catalyst is required in an aqueous crosslinking solution.
  • acids such as sulfuric acid or acetic acid
  • the acetic acid is preferable in view of reaction rate adjustment and stability.
  • the acid catalyst is preferably used at the amount of 5-30 wt% relative to the aqueous crosslinking solution. If the acid catalyst is used at less than 5 wt%, crosslinking reaction will progress too slowly, and if it is used at more than 30 wt%, it will be difficult to remove the acid catalyst in a water-washing process after reaction.
  • crosslinking is performed with the addition of alcohol to the aqueous crosslinking solution containing the aromatic aldehyde compound and the acid catalyst.
  • the addition of alcohol to the crosslinking solution allows significant prevention of a reduction in tenacity after crosslinking.
  • Examples of preferred alcohols, which are added to the aqueous crosslinking solution in the present invention, include methanol, ethanol, propanol and butanol. Methanol is more preferred.
  • the alcohol is added at the amount of 1-30 wt% relative to the aqueous crosslinking solution. At less than 1 wt%, a great reduction in tenacity will be caused during crosslinking to make the use for the high-tenacity tire cord difficult, and at more than 30 wt%, a cost disadvantage will be caused and also crosslinking will progress at a too slow rate.
  • Another key technical point in the present invention is that a polyvinyl alcohol drawn yarn is plied into a 2-ply or 3-ply yarn to produce a raw cord wound on a bobbin for crosslinking, and then, the raw cord wound on the bobbin for crosslinking is crosslinked by dipping it into the crosslinking solution.
  • crosslinking compound To infiltrate the crosslinking compound into the non-crystalline region of a PVA fiber having high crystallinity, a method is used in which the reaction solution is heated to 50 °C to increase the activity of the crosslinking compound, and a reactor is pressurized before use.
  • crosslinking time varies depending on the crosslinking compound and conditions, but is preferably longer than 30 minutes. However, if the crosslinking is performed for too long time, a great reduction in tenacity will be caused.
  • the crosslinked PVA raw cord is washed and dried.
  • the dried raw cord is dipped in a RFL solution, dried and thermally treated.
  • the dipping process is achieved by impregnating the fiber surface with a resin solution called resorcinol-formaline-latex (RFL), and this dipping process is performed in order to improve the problem of low adhesion to rubber of the tire cord fiber.
  • RFL resorcinol-formaline-latex
  • the dipping solution which is used for the adhesion between the PVA raw cord and rubber in the present invention, can be prepared by, for example, the following method.
  • the following preparation example is given to more fully understand the present invention and is not intended to limit the present invention.
  • Resorcinol of 29.4 wt% 45.6 weight part Pure water 255.5 weight part
  • the solution containing the above components is aged at 25 °C for 20 hours, and maintained at a solid concentration of 19.05%.
  • the raw cord is stretched to a stretch ratio of 0.5-3%, and a dip pick up (DPU) of the RFL is 3.0-9.0 wt%.
  • DPU dip pick up
  • the raw cord is stretched to a stretch ratio of 0.5-3%, and a dip pick up (DPU) of the RFL is 3.0-9.0 wt%.
  • DPU dip pick up
  • a stretch ratio of more than 3% excessive tension will be applied to the raw cord and thus will cause damages to the raw cord.
  • Thermal treatment should be performed at a temperature of 170-230 °C, and preferably 200-220 °C where the movement of PVA molecules is the best.
  • the production of a treated high-tenacity PVA cord becomes possible.
  • a heat treatment process conducted after dipping the raw cord in the RFL solution it is important that the dipped cord is maintained at a stretch ratio of 0 to -5%. If the stretch ratio in the heat treatment process is above 0%, when the dipped cord is used in a tire cord requiring high fatigue resistance, a cord cutting or separation phenomenon will occur which is due to low fatigue resistance below 60% resulting from the low elongation of the dipped cord.
  • crosslinker is present within the fiber not having been washed in the water-washing process after the crosslinking process, it acts as an impurity in a product where the PVA fiber was used.
  • heat treatment is performed above 200 °C such that the remaining crosslinker can be reacted or volatilized to further improve crosslinking efficiency.
  • FIG. 1 is a perspective diagram showing the bobbin for crosslinking according to the present invention
  • FIG. 2 is a use state diagram showing the use state of the bobbin for crosslinking according to the present invention.
  • a bobbin for crosslinking 10 is provided.
  • the bobbin for crosslinking 10 comprises a first bobbin 10a forming one portion of the crosslinking bobbin 10, and a second bobbin 10b, which is detachably coupled to the first bobbin 10a and forms the other portion of the crosslinking bobbin 10.
  • hollows 16a and 16b are formed, respectively, a plurality of through-holes 13a and 13b are formed in the circumferential portion of the first and second bobbins so that cylindrical bobbin axes 12a and 12b on which a PVA raw cord is wound up are provided.
  • a coupling protrusion 18a and a coupling groove 18b are formed which correspond to each other such that the second bobbin 10b is coupled to the first bobbin 10a.
  • the first bobbin wheel 14a coupled to the first bobbin 10a serves to close the hollow 16a of the bobbin for crosslinking
  • the second bobbin wheel 14b coupled to the second bobbin 10b serves to be connected with a crosslinker-feeding pipeline 30 in order to supply the crosslinker 2 into the inside of the PVA raw cord 1 wound on a bobbin for crosslinking 10 through a hollow 16a and 16b formed in a bobbin for crosslinking 10 by pressurizing or depressurizing with supplying apparatus by which crosslinker 2 is supplied in a specified pressure.
  • the bobbin for crosslinking 10 on which the PVA raw cord 1 was wound is provided in such a manner that it is dipped in a crosslinker 2 contained in a closed container 40 charged with the crosslinker 2.
  • the crosslinker 2 is pressurized or depressurized to a specified pressure and supplied through a crosslinker-feeding pipeline 30.
  • the supplied crosslinker is moved from inside to outside of the wound PVA raw cord 1 through the through-holes 13a and 13b formed in the respective bobbin axes 12a and 12b or moved from the outside to inside of the PVA raw cord 1, so that the inside and outside of the PVA raw cord 1 wound on the crosslinking bobbin 10 can be uniformly crosslinked.
  • FIG. 1 is a perspective diagram showing a bobbin for crosslinking according to the present invention.
  • FIG. 2 is a use state diagram showing a crosslinker-introducing system using the bobbin for crosslinking according to the present invention.
  • the tenacity of the filament is measured using low speed elongation tester, and the filament is tested after being dried at 107 °C for 2 hours.
  • the filament is twisted by 80TPM(80turns/meter) and the length of the filament is 250mm and the elongation speed is 300m/min.
  • a twisted raw cord with 3,000 deniers is selected, cut into a 4-cm size, and then applied with a load of 3g/ply.
  • the cord is dipped in water contained in a glass container for pressurization, and the temperature at which the fiber is broken is measured while elevating the temperature at a rate of 2 °C/minute.
  • Samples were subjected a fatigue test using a Goodrich disc fatigue tester which is conventionally used for the fatigue test of tire cords. Then, they were measured for residual tenacity, and fatigue resistances were compared.
  • the fatigue test was conducted under the following conditions: 120 °C, 2,500 rpm, and 10% and 18% compression. After the fatigue test, the samples were submerged in tetrachloroethylene solution to swell rubber, and then, a cord was separated from the rubber and measured for residual tenacity. This residual tenacity was measured after drying at 107 °C for 2 hours using a conventional tensile strength tester by the above-described measurement method (a).
  • PVA was used in a powder form with a degree of saponification of 99.9 mol% and a degree of polymerization of 2,000, and methyl alcohol and DMSO were used in a purified solvent mixture form with a water content of less than 100 ppm.
  • solvent mixture DMSO and methyl were mixed such that the content of methyl alcohol content in the solvent was 5% by volume.
  • PVA was dissolved in the solvent mixture such that it was 22 wt% relative to a PVA spinning dope.
  • the PVA solution was produced into a PVA fiber by a dry and wet spinning technique, using gel spinning.
  • a circular nozzle with a nozzle hole number of 500, a nozzle hole diameter of 0.5 mm and a L/D ratio of 5 was used.
  • air-gap was 50 mm, and methanol was used as a solvent in a coagulation bath.
  • the coagulation bath was maintained at a solvent/methanol mixing ratio of 20/80 and a temperature of 0 °C.
  • the PVA fiber After passing through an extraction tank, the PVA fiber must be free of the DMSO solvent. If the solvent remains in the filament, it is discolored in a thermal drawing process at high temperature to act as a main cause of deteriorating the physical properties of the final filament.
  • the raw cord wound on a bobbin for crosslinking was crosslinked by dipping it in terephthaldicarboxaldehyde (TDA) as aromatic aldehyde through a crosslinker-introducing apparatus capable of effectively inducing crosslinking.
  • TDA terephthaldicarboxaldehyde
  • 2 wt% of terephthaldicarboxaldehyde (TDA) and 10 wt% of acetic acid were dissolved in water to prepare an aqueous crosslinking solution, and 10 wt% of methanol was added to the aqueous crosslinking solution, and then, the raw cord wound on the bobbin for crosslinking was crosslinked by dipping it in the aqueous crosslinking solution at 70 °C for one hour and washed with water.
  • the crosslinked raw cord with tenacity of 33.6 kgf was impregnated with a RFL solution to produce a treated PVA cord.
  • the treated PVA cord was measured for its physical properties and
  • the ratio between terephthaldicarboxaldehyde, acetic acid and methanol was adjusted to a ratio given in Table 1, and the resulting raw cord was crosslinked and then measured for its physical properties, including tenacity and fatigue resistance.
  • Comparative Example 1 is a non-crosslinked case and the results are given in Table 1, and Comparative Example 2 is a case where methanol was not used in the aqueous crosslinking solution. The results for Comparative Example 1 and 2 are given in Table 1.
  • the present invention provides the crosslinked raw cord which is produced by the method comprising the steps of: twisting a polyvinyl alcohol drawn yarn with 500-3,000 deniers to prepare a cabling yarn; plying the cabling yarn into a 2-ply or 3-ply yarn to prepare a raw cord; winding the raw cord on a bobbin for crosslinking; and crosslinking the raw cord wound on the bobbin for crosslinking, in an aqueous crosslinking solution containing an aromatic aldehyde compound and an acid catalyst, while adding alcohol to the aqueous crosslinking solution.
  • the crosslinked raw cord has excellent hot water resistance, and thus, can be suitably used for tire cords.
EP04008282A 2003-11-27 2004-04-06 Vernetzte Polyvinylalkoholfaser und Verfahren zur Herstellung derselben Withdrawn EP1544330A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2003-0084832A KR100511724B1 (ko) 2003-11-27 2003-11-27 가교제 투입장치 및 이를 이용한 폴리비닐알코올 섬유의제조방법
KR2003084832 2003-11-27

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EP1544330A1 true EP1544330A1 (de) 2005-06-22

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FR2935638A1 (fr) * 2008-09-09 2010-03-12 Goodyear Tire & Rubber Bandage pneumatique avec une carcasse renforcee par une nappe a base d'alcool polyvinylique

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CN102337605B (zh) * 2011-08-18 2013-03-06 安徽皖维高新材料股份有限公司 一种高强度、高模量、高熔点pva纤维及其制造方法
US9777129B2 (en) * 2014-04-11 2017-10-03 Georgia-Pacific Consumer Products Lp Fibers with filler
US9777143B2 (en) 2014-04-11 2017-10-03 Georgia-Pacific Consumer Products Lp Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles
CN107287668B (zh) * 2016-04-12 2019-08-30 中国石油化工集团公司 一种耐温型pva纤维及其用途
CN112095159B (zh) * 2020-08-04 2022-09-16 东华大学 一种湿法纺丝的高强粗旦聚乙烯醇纤维及其制备方法

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CA2462991C (en) 2008-09-16
CA2462991A1 (en) 2005-05-27
JP4025742B2 (ja) 2007-12-26
US20050118419A1 (en) 2005-06-02
CN1621584A (zh) 2005-06-01
CN1301350C (zh) 2007-02-21
JP2005154995A (ja) 2005-06-16
KR20050051105A (ko) 2005-06-01

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