EP2716800A1 - Fibres de poly(sulfure de phénylène) et tissu non tissé - Google Patents

Fibres de poly(sulfure de phénylène) et tissu non tissé Download PDF

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Publication number
EP2716800A1
EP2716800A1 EP12792614.5A EP12792614A EP2716800A1 EP 2716800 A1 EP2716800 A1 EP 2716800A1 EP 12792614 A EP12792614 A EP 12792614A EP 2716800 A1 EP2716800 A1 EP 2716800A1
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EP
European Patent Office
Prior art keywords
nonwoven fabric
crystallinity
pps
thermal
nonwoven web
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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.)
Withdrawn
Application number
EP12792614.5A
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German (de)
English (en)
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EP2716800A4 (fr
Inventor
Yohei Nakano
Yoshikazu Yakake
Masashi Ito
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Toray Industries Inc
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Toray Industries Inc
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Publication of EP2716800A1 publication Critical patent/EP2716800A1/fr
Publication of EP2716800A4 publication Critical patent/EP2716800A4/fr
Withdrawn legal-status Critical Current

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    • 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
    • D01F6/765—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products from polyarylene sulfides
    • 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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/69—Autogenously bonded nonwoven fabric

Definitions

  • the present invention relates to a fiber comprising a resin comprising polyphenylene sulfide (hereinafter sometimes abbreviated to "PPS”) as a main component, and a nonwoven fabric comprising the fiber.
  • PPS polyphenylene sulfide
  • PPS resins are excellent in heat resistance, flame retardancy and chemical resistance and are therefore suitably used as engineering plastics, films, fibers, nonwoven fabrics, or the like. Especially nonwoven fabrics utilizing these excellent properties are expected to be used in industrial applications such as heat-resistant filters, electrical insulation materials, and battery separators.
  • a filament nonwoven fabric produced by spun bonding in which a PPS resin is spun and drawn into filaments, the filaments are temporarily bonded at a temperature not more than the first crystallization temperature of the fabric to be produced, the obtained fabric is subjected to heat treatment under strain at a temperature not less than the first crystallization temperature to promote the crystallization of the filaments, and the fabric is subjected to permanent bonding (see, for example, Patent Literature 1).
  • an object of the present invention is to provide a fiber comprising a PPS resin as a main component and having both excellent heat resistance and excellent thermal bonding properties, and a nonwoven fabric comprising the fiber.
  • a first aspect of the present invention relates to a polyphenylene sulfide fiber comprising polyphenylene sulfide as a main component and having the sum of the crystallinity and the rigid amorphous fraction of 30% to 90%.
  • a second aspect of the present invention relates to a nonwoven fabric comprising the polyphenylene sulfide fiber according to the first aspect of the present invention.
  • the crystallinity is not limited to a specific range. However, the crystallinity is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more. When a nonwoven web of the fiber having such crystallinity is thermally bonded, the resulting sheet is prevented from breakage due to being wound up around a roll.
  • the crystallinity is preferably less than 25%, more preferably 23% or less, and still more preferably 20% or less so that a large amount of the amorphous phase (including the rigid amorphous fraction) is present in the fiber and contributes to excellent thermal bonding properties for thermal bonding of the nonwoven web.
  • the nonwoven fabric can be produced by spun bonding in which the PPS fibers are consolidated by thermal bonding or mechanical entanglement.
  • the PPS fiber of the present invention has excellent thermal bonding properties while maintaining the properties of a PPS resin, namely, heat resistance, chemical resistance, and flame retardancy. Consequently, the nonwoven fabric of the present invention also has excellent mechanical strength while maintaining the properties of a PPS resin, namely, heat resistance, chemical resistance, and flame retardancy and is therefore usable for various industrial applications.
  • the resin used in the present invention comprises PPS as a main component.
  • PPS resin the resin that is used in the present invention and comprises PPS is also referred to as the "PPS resin”.
  • PPS is a polymer having, as the repeating unit, a phenylene sulfide unit such as a p-phenylene sulfide unit and a m-phenylene sulfide unit.
  • Preferred is a substantially linear polymer containing 90 mol% or more of a p-phenylene sulfide unit because of its heat resistance and spinnability.
  • preparation of a polymer by copolymerization of a p-phenylene sulfide unit with a m-phenylene sulfide unit is preferred in that the flame retardancy and chemical resistance of PPS are not impaired.
  • the copolymerized PPS can be suitably used as a component for a composite fiber.
  • PPS is substantially not copolymerized with trichlorobenzene.
  • trichlorobenzene has three or more halogen substituents per benzene ring and thus the copolymerization of PPS with trichlorobenzene results in a branched structure, leading to poor spinnability of the resulting PPS resin and frequent breakage of the resulting fibers during spinning and drawing.
  • the copolymerized trichlorobenzene content is preferably 0.05 mol% or less, and more preferably 0.01 mol% or less.
  • the PPS content of the PPS resin is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in view of heat resistance, chemical resistance, and the like.
  • a nucleator preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in view of heat resistance, chemical resistance, and the like.
  • a nucleator preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in view of heat resistance, chemical resistance, and the like.
  • the PPS resin used in the present invention preferably has a melt flow rate (hereinafter sometimes abbreviated to MFR) measured in accordance with ASTM D1238-70 (measurement temperature: 315.5°C, measurement load: 5 kg) of 100 to 300 g/10 min.
  • MFR melt flow rate
  • the PPS resin having an MFR of 300 g/10 min or less, more preferably 225 g/10 min or less has a moderately high polymerization degree or molecular weight, which contributes to increase in strength and heat resistance sufficient for practical use.
  • the PPS fiber of the present invention it is important for the PPS fiber of the present invention to have the sum of the crystallinity and the rigid amorphous fraction of 30% to 90%.
  • crystallinity herein refers to those determined by measuring with a differential scanning calorimetry (DSC) as described later in Examples.
  • the mobile amorphous fraction herein refers to those determined by measuring with a temperature modulated DSC as described later in Examples.
  • the boiling water shrinkage greatly varies; however, as shown in the relation of the boiling water shrinkage to the sum of the crystallinity and the rigid amorphous fraction in Fig. 2 , when the rigid amorphous fraction is used as an evaluation factor in addition to the crystallinity, a strong correlation is observed, which reveals that the rigid amorphous fraction significantly affects the thermal dimensional stability. Although the mechanism is unclear, the rigid amorphous fraction is an amorphous yet is considered to play a similar role to that of the crystal fraction for the thermal dimensional stability.
  • the boiling water shrinkage is less than 20% when the sum of the crystallinity and the rigid amorphous fraction is 30% or more, and the boiling water shrinkage is less than 10% when the sum of the crystallinity and the rigid amorphous fraction is 35% or more.
  • the boiling water shrinkage is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Consequently, a fiber having the sum of the crystallinity and the rigid amorphous fraction of 30% or more, preferably 35% or more, has excellent thermal dimensional stability.
  • the mobile amorphous fraction in addition to the rigid amorphous fraction, preferably is also contained in an amount of 10% or more, more preferably 30% or more, still more preferably 50% or more.
  • the mechanism is unclear, it is considered that, in thermal bonding, fibers comprising a certain amount of the mobile amorphous fraction more easily undergo plastic deformation in accordance with the magnitude of the pressure applied to the fibers for bonding. That is, the sum of the crystallinity and the rigid amorphous fraction in the PPS fiber is preferably 90% or less, more preferably 70% or less, and still more preferably 50% or less.
  • the crystallinity of the PPS fiber of the present invention is preferably not less than 5% and less than 25%.
  • the crystallinity needs to be 25% or more to stably impart thermal dimensional stability to a PPS fiber.
  • thermal shrinkage of a PPS fiber can be reduced by increasing the amount of the rigid amorphous fraction.
  • low crystallinity of a PPS fiber means the presence of a large amount of the amorphous phase, which results in poor thermal dimensional stability; whereas high crystallinity of a PPS fiber means the presence of a small amount of the amorphous phase, which results in poor thermal bonding properties.
  • the amorphous phase, especially the rigid amorphous fraction is increased to impart thermal dimensional stability, thereby achieving both excellent thermal dimensional stability and excellent thermal bonding properties.
  • the crystallinity of the PPS fiber of the present invention is 5% or more, more preferably 10% or more, and still more preferably 15% or more.
  • the crystallinity is less than 25%, more preferably 23% or less, and still more preferably 20% or less so that a large amount of the amorphous phase (including the rigid amorphous fraction) is present in the fiber and contributes to excellent thermal bonding properties for thermal bonding of the nonwoven web.
  • the cross section of the PPS fiber of the present invention may be any shape such as a circular shape, a hollow round shape, an oval shape, a flat shape, a polygonal shape, and a multilobal shape (such as an X shape and a Y shape).
  • the PPS fiber of the present invention may be in a composite form.
  • the composite form include a core-sheath type, an eccentric core-sheath type, an Umishima type, a parallel type, a radial type, and a multilobal type.
  • a core-sheath type which is suitable for achieving excellent spinnability.
  • the average single fiber fineness of the PPS fiber of the present invention is preferably 0.5 to 10 dtex.
  • the discharge rate of a molten resin per hole of a spinneret can be suitably reduced to allow the resulting fibers to sufficiently cool down, thereby preventing reduction in spinnability due to fusion bonding between the fibers.
  • the variation in the mass per unit area of the nonwoven fabric can be reduced, thereby providing excellent quality for the surfaces of the nonwoven fabric.
  • the average single fiber fineness is preferably 10 dtex or less, more preferably 5 dtex or less, and still more preferably 4 dtex or less.
  • the PPS fiber of the present invention can be used as a fiber for forming any type of fabric such as woven fabrics and nonwoven fabrics but, because of its excellent thermal bonding properties, the PPS fiber of the present invention can be more suitably used as a component fiber of a nonwoven fabric whose structure is fixed by thermal press-bonding.
  • the PPS nonwoven fabric of the present invention may be a filament nonwoven fabric or a staple nonwoven fabric, but a filament nonwoven fabric produced by spun bonding is preferred for its excellent productivity.
  • the mass per unit area of the nonwoven fabric of the present invention is preferably 10 to 1000 g/m 2 .
  • the mass per unit area is 1000 g/m 2 or less, more preferably 700 g/m 2 or less, and still more preferably 500 g/m 2 or less.
  • the nonwoven fabric having such a mass per unit area has moderate air permeability and thus prevents pressure loss from increasing.
  • the thermal shrinkage rate at 200°C of the PPS nonwoven fabric of the present invention is preferably 5% or less both in the longitudinal and transverse directions. Because of its properties, PPS nonwoven fabrics are often used under high temperature. When the thermal shrinkage rate at 200°C of the PPS nonwoven fabric of the present invention is 5% or less, more preferably 3% or less, reduction in its performance due to dimensional change can be prevented, and such a PPS nonwoven fabric is suitable for practical use.
  • the PPS nonwoven fabric of the present invention preferably has a longitudinal tensile strength retention rate measured by a heat-exposure resistance test in the air, at 210°C for 1500 hours of 80% or more.
  • the PPS nonwoven fabric having a longitudinal tensile strength retention rate of 80% or more, more preferably 85% or more, still more preferably 90% or more, can be used as a heat-resistant filter or the like that is used under high temperature for a long period of time.
  • the upper limit value of the longitudinal tensile strength retention rate is not particularly limited but is preferably 150% or less.
  • Spun bonding is a production method that requires the steps of: melting a resin, spinning the molten resin from a spinneret, solidifying the resulting filamentary streams by cooling, pulling and drawing the filamentary streams by means of an ejector, collecting the filaments on a moving net to form a nonwoven web, and consolidating the nonwoven web by thermal bonding or mechanical entanglement.
  • the spinneret and the ejector may be in various shapes such as a circular shape and a rectangular shape. Inter alia, a combination of a rectangular spinneret and a rectangular ejector is preferred because the amount of compressed air to be used is relatively small and the filaments are hardly fusion-bonded or scratch each other.
  • the spinning temperature for melting and spinning PPS is preferably 290 to 380°C, more preferably 295 to 360°C, and still more preferably 300 to 340°C.
  • the spinning temperature within the above range allows PPS to be brought into a stable molten state and to exhibit excellent spinning stability.
  • Examples of the method for cooling the spun filamentary streams include, for example, a method in which cold air is forced to blow over the filamentary streams, a method in which the filamentary streams are allowed to cool down at atmospheric temperature around the filamentary streams, a method in which the distance between the spinneret and the ejector is adjusted, and a combination thereof.
  • the cooling conditions can be appropriately adjusted and adopted in consideration of the discharge rate per hole of the spinneret, the spinning temperature, the atmospheric temperature, and the like.
  • the filamentary streams that have solidified by cooling are pulled and drawn by compressed air blown from the ejector.
  • the method for pulling and drawing the filamentary streams by means of the ejector and the conditions therefor are not particularly limited, but a method in which the filamentary streams are pulled and drawn by compressed air heated and blown from the ejector, the compressed air being heated to 100°C or more, preferably 140°C or more, more preferably 180°C or more, is preferred in that the crystallization of the PPS fiber is suppressed and at the same time the rigid amorphous fraction is increased. Since heated compressed air is used, the filamentary streams that are being pulled and drawn are simultaneously heat treated. However, the heat treatment duration is extremely short and therefore the rigid amorphous fraction, which is an intermediate phase between the crystal phase and the amorphous phase, can be specifically increased.
  • the upper limit of the temperature of the heated compressed air is not more than the melting point of PPS.
  • Another method for heat treating the filamentary streams during pulling and drawing include a method in which a heater is disposed before or after the ejector.
  • this method is not preferred because the thermal conductivity is inferior to that in the above method in which a hot air of high temperature is directly blown over the fibers, and consequently the heat does not contribute to increase in the rigid amorphous fraction.
  • the spinning speed is preferably not less than 3,000 m/min and less than 6,000 m/min.
  • Spinning at a spinning speed of 3,000 m/min or more, more preferably 3,500 m/min or more, still more preferably 4,000 m/min or more, can produce a PPS fiber having high crystallinity. Consequently, when a resulting nonwoven web is thermally bonded, the resulting sheet is prevented from breakage due to being wound up around a roll.
  • Spinning at a spinning speed less than 6,000 m/min is preferred because excessive increase in the crystallinity can be prevented and excellent spinning stability can be achieved.
  • the PPS fibers obtained by drawing are collected on a moving net to form a nonwoven web, and the obtained nonwoven web is consolidated by thermal bonding or mechanical entanglement to form a nonwoven fabric.
  • Preferred method for consolidation into a nonwoven fabric are a thermal bonding method in which thermal press-bonding is performed using various types of rolls such as a roll pair for thermal embossing that is composed of upper and lower rolls each having embossment on their surfaces, a roll pair for thermal embossing that is composed of a roll having a flat (smooth) surface and a roll having embossment on its surface, or a roll pair for thermal calendering that is composed of upper and lower flat (smooth) rolls; and a mechanical entanglement method using needle punching or water jet punching.
  • the embossment pattern on the embossing roll(s) may be circle, oval, square, rectangle, parallelogram, diamond, regular hexagon, or regular octagon, or the like.
  • the surface temperature of the thermal embossing roll pair is preferably 5 to 30°C lower than the melting point of PPS.
  • the thermal embossing roll pair having a surface temperature not lower than the temperature that is 30°C lower than the melting point of PPS, more preferably a surface temperature not lower than the temperature that is 25°C lower than the melting point of PPS, still more preferably a surface temperature not lower than the temperature that is 20°C lower than the melting point of PPS, the nonwoven web is thermally bonded to a sufficient extent and thereby flaking off and fluffing of the resulting nonwoven fabric can be prevented.
  • the thermal embossing roll pair having a surface temperature not higher than the temperature that is 5°C lower than the melting point of PPS, perforation in the press-bonded parts due to fusion of the fibers can be prevented.
  • the linear pressure applied by the thermal embossing roll pair during thermal bonding is preferably 200 to 1500 N/cm.
  • the rolls with a linear pressure of 200 N/cm or more, more preferably 300 N/cm or more the nonwoven web is thermally bonded to a sufficient extent and thereby flaking off and fluffing of the resulting sheet can be prevented.
  • the rolls with a linear pressure of 1500 N/cm or less, more preferably 1000 N/cm or less the raised portions of the embossment are prevented from biting into the nonwoven fabric and thereby trouble removing the nonwoven fabric from the rolls or the breakage of the nonwoven fabric can be prevented.
  • the bonding area provided by means of the thermal embossing roll pair is preferably 8 to 40%.
  • Thermal bonding with the roll pair so as to provide a bonding area of 8% or more, more preferably 10% or more, still more preferably 12% or more, can produce a nonwoven fabric having a sufficient strength for practical use.
  • Thermal bonding with the roll pair so as to provide a bonding area of 40% or less, more preferably 30% or less, still more preferably 20% or less, can prevent the resulting nonwoven fabric from being formed into a film-like shape that hardly has the advantages of a nonwoven fabric, such as air permeability.
  • the bonding area herein refers to the ratio of the area where the nonwoven web is in contact with both of the raised portions of the upper roll and the raised portions of the lower roll, relative to the total area of the nonwoven fabric.
  • the bonding area herein refers to the ratio of the area where the nonwoven web is in contact with the raised portions of the roll having raised and recessed portions, relative to the total area of the nonwoven fabric.
  • the shape of the needles and the number of needles per unit area can be appropriately selected and adjusted to perform the entanglement.
  • the number of needles per unit area is preferably at least 100 per cm 2 or more in view of the strength and the retention of the shape of the needles.
  • a silicone-based oil agent is sprayed on the nonwoven web before needle punching to prevent cutting of the fibers with the needles and to enhance the entanglement of the fibers.
  • columnar jets of water is preferably used.
  • a method in which water is forced out of nozzles 0.05 to 3.0 mm in diameter at a pressure of 1 to 60 MPa is suitably used.
  • the nonwoven web is preferably treated, at least once, at a pressure of 10 MPa or more, more preferably 15 MPa or more.
  • the nonwoven web before thermal bonding or mechanical entanglement can be temporarily bonded with calender rolls at 70 to 170°C and at a linear pressure of 50 to 700 N/cm.
  • the calender rolls may be a combination of upper and lower metallic rolls or of a metallic roll with a resin or paper roll.
  • the nonwoven web before thermal bonding or before or after mechanical entanglement or the nonwoven fabric can be heat treated under strain using a pin tenter, a clip tenter, or the like, or heat treated without strain (under a strain-free condition) using a hot air dryer or the like.
  • the temperature for the heat treatment is preferably in the range of from the crystallization temperature to the melting point of the PPS fiber that forms the nonwoven web or nonwoven fabric.
  • the MFR of PPS was measured in accordance with ASTM D1238-70 under the conditions of a measurement temperature of 315.5°C and a measurement load of 5 kg.
  • the spinning speed was calculated based on the following formula using the average single fiber fineness (dtex) of a fiber and the discharge rate of the resin per hole of a spinneret having various settings (hereinafter abbreviated to discharge rate per hole) (g/min).
  • Spinning speed 10000 ⁇ discharge rate per hole / average single fiber fineness
  • a 100 mol% linear polyphenylene sulfide resin that was intentionally not copolymerized with trichlorobenzene (made by Toray Industries, Inc., Product No. E2280, MFR: 160 g/10 min) was dried in a nitrogen atmosphere at 160°C for 10 hours, and used in the following procedure.
  • the PPS resin was molten in an extruder, and spun from a rectangular spinneret having a hole diameter of 0.50 mm at a spinning temperature of 320°C and at a discharge rate per hole of 1.38 g/min.
  • the spun filamentary streams were allowed to cool down and solidify between the rectangular spinneret and a rectangular ejector at a distance of 55 cm in an atmosphere at room temperature (20°C).
  • the filamentary streams that had cooled down and solidified were passed through the rectangular ejector and were pulled and drawn by compressed air that was heated to 230°C with an air heater and blown out from the ejector at an ejector pressure of 0.15 MPa.
  • the filaments were collected on a moving net to form a nonwoven web.
  • the obtained filaments had an average single fiber fineness of 2.8 dtex, a crystallinity of 18.4%, the sum of the rigid amorphous fraction and the crystallinity of 38.2%, and a boiling water shrinkage of 2.3%.
  • the spinning speed was 4,998 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • the obtained nonwoven web was temporarily bonded at a linear pressure of 200 N/cm and a temporary bonding temperature of 100°C with a pair of upper and lower metallic calender rolls installed in the production line.
  • the nonwoven fabric was then thermally bonded at a linear pressure of 1000 N/cm and a thermal bonding temperature of 270°C with a roll pair for embossing which provides a bonding area of 12% and which is composed of an upper metallic embossing roll engraved with a polka dot pattern and a lower metallic roll having a flat surface.
  • a filament nonwoven fabric of Example 1 was obtained.
  • the obtained nonwoven fabric had no significant shrinkage in width due to thermal shrinkage by thermal bonding with the embossing roll pair and showed good quality without wrinkles.
  • the obtained filament nonwoven fabric had a mass per unit area of 248 g/m 2 , a longitudinal tensile strength of 434 N/5 cm, thermal shrinkage rates of 0.0% in the longitudinal direction and 0.1% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the temperature of the compressed air was 200°C.
  • the obtained filaments had an average single fiber fineness of 2.8 dtex, a crystallinity of 17.3%, the sum of the rigid amorphous fraction and the crystallinity of 37.3%, and a boiling water shrinkage of 7.0%.
  • the spinning speed was 4,991 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 2 the nonwoven web was temporarily bonded and then thermally bonded in the same manner as in Example 1 to produce a filament nonwoven fabric of Example 2.
  • the obtained nonwoven fabric had no significant shrinkage in width due to thermal shrinkage by thermal bonding with the embossing roll pair and showed good quality without wrinkles.
  • the obtained filament nonwoven fabric had a mass per unit area of 253 g/m 2 , a longitudinal tensile strength of 454 N/5 cm, thermal shrinkage rates of 0.1% in the longitudinal direction and 0.2% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the temperature of the compressed air was 140°C.
  • the obtained filaments had an average single fiber fineness of 2.9 dtex, a crystallinity of 15.1%, the sum of the rigid amorphous fraction and the crystallinity of 31.3%, and a boiling water shrinkage of 17.5%.
  • the spinning speed was 4,824 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 3 the nonwoven web was temporarily bonded and then thermally bonded in the same manner as in Example 1 to produce a filament nonwoven fabric of Example 3.
  • the obtained nonwoven fabric had no significant shrinkage in width due to thermal shrinkage by thermal press-bonding with the embossing roll pair and showed good quality without wrinkles.
  • the obtained filament nonwoven fabric had a mass per unit area of 245 a longitudinal tensile strength of 472 N/5 cm, thermal shrinkage rates of 0.0% in the longitudinal direction and 0.1% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the temperature of the compressed air was 200°C and that the ejector pressure was 0.21 MPa.
  • the obtained filaments had an average single fiber fineness of 2.4 dtex, a crystallinity of 24.1%, the sum of the rigid amorphous fraction and the crystallinity of 49.2%, and a boiling water shrinkage of 2.2%.
  • the spinning speed was 5,663 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 4 the nonwoven web was temporarily bonded and then thermally bonded in the same manner as in Example 1 to produce a filament nonwoven fabric of Example 4.
  • the obtained nonwoven fabric had no significant shrinkage in width due to thermal shrinkage by thermal press-bonding with the embossing roll pair and showed good quality without wrinkles.
  • the obtained filament nonwoven fabric had a mass per unit area of 256 a longitudinal tensile strength of 421 N/5 cm, thermal shrinkage rates of 0.0% in the longitudinal direction and 0.1% in the transverse direction, and a longitudinal tensile strength retention rate of 98%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the temperature of the compressed air was 200°C and that the ejector pressure was 0.25 MPa.
  • the obtained filaments had an average single fiber fineness of 2.2 dtex, a crystallinity of 33.0%, the sum of the rigid amorphous fraction and the crystallinity of 67.4%, and a boiling water shrinkage of 2.0%.
  • the spinning speed was 6,198 m/min. In terms of spinnability, during the one-hour spinning, the breakage of the filaments was observed twice.
  • Example 5 the nonwoven web was temporarily bonded and then thermally bonded in the same manner as in Example 1 to produce a filament nonwoven fabric of Example 5.
  • the obtained nonwoven fabric had no significant shrinkage in width due to thermal shrinkage by thermal press-bonding with the embossing roll pair and showed good quality without wrinkles.
  • the obtained filament nonwoven fabric had a mass per unit area of 254 a longitudinal tensile strength of 245 N/5 cm, thermal shrinkage rates of 0.0% in the longitudinal direction and 0.1% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1.
  • Example 6 the nonwoven web was temporarily bonded in the same manner as in Example 1.
  • An oil agent (SM7060: made by Dow Corning Toray Silicone Co., Ltd.) in an amount of 2% by weight relative to the weight of the fibers was applied to the nonwoven web.
  • the nonwoven web was entangled by needle punching at a density of 300 needles/cm 2 with a needle having one barb and a barb depth of 0.06 mm to produce a filament nonwoven fabric of Example 6.
  • the obtained filament nonwoven fabric had a mass per unit area of 301 a longitudinal tensile strength of 490 N/5 cm, thermal shrinkage rates of 1.6% in the longitudinal direction and 1.8% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1.
  • the nonwoven web was temporarily bonded in the same manner as in Example 1.
  • the front and back surfaces of the nonwoven web were alternately entangled at a pressure of 15 MPa with a water jet punching (WJP) machine having nozzles with a diameter of 0.10 mm and a pitch of 0.1 mm.
  • the entangled nonwoven web was dried with a hot air dryer whose temperature was set at 100°C to produce a filament nonwoven fabric of Example 7.
  • the obtained filament nonwoven fabric had a mass per unit area of 285 a longitudinal tensile strength of 462 N/5 cm, thermal shrinkage rates of 1.4% in the longitudinal direction and 1.7% in the transverse direction, and a longitudinal tensile strength retention rate of 99%.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the compressed air was at normal temperature (30°C) and that the ejector pressure was 0.15 MPa.
  • the obtained filaments had an average single fiber fineness of 3.1 dtex, a crystallinity of 8.9%, the sum of the rigid amorphous fraction and the crystallinity of 10.7%, and a boiling water shrinkage of 61.2%.
  • the spinning speed was 4,435 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the compressed air was at normal temperature (30°C) and that the ejector pressure was 0.20 MPa.
  • the obtained filaments had an average single fiber fineness of 2.6 dtex, a crystallinity of 18.2%, the sum of the rigid amorphous fraction and the crystallinity of 25.3%, and a boiling water shrinkage of 28.5%.
  • the spinning speed was 5,331 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 2 The same PPS resin as in Example 1 was spun and formed into a nonwoven web in the same manner as in Example 1 except that the temperature of the compressed air was 230°C and that the ejector pressure was 0.10 MPa.
  • the obtained filaments had an average single fiber fineness of 4.9 dtex, a crystallinity of 9.4%, the sum of the rigid amorphous fraction and the crystallinity of 26.8%, and a boiling water shrinkage of 25.0%.
  • the spinning speed was 2,794 m/min. During the one-hour spinning, the occurrence of the breakage of the filaments was zero and thus good spinnability was observed.
  • Example 3 the nonwoven web was temporarily bonded in the same manner as in Example 1 and then needle punched in the same manner as in Example 6 to produce a filament nonwoven fabric of Comparative Example 3.
  • the thermal shrinkage rates of the obtained filament nonwoven fabric were significantly high and were 21.2% in the longitudinal direction and 23.4% in the transverse direction. Moreover, the surfaces of the nonwoven fabric after the heat treatment became wrinkled and irregular.
  • the filament nonwoven fabric had a mass per unit area of 295 g/m 2 and a longitudinal tensile strength of 472 N/5 cm. The heat-exposure resistance test could not be performed because of the significant thermal shrinkage.
  • the PPS fibers in Examples 1 to 5 having the sum of the crystallinity and the rigid amorphous fraction of 31.3 to 67.4% could be thermally bonded with the embossing roll pair and moreover thermal shrinkage at 200°C was hardly observed, indicating excellent thermal dimensional stability.
  • the fibers of Examples 1 to 4 having the crystallinity of 15.1 to 24.1% were excellent in thermal bonding properties and the resulting fabrics had excellent mechanical strength.
  • the polyphenylene sulfide fiber and the nonwoven fabric comprising the fiber described in the above embodiments and Examples are illustrated to demonstrate the technical ideas of the present invention.
  • the composition of the resin, the spinning and drawing conditions, the nonwoven web forming conditions, the single fiber fineness, the crystallinity, the rigid amorphous fraction, and the like are not limited to those in the above embodiments and Examples and can be modified in various ways within the scope of the claims of the present invention.
  • the nonwoven web is formed by spun bonding.
  • the nonwoven web may be formed by other methods.
  • the type of the PPS resin to be used is not limited to those in the above Examples.
  • the nonwoven fabric comprising the polyphenylene sulfide fiber of the present invention has excellent mechanical strength while maintaining the properties of a PPS resin, namely, heat resistance, chemical resistance, and flame retardancy. Therefore, the nonwoven fabric is useful for various industrial applications including heat-resistant filters, electrical insulation materials, and battery separators.
EP12792614.5A 2011-06-02 2012-06-01 Fibres de poly(sulfure de phénylène) et tissu non tissé Withdrawn EP2716800A4 (fr)

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Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
JP5725426B2 (ja) * 2011-03-22 2015-05-27 東レ株式会社 ポリフェニレンスルフィド複合繊維および不織布
KR101958692B1 (ko) * 2012-02-24 2019-03-15 도레이 카부시키가이샤 폴리페닐렌설파이드 섬유, 폴리페닐렌설파이드 섬유로 이루어지는 여포 및 폴리페닐렌설파이드 섬유의 제조 방법
JP6357747B2 (ja) * 2013-09-26 2018-07-18 東レ株式会社 ポリフェニレンスルフィド繊維からなるメルトブロー不織布
US10501875B2 (en) 2014-08-27 2019-12-10 Toray Industries, Inc. Melt-blown nonwoven fabric and method of manufacturing same
AU2015325717B2 (en) 2014-09-30 2018-12-06 Toray Industries, Inc. Polyphenylene sulfide fiber
WO2017170791A1 (fr) * 2016-03-30 2017-10-05 株式会社クラレ Structure de fibres résistant à la chaleur
JP6997527B2 (ja) * 2017-03-30 2022-01-17 旭化成株式会社 ポリフェニレンサルファイド不織布
JPWO2020022260A1 (ja) * 2018-07-27 2021-08-05 東レ株式会社 スパンボンド不織布、および、スパンボンド不織布から構成されるエアフィルター
KR20210060458A (ko) 2018-09-27 2021-05-26 도레이 카부시키가이샤 공중합 폴리페닐렌술피드 섬유

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5024797A (en) * 1989-05-17 1991-06-18 Bayer Aktiengesellschaft Processes for the production of mono- and multifilaments and staple fibers based on polyarylene sulfides
JP2008223209A (ja) * 2007-02-13 2008-09-25 Toyobo Co Ltd 長繊維不織布およびそれを用いた繊維資材
CN101532212A (zh) * 2009-04-23 2009-09-16 华南理工大学 Pps纺粘非织造布及其复合产品以及制备方法
WO2011070999A1 (fr) * 2009-12-09 2011-06-16 東レ株式会社 Procédé pour produire un non tissé à longues fibres

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1260174A (fr) * 1984-06-29 1989-09-26 Kureha Chemical Ind Co Ltd Copolymeres sequences de sulfure de para-phenylene; methode de preparation et utilisation
DE3942416A1 (de) * 1989-09-14 1991-03-28 Bayer Ag Hochmolekulare copolyarylensulfide und ihre verwendungen
JP2001329076A (ja) * 2000-05-25 2001-11-27 Toray Ind Inc ポリフェニレンスルフィドフィルムおよびコンデンサー
US7279440B2 (en) * 2002-05-20 2007-10-09 3M Innovative Properties Company Nonwoven amorphous fibrous webs and methods for making them
TWI340187B (en) * 2006-09-21 2011-04-11 Asahi Kasei Fibers Corp Heat resistant nonwoven fabric
CN102099514B (zh) * 2008-07-18 2013-03-13 东丽株式会社 聚苯硫醚纤维及其制备方法、湿式非织布、湿式非织布的制备方法
BRPI1006538A2 (pt) 2009-03-25 2016-03-29 Toray Industries método para produzir um tecido não-tecido de filamento
CN105442185B (zh) * 2009-03-31 2018-01-16 3M创新有限公司 尺寸上稳定的非织造纤维幅材及其制造和使用方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5024797A (en) * 1989-05-17 1991-06-18 Bayer Aktiengesellschaft Processes for the production of mono- and multifilaments and staple fibers based on polyarylene sulfides
JP2008223209A (ja) * 2007-02-13 2008-09-25 Toyobo Co Ltd 長繊維不織布およびそれを用いた繊維資材
CN101532212A (zh) * 2009-04-23 2009-09-16 华南理工大学 Pps纺粘非织造布及其复合产品以及制备方法
WO2011070999A1 (fr) * 2009-12-09 2011-06-16 東レ株式会社 Procédé pour produire un non tissé à longues fibres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2012165608A1 *

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AU2012263373A1 (en) 2014-01-09
JPWO2012165608A1 (ja) 2015-02-23
AU2012263373B2 (en) 2016-11-17
US20140187115A1 (en) 2014-07-03
CN103562446A (zh) 2014-02-05
CN103562446B (zh) 2015-11-25
JP5867400B2 (ja) 2016-02-24
KR101948637B1 (ko) 2019-02-15
KR20140032452A (ko) 2014-03-14
EP2716800A4 (fr) 2014-11-05

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