EP4006216A1 - Polyamidverbundfaser und fertiggarn - Google Patents

Polyamidverbundfaser und fertiggarn Download PDF

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Publication number
EP4006216A1
EP4006216A1 EP20847355.3A EP20847355A EP4006216A1 EP 4006216 A1 EP4006216 A1 EP 4006216A1 EP 20847355 A EP20847355 A EP 20847355A EP 4006216 A1 EP4006216 A1 EP 4006216A1
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EP
European Patent Office
Prior art keywords
polyamide
composite fiber
crystalline
polyamide composite
crystalline polyamide
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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.)
Pending
Application number
EP20847355.3A
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English (en)
French (fr)
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EP4006216A4 (de
Inventor
Ru Huang
Sumio Yamaguchi
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Toray Industries Inc
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Toray Industries Inc
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Publication of EP4006216A1 publication Critical patent/EP4006216A1/de
Publication of EP4006216A4 publication Critical patent/EP4006216A4/de
Pending 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • 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
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • 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
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • 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
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
    • 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
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool

Definitions

  • the present invention relates to an eccentric sheath-core type composite fiber made of polyamide, and a finished yarn made of the eccentric sheath-core type composite fiber.
  • Polyamide fibers are softer and better in touch than polyester fibers, and have been conventionally widely used for clothing.
  • a single-kind fiber yarn that is made of one kind of polymer such as nylon 6 and nylon 66, which are representatives of the polyamide fibers for clothing, has almost no stretchability in the fiber itself. Therefore, the single-kind fiber yarn is given stretchability by false twisting, and has been used for a stretchable woven or knitted fabric.
  • Patent Literature 1 proposes a method of obtaining a stretchable woven or knitted fabric by using an elastic fiber, or a method of obtaining a stretchable woven or knitted fabric by using two kinds of polymers having different properties in combination and forming a composite fiber having a latent crimpability to cause crimping by a heat treatment such as a dyeing step. Further, as a polyamide composite fiber having the latent crimpability, Patent Literature 2 proposes a composite fiber obtained by arranging two kinds of polyamides having different viscosities in a side-by-side type or an eccentric sheath-core type configuration.
  • Patent Literature 3 proposes a highly heat-shrinkable polyamide composite fiber containing amorphous polyamide or a finished yarn made of the polyamide composite fiber, which shrinks due to a stress exceeding the binding force of the woven or knitted fabric even when a wet heat treatment or a dry heat treatment is performed in a state where high tension is applied in the warp direction, and can exhibit crimpability in the warp direction.
  • Patent Literature 1 when the composite fiber described in Patent Literature 1 is obtained from two kinds of polyamides having different properties, the stretchability may be lost when the composite fiber undergoes a processing step such as a refining step or a dyeing step due to swelling properties unique to the polyamide, and a sufficient stretch is not necessarily obtained in a product.
  • a processing step such as a refining step or a dyeing step due to swelling properties unique to the polyamide, and a sufficient stretch is not necessarily obtained in a product.
  • Patent Literature 2 the same applies to the polyamide composite fiber described in Patent Literature 2.
  • the polyamide composite fiber described in Patent Literature 2 has a problem in that, by applying tension to the woven or knitted fabric in the wet heat treatment step, the crimping of the raw yarn or the finished yarn cannot be sufficiently exhibited, and as a result, the woven or knitted fabric has poor stretchability.
  • an object of the present invention is to solve the above problems, and to provide a polyamide composite fiber from which a woven or knitted fabric having excellent stretchability can be obtained, and a finished yarn made of the polyamide composite fiber.
  • the polyamide composite fiber of the present invention is an eccentric sheath-core type polyamide composite fiber containing two kinds of crystalline polyamides having different compositions, crystalline polyamide (A) and crystalline polyamide (B), in which a water absorption rate after the polyamide composite fiber is allowed to stand for 72 hours under a condition of a temperature being 30°C and a relative humidity being 90 RH% is 5.0% or less, and a thermal shrinkage stress is 0.15 cN/dtex or more.
  • the polyamide composite fiber has a rigid amorphous fraction of 40% to 60% and a stretch elongation ratio of 30% or more.
  • the crystalline polyamide (A) is nylon 6 or a copolymer thereof.
  • the crystalline polyamide (B) is nylon 610 or a copolymer thereof.
  • the crystalline polyamide (A) is a core component
  • the crystalline polyamide (B) is a sheath component
  • the stretch elongation ratio thereof is 100% or more.
  • the present invention can provide a polyamide composite fiber and a finished yarn from which a woven or knitted fabric having excellent stretchability can be obtained.
  • the present invention can further provide a polyamide composite fiber and a finished yarn which shrinks due to a stress exceeding the binding force of the woven or knitted fabric even when a wet heat treatment or a dry heat treatment is performed in a state where high tension is applied in the warp direction, and can sufficiently exhibit crimpability in the warp direction, and from which a woven or knitted fabric having excellent stretchability can be obtained.
  • the polyamide composite fiber of the present invention is an eccentric sheath-core type polyamide composite fiber containing two kinds of crystalline polyamides having different polymer compositions, crystalline polyamide (A) and crystalline polyamide (B), in which a water absorption rate after the polyamide composite fiber is allowed to stand for 72 hours under a condition of a temperature being 30°C and a relative humidity being 90 RH% is 5.0% or less, and a thermal shrinkage stress is 0.15 cN/dtex or more.
  • the polyamide composite fiber of the present invention is an eccentric sheath-core type composite fiber and is constituted by two kinds of crystalline polyamides having different polymer compositions, crystalline polyamide (A) and crystalline polyamide (B).
  • the eccentric sheath-core type polyamide composite fiber refers to a composite fiber in which two or more kinds of polyamides form an eccentric sheath-core structure.
  • the polyamide composite fiber of the present invention is required to have a composite cross section formed by bonding two kinds of crystalline polyamides, and two kinds of crystalline polyamides having different polymer compositions are present in a bonded state without being substantially separated.
  • the polyamide composite fiber is preferably an eccentric sheath-core type composite fiber in which the crystalline polyamide (A) is used as a core component, the crystalline polyamide (B) is used as a sheath component, and the crystalline polyamide (A) is covered with the crystalline polyamide (B).
  • centroid means that the position of the center of gravity of the core component is different from the center of the cross section of the composite fiber in the cross section of the polyamide composite fiber.
  • FIG. 1 is a model cross-sectional view illustrating a cross section of an eccentric sheath-core type polyamide composite fiber (hereinafter, also referred to as "polyamide eccentric sheath-core type composite fiber") of the present invention.
  • a polyamide eccentric sheath-core type composite fiber 10A is constituted by a core component (crystalline polyamide (A)) 1 and a sheath component (crystalline polyamide (B)) 2, and the position of the center of gravity of the crystalline polyamide (A) as the core component is different from the center of the cross section of the composite fiber.
  • FIGs. 2(A) to 2(C) are model cross-sectional views respectively illustrating cross-sections of other polyamide eccentric sheath-core type composite fibers of the present invention.
  • FIGs. 2(A), 2(B), and 2(C) respectively illustrate modes of polyamide eccentric sheath-core type composite fibers 10B to 10C that are different in shape arrangement states of the core component (crystalline polyamide (A)) 1 and the sheath component (crystalline polyamide (B)) 2 of the eccentric sheath-core type composite fiber, and similarly to FIG. 1 , the position of the center of gravity of the crystalline polyamide (A) as the core component is different from the center of the cross section of the composite fiber.
  • a composite ratio between the crystalline polyamide (A) and the crystalline polyamide (B) is preferably within a range of 6:4 to 4:6 (mass ratio).
  • mass ratio is set to 6:4 to 4:6 in this manner, the water absorption rate of the polyamide composite fiber of the present invention can be controlled to 5.0% or less, and the obtained woven or knitted fabric is provided with excellent stretchability.
  • the polyamide composite fiber of the present invention is constituted by two kinds of crystalline polyamides having different polymer compositions.
  • the crystalline polyamide is a polyamide that forms crystals and has a melting point, and is a polymer in which so-called hydrocarbon groups are linked to a main chain via amide bonds.
  • Specific examples of the crystalline polyamide include polycapramide, polyhexamethylene adipamide, polyhexamethylene sebacamide, polytetramethylene adipamide, and a condensation polymerization type polyamide of 1,4-cyclohexanebis and a linear aliphatic dicarboxylic acid, and copolymers thereof or mixtures thereof.
  • the crystalline polyamide (A) is a kind of polyamide different from the crystalline polyamide (B), and examples thereof include nylon 6, nylon 66, nylon 4, nylon 610, nylon 11, nylon 12, and copolymers containing these as main components.
  • the crystalline polyamide (A) may contain components besides lactams, aminocarboxylic acids, diamines, and dicarboxylic acids in a repeating structure thereof as long as the effects of the present invention are not inhibited.
  • an elastomer containing a polyol or the like in a repeating structure is excluded from the viewpoint of the silk-reeling property and the strength.
  • the crystalline polyamide (A) is preferably a polymer in which a content of a single kind of lactam, an aminocarboxylic acid, or a combination of a diamine and a dicarboxylic acid in the repeating structure is 90% or more, more preferably 95% or more.
  • the components are particularly preferably nylon 6 or a copolymer thereof from the viewpoint of thermal stability.
  • the crystalline polyamide (B) is obtained by, for example, a combination of diamine units and dicarboxylic acid units containing sebacic acid units as a main component.
  • nylon 610 which has stable polymerizability, less yellowing of crimped finished yarns and good dyeability, and a copolymer thereof are most preferably used.
  • the sebacic acid can be produced, for example, by refining seeds of castor oil, and is regarded as a plant-derived raw material.
  • dicarboxylic acid constituting the dicarboxylic acid units other than the sebacic acid units examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, phthalic acid, isophthalic acid, and terephthalic acid, and these dicarboxylic acids can be blended within a range that does not impair the effects of the present invention.
  • dicarboxylic acids are also preferably plant-derived dicarboxylic acids.
  • the copolymerization amount of the dicarboxylic acid units other than the sebacic acid units is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and still more preferably 0 to 10 mol%, based on all the dicarboxylic acid units.
  • the diamines that constitute the diamine units are diamines having two or more carbon atoms, preferably diamines having 4 to 12 carbon atoms, and specific examples thereof include putrescine, 1,5-pentanediamine, hexamethylenediamine, trimethylenediamine, nonanediamine, methylpentanediamine, phenylenediamine, and ethambutol. These diamines are also preferably plant-derived diamines.
  • a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a plasticizer, a release agent, a lubricant, a foaming agent, an antistatic agent, a moldability improver, a reinforcing agent, and the like may be added to and blended with the crystalline polyamide (A) and the crystalline polyamide (B).
  • the polyamide composite fiber of the present invention is required to have a water absorption rate of 5.0% or less after being allowed to stand for 72 hours under a condition of a temperature being 30°C and a relative humidity being 90 RH% (a temperature of 30°C ⁇ a relative humidity of 90 RH%).
  • the water absorption rate herein is a value measured in accordance with JIS L 1013.
  • the swelling of the polyamide fiber under a wet heat condition of a refining step and a dyeing step is reduced, and the elongation of the woven or knitted fabric during these steps is reduced. Accordingly, it is possible to perform steps such as a refining step and a dyeing step without applying extra tension to the woven or knitted fabric. As a result, a woven or knitted fabric having excellent stretchability is obtained.
  • the polyamide fiber tends to swell with water.
  • the water absorption rate is more than 5.0%, wrinkles and textures are likely to occur in the refining or relaxing treatment step and the dyeing step, and the polyamide fibers are generally subjected to a stretching treatment, causing the stretchability to be reduced.
  • the water absorption rate is preferably 4% or less.
  • the lower limit of the water absorption rate cannot be specified, and is practically about 1.0%.
  • the water absorption rate can be controlled depending on the polymer selection of the crystalline polyamide (A) and the crystalline polyamide (B) and the core/sheath composite ratio.
  • the polyamide composite fiber of the present invention is required to have a thermal shrinkage stress of 0.15 cN/dtex or more.
  • a thermal shrinkage stress measuring machine for example, model "KE-2", manufactured by Kanebo Engineering Ltd.
  • the thermal shrinkage stress is measured by connecting fiber yarns to be measured to form a loop having a circumferential length of 16 cm, applying an initial load of 1/30 g of fineness (dtex) of yarns to the loop, performing measurement with a temperature rising rate of 100°C/min from a temperature of 40°C to a temperature of 210°C, and a peak value of the obtained thermal stress curve is regarded as the maximum thermal stress (cN/dtex).
  • the thermal shrinkage stress is 0.15 cN/dtex or more
  • a woven or knitted fabric shrinks due to a stress exceeding the binding force of the woven fabric even when a wet heat treatment or a dry heat treatment is performed in a state in which high tension is applied in the warp direction. Therefore, it is possible to obtain a woven or knitted fabric that can sufficiently exhibit crimpability in the warp direction and has good stretchability.
  • the thermal shrinkage stress is less than 0.15 cN/dtex, sufficient crimping is not exhibited in the wet heat treatment step in which high tension is applied. Therefore, a woven or knitted fabric having poor stretchability is obtained.
  • the thermal shrinkage stress is preferably 0.20 cN/dtex or more, more preferably 0.25 cN/dtex or more.
  • the upper limit of the thermal shrinkage stress is preferably 0.50 cN/dtex.
  • the thermal shrinkage stress can be controlled by using a high-viscosity polymer, controlling rigid amorphous fractions of fibers under the thermal stretching conditions of a low spinning temperature, and a low spinning speed and a high stretching ratio, or the like.
  • a rigid amorphous fraction of the polyamide composite fibers of the present invention is preferably 40% to 60%.
  • the rigid amorphous phase refers to an amorphous phase whose amount is determined according to a method described in the items of Examples, and is an intermediate state between a crystalline state and a mobile amorphous state (a completely amorphous state in related arts).
  • the molecular motion in the rigid amorphous fractions is frozen even at the glass transition temperature (Tg) or higher, and the rigid amorphous fractions are in a fluid state at a temperature higher than Tg (for example, see " DSC (3)-Glass transition behavior of polymers-", Journal of the Textile Society (Fibers and Industry), TODOKI Minoru, Vol. 65, No. 10 (2009 )).
  • the rigid amorphous fraction is represented by "100% - crystallinity - mobile amorphous fraction".
  • the polyamide composite fiber includes a crystalline portion, a rigid amorphous portion, and a mobile amorphous portion.
  • the thermal shrinkage stress depends on the binding force of a rigid amorphous chain at the time of forming a fiber structure and the shrinkage of a mobile amorphous chain that is exhibited when the heat treatment is performed.
  • the thermal shrinkage stress can be exhibited by setting the rigid amorphous fraction within the above range.
  • the rigid amorphous fraction can be controlled by spinning.
  • the rigid amorphous fraction can be controlled by the use of high-viscosity polymers and the design of production methods, similarly to the thermal shrinkage stress.
  • the rigid amorphous fraction When the rigid amorphous fraction is 40% or more, the binding force of the rigid amorphous chain can be exhibited, and the desired thermal shrinkage stress can be obtained without impairing the shrinkability of the mobile amorphous chain. When the rigid amorphous fraction is 60% or less, the binding force of the rigid amorphous chain can be exhibited, the shrinkage force of the mobile amorphous chain can be retained, and the desired thermal shrinkage stress can be obtained.
  • the rigid amorphous fraction is preferably 45% to 55%.
  • the polyamide composite fiber of the present invention preferably has a stretch elongation ratio of 30% or more.
  • the stretch elongation ratio is an index of crimpability of a raw yarn, and a higher value indicates a higher crimping-exhibiting ability.
  • the polyamide composite fiber of the present invention a difference in shrinkage is exhibited depending on a difference in orientation between the crystalline polyamide (A) and the crystalline polyamide (B) when the fibers are formed, and crimping is exhibited.
  • polyamide fibers are likely to be wrinkled in the refining or dyeing step of a woven or knitted fabric in general, and in order to maintain the quality of the woven or knitted fabric, the processing is performed in a state in which high tension is applied in the warp direction. Therefore, the difference in shrinkage may decrease due to the influence of external force (high tension).
  • the raw yarn has a constant thermal shrinkage stress to maintain the difference in shrinkage, so that crimpability of the raw yarn can be maintained.
  • the stretch elongation ratio is 30% or more, a woven or knitted fabric having more excellent stretchability can be obtained.
  • the stretch elongation ratio is more preferably 100% to 200%. Since the stretch elongation ratio is exhibited by the difference in shrinkage between both components of the crystalline polyamide (A) and the crystalline polyamide (B), the larger the difference in shrinkage, the higher the stretch elongation ratio.
  • the polyamide composite fiber of the present invention preferably has a total fineness of a yarn of 20 to 120 dtex.
  • the total fineness is more preferably 30 to 90 dtex.
  • the single fiber fineness of polyamide composite fiber cannot be specified, and is generally within a range of 1.0 to 5.0 dtex.
  • the relative viscosity of the crystalline polyamide (A) is preferably 3.1 to 3.8.
  • the relative viscosity of the crystalline polyamide (B) is preferably 2.6 to 2.8.
  • the relative viscosity ratio (A/B) of the crystalline polyamide (A) to the crystalline polyamide (B) is more preferably 1.2 to 1.4.
  • a crystalline polyamide having a relative viscosity within such a range When a crystalline polyamide having a relative viscosity within such a range is selected, a difference in shrinkage is exhibited after the heat treatment, and a three-dimensional spiral structure is formed to exhibit the crimping.
  • the polyamide makes a transition from the amorphous state to the crystalline state by receiving the melting heat during the yarn producing step.
  • the crystalline polyamide (A) having a high relative viscosity has a high molecular binding force, the rate of transition from the amorphous state to the crystalline state is lower than that of the crystalline polyamide (B) having a low relative viscosity.
  • the polyamide composite fiber of the present invention has a composite cross section formed by bonding two kinds of crystalline polyamides, and has an eccentric sheath-core type structure in which the crystalline polyamide (A) as a core component is covered with the crystalline polyamide (B) as a sheath component.
  • the crystalline polyamides having a difference in relative viscosity described above are melted to form a composite cross section in the spinning pack, and at the time of ejection from the spinneret, the polymer flow resistances are different and a difference in the flow rate is generated.
  • the crystalline polyamide (A) and the crystalline polyamide (B) are separately melted, weighed and transported using a gear pump to form a composite flow so that a sheath-core structure is formed by a normal method as it is, and using a spinneret for eccentric sheath-core type composite fibers, polyamide composite fiber yarns are ejected from the spinneret so as to have a cross section illustrated in FIG. 1 .
  • the ejected polyamide composite fiber yarns are cooled to reach a temperature of 30°C by being blown with cooling air by means of a yarn cooling device such as chimney.
  • the cooled yarns are coated with oil by an oil supply device, converged, drawn by a drawing roller at 1500 to 4000 m/min, passed through the drawing roller and a stretching roller, and stretched at 1.5 to 3.0 times in accordance with a ratio of the circumferential speed of the drawing roller to the circumferential speed of the stretching roller at that time.
  • the yarns are heat-set by a stretching roller and are wound into a package at a winding rate of 3000 m/min or more.
  • the crystalline polyamide (A) and the crystalline polyamide (B) are separately melted, weighed and transported using a gear pump to form a composite flow so that a sheath-core structure is formed by a normal method as it is, and using a spinneret for eccentric sheath-core type composite fibers, polyamide composite fiber yarns are ejected from the spinneret so as to have a cross section illustrated in FIG. 1 .
  • the ejected polyamide composite fiber yarns are cooled to reach a temperature of 30°C by being blown with cooling air by means of a yarn cooling device such as chimney.
  • the cooled yarns are coated with oil by an oil supply device, converged, drawn by a drawing roller at 3000 to 4500 m/min, passed through the drawing roller and a stretching roller, and stretched slightly at 1.0 to 1.2 times in accordance with a ratio of the circumferential speed of the drawing roller to the circumferential speed of the stretching roller at that time. Further, the yarns are wound into a package at a winding rate of 3000 m/min or more.
  • the spinning temperature is appropriately designed based on the melting point of the crystalline polyamide (A) having a high relative viscosity.
  • the spinning temperature rises, the crystalline portion tends to increase, and the rigid amorphous fraction tends to decrease.
  • the spinning temperature decreases, the mobile amorphous fraction tends to increase, and the rigid amorphous fraction tends to decrease slightly. Therefore, the spinning temperature is preferably 35°C to 70°C higher than the melting point of the crystalline polyamide (A), and more preferably 45°C to 60°C higher than the melting point of the crystalline polyamide (A).
  • the rigid amorphous fraction of the polyamide composite fiber of the present invention is increased, and the thermal shrinkage stress and the stretch elongation ratio are improved.
  • the drawing rate is preferably 1500 to 4000 m/min.
  • the rigid amorphous fraction in the polyamide composite fiber of the present invention is increased, and the thermal shrinkage stress is improved.
  • the stretching ratio is preferably 1.5 to 3.0 times, more preferably 2.0 to 3.0 times.
  • the thermal stretching temperature is preferably 30°C to 90°C, more preferably 40°C to 60°C.
  • the thermal shrinkage stress of the polyamide composite fiber of the present invention can be appropriately designed.
  • the heat-setting temperature is preferably 130°C to 180°C.
  • the entanglement may also be performed by using a known entanglement apparatus in the steps up to the winding. If necessary, the number of entanglements may also be increased by applying entanglements multiple times. Furthermore, an oil agent may also be additionally applied immediately before the winding.
  • the eccentric sheath-core type polyamide composite fiber of the present invention is used as at least a part of the yarns.
  • the production method in the yarn processing is not limited, and examples thereof include a mixed fiber spinning method and a false twisting method.
  • the mixed fiber spinning method air-mixed spinning, twisting or composite false twisting may be applied, and the air-mixed spinning is preferably used since the control of the air-mixed spinning is easy and the production cost is low.
  • the false twisting method it is preferable to perform false twisting by using a pin type, a friction type, a belt type or the like according to the fineness and the number of twists.
  • the finished yarn made of the polyamide composite fiber of the present invention preferably has a stretch elongation ratio of 100% or more.
  • the stretch elongation ratio is set to 100% or more, sufficient exhibition of crimping and crimping of the false-twisted yarn are combined, and a woven or knitted fabric having excellent stretchability is obtained.
  • the crimpability increases as the stretch elongation ratio is increased, but processing wrinkles are likely to occur, and production is carried out in a state in which high tension is applied in the warp direction to prevent the wrinkles, resulting in inhibition of the stretchability of the woven or knitted fabric. Therefore, the stretch elongation ratio is more preferably 120% to 200%.
  • the finished yarn made of the polyamide composite fiber of the present invention preferably has a stretch elongation ratio of 100% or more as described above.
  • the stretchable woven or knitted fabric is formed by using the polyamide composite fiber or the finished yarn of the present invention in at least a part thereof. According to the present invention, it is possible to provide a woven or knitted fabric that can sufficiently exhibit the crimping even when a high tension is applied in the warp direction in the wet heat treatment step, and have excellent stretchability.
  • the stretchable woven or knitted fabric made of the polyamide composite fiber or the finished yarn of the present invention can be woven and knitted according to a known method.
  • the weave of the woven or knitted fabric is not limited.
  • the weave thereof may be any of a plain weave, a twill weave, a sateen weave, a modified weave thereof, and a mixed weave thereof depending on the intended application.
  • the plain weave with many restraint points, or the ripstop weave obtained by combing plain weave, flat cords, and further mat weave is preferred.
  • the weave thereof may be any of plain weave of a circular knitted fabric, interlock weave, half weave of a warp knitted fabric, satin weave, jacquard weave, modified weave thereof, and mixed weave thereof depending on the intended application, and the half weave of a single tricot knitted fabric or the like is preferred from the viewpoint that the knitted fabric is thin, stable, and excellent in the stretch ratio.
  • the application of the woven or knitted fabric made of the polyamide composite fiber or the finished yarn of the present invention is not limited, and the application for clothing is preferred, and applications for sport clothing represented by down jackets, windbreakers, golf wear, and rainwear, casual wear, and women's and men's clothing are more preferred.
  • the polyamide composite fiber or the finished yarn can be suitably used for sportswear and down jackets.
  • the rigid amorphous fraction (Xra) was calculated by the following formula (3). Note that the rigid amorphous fraction was calculated based on an average value obtained by measuring these two times.
  • Xc % ⁇ Hm ⁇ ⁇ Hc / ⁇ Hm 0 ⁇ 100
  • Xma % ⁇ Cp / ⁇ Cp 0 ⁇ 100
  • Xra % 100 ⁇ Xc + Xma
  • G. Strength and Elongation The fiber sample was measured using "TENSILON” (registered trademark) UCT-100 manufactured by Orientec Co., Ltd. under a constant speed elongation condition specified in JIS L1013 (chemical fiber filament yarn testing method, 2010). The elongation was determined from the elongation at a point at which the maximum strength in the tensile strength-elongation curve is shown. As the strength, a value obtained by dividing the maximum strength by the fineness was defined as the strength. The measurement was performed 10 times, and the average values were defined as the strength and the elongation.
  • the obtained woven fabric was refined at a temperature of 80°C for 20 minutes, then stained at a temperature of 100°C for 30 minutes using a dye of Kayanol Yellow N5G 1%owf whose pH is adjusted to 4 with acetic acid, followed by being subjected to a Fix treatment at a temperature of 80°C for 20 minutes, and finally heat-treated at a temperature of 170°C for 30 seconds to improve the texture.
  • each of the woven fabric samples having a width of 50 mm ⁇ 300 mm obtained in Examples 1 to 10 and Comparative Examples 1 to 4 was stretched to 14.7 N at a tensile rate of 200 mm/min in the warp direction of the woven fabric at a grip interval of 200 mm and the stretch rate was measured.
  • the stretch rate was evaluated in the following three grades "A", "B", and "C”.
  • a woven fabric with a stretch rate of 15% or more was determined to have stretchability.
  • the yarns ejected from the spinneret were cooled and solidified by a yarn cooling device, coated with a hydrous oil agent by an oil supply device, entangled by a fluid entangling nozzle device, followed by being drawn at 3700 m/min with a drawing roller (room temperature: 25°C) and being stretched by 1.1 times with a stretching roller (room temperature: 25°C), and then wound into a package at a winding rate of 4000 m/min.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 49%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.16 cN/dtex, and a rigid amorphous fraction of 41%, were obtained.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 53%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.21 cN/dtex, and a rigid amorphous fraction of 46%, were obtained in the same method as in Example 1 except that nylon 6 (N6) with a relative viscosity of 3.6 and a melting point of 222°C was used as the crystalline polyamide (A).
  • the obtained polyamide composite fiber yarns were subjected to disc false twisting in the same method as in Example 1 to obtain false-twist finished yarns having a stretch elongation ratio of 150%.
  • the obtained false-twist finished yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability. The results are shown in Table 1.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 67%, a water absorption rate of 3.6%, a thermal shrinkage stress of 0.25 cN/dtex, and a rigid amorphous fraction of 53%, were obtained in the same method as in Example 1 except that a copolymerized product of nylon 6 and nylon 66 (N6/N66) with a relative viscosity of 3.6 and a melting point of 200°C was used as the crystalline polyamide (A).
  • the obtained polyamide composite fiber yarns were subjected to disc false twisting in the same method as in Example 1 to obtain false-twist finished yarns having a stretch elongation ratio of 200%.
  • the obtained false-twist finished yarns were used as warps to form a woven fabric.
  • the obtained woven fabric had more excellent stretchability than those of Examples 1 and 2. The results are shown in Table 1.
  • a copolymerized product of nylon 6 and nylon 66 (N6/N66) with a relative viscosity of 3.6 and a melting point of 200°C was used as the crystalline polyamide (A), and nylon 610 (N610) with a relative viscosity of 2.7 and a melting point of 225°C was used as the crystalline polyamide (B).
  • the crystalline polyamide (A) was used as a core component and the crystalline polyamide (B) was used as a sheath component.
  • the yarns ejected from the spinneret were cooled and solidified by a yarn cooling device, coated with a non-hydrous oil agent by an oil supply device, entangled by a fluid entangling nozzle device, followed by being drawn at 1700 m/min with a slightly-heating drawing roller (temperature: 50°C) and being stretched by 2.4 times with a heating stretching roller (heat-setting temperature: 150°C), and then wound into a package at a winding rate of 4000 m/min.
  • a yarn cooling device coated with a non-hydrous oil agent by an oil supply device, entangled by a fluid entangling nozzle device, followed by being drawn at 1700 m/min with a slightly-heating drawing roller (temperature: 50°C) and being stretched by 2.4 times with a heating stretching roller (heat-setting temperature: 150°C), and then wound into a package at a winding rate of 4000 m/min.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 117%, a water absorption rate of 3.6%, a thermal shrinkage stress of 0.29 cN/dtex, and a rigid amorphous fraction of 55%, were obtained.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric had more excellent stretchability than that of Example 5.
  • the results are shown in Table 2.
  • the yarns ejected from the spinneret were cooled and solidified by a yarn cooling device, coated with a non-hydrous oil agent by an oil supply device, entangled by a fluid entangling nozzle device, followed by being drawn at 1700 m/min with a slightly-heating drawing roller (temperature: 50°C) and being stretched by 2.4 times with a heating stretching roller (heat-setting temperature: 150°C), and then wound into a package at a winding rate of 4000 m/min.
  • a yarn cooling device coated with a non-hydrous oil agent by an oil supply device, entangled by a fluid entangling nozzle device, followed by being drawn at 1700 m/min with a slightly-heating drawing roller (temperature: 50°C) and being stretched by 2.4 times with a heating stretching roller (heat-setting temperature: 150°C), and then wound into a package at a winding rate of 4000 m/min.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 83%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.20 cN/dtex, and a rigid amorphous fraction of 46%, were obtained.
  • the obtained composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability. The results are shown in Table 2.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability.
  • Table 2 The results are shown in Table 2.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability.
  • Table 2 The results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 103%, a water absorption rate of 4.1%, a thermal shrinkage stress of 0.20 cN/dtex, and a rigid amorphous fraction of 46%, were obtained in the same method as in Example 5 except that nylon 6 (N6) with a relative viscosity of 3.6 and a melting point of 222°C was used as the crystalline polyamide (A), and a copolymerized product of nylon 610 and nylon 510 (N610/N510) with a relative viscosity of 2.7 and a melting point of 225°C was used as the crystalline polyamide (B).
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric had more excellent stretchability than that of Example 5.
  • the results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 82%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.18 cN/dtex, and a rigid amorphous fraction of 43%, were obtained in the same method as in Example 5 except that the yarns were drawn at 2050 m/min with a slightly-heating drawing roller (50°C) and stretched by 2.0 times with a heating stretching roller (heat-setting temperature: 150°C). The obtained polyamide composite fiber yarns were used as warps to form a woven fabric. The obtained woven fabric was excellent in the stretchability. The results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 82%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.18 cN/dtex, and a rigid amorphous fraction of 43%, were obtained in the same method as in Example 5 except that the spinning temperature was changed to 280°C.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability. The results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 95%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.22 cN/dtex, and a rigid amorphous fraction of 49%, were obtained in the same method as in Example 5 except that the spinning temperature was changed to 260°C.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was excellent in the stretchability. The results are shown in Table 2.
  • Polyamide composite yarns of 62 dtex/12 filaments were obtained in the same method as in Example 5 except that nylon 6 (N6) with a relative viscosity of 2.7 and a melting point of 222°C was used as the crystalline polyamide (A).
  • the composite yarns of Comparative Example 1 which had almost no difference in relative viscosity, had a small difference in shrinkage after the heat treatment and had crimping with a low stretch elongation ratio of 13%, a thermal shrinkage stress of 0.13 cN/dtex, and a low rigid amorphous fraction of 39%.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric, and the obtained woven fabric was inferior in stretchability. The results are shown in Table 2.
  • the polyamide composite yarns of Comparative Example 2 in which the ratio of the polyamide (A) having a high water absorption rate was increased had a high water absorption rate of 5.8%.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric in the same manner as in Example 5. However, since wrinkles remained, processing was performed to increase the tension in the warp direction to an extent that no wrinkles remained. As a result, a woven fabric having poor stretchability was obtained. The results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments were obtained in the same method as in Example 5 except that nylon 6 (N6) with a relative viscosity of 3.3 and a melting point of 222°C was used as the crystalline polyamide (A), and nylon 6 (N6) with a relative viscosity of 2.7 and a melting point of 225°C was used as the crystalline polyamide (B).
  • the polyamide composite fiber yarns of Comparative Example 3 produced by using polyamides having high water absorption rate had a high water absorption rate of 6.2%.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric in the same manner as in Example 5. However, since wrinkles remained, processing was performed to increase the tension in the warp direction to an extent that no wrinkles remained. As a result, a woven fabric having poor stretchability was obtained. The results are shown in Table 2.
  • Polyamide composite fiber yarns of 62 dtex/12 filaments which had a stretch elongation ratio of 53%, a water absorption rate of 3.8%, a thermal shrinkage stress of 0.13 cN/dtex, and a rigid amorphous fraction of 36%, were obtained in the same method as in Example 5 except that the spinning temperature was changed to 300°C.
  • the obtained polyamide composite fiber yarns were used as warps to form a woven fabric.
  • the obtained woven fabric was inferior in stretchability. The results are shown in Table 2.

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WO2016104278A1 (ja) * 2014-12-26 2016-06-30 東レ株式会社 高収縮性ポリアミド繊維およびそれを一部に用いた混繊糸および織編物
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