CN108138378B - Core-sheath composite cross-section fiber having excellent moisture absorption and wrinkle resistance - Google Patents
Core-sheath composite cross-section fiber having excellent moisture absorption and wrinkle resistance Download PDFInfo
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- CN108138378B CN108138378B CN201680061247.1A CN201680061247A CN108138378B CN 108138378 B CN108138378 B CN 108138378B CN 201680061247 A CN201680061247 A CN 201680061247A CN 108138378 B CN108138378 B CN 108138378B
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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
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- 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
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/292—Conjugate, i.e. bi- or multicomponent, fibres or filaments
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
- D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/573—Tensile strength
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/022—Moisture-responsive characteristics hydrophylic
Abstract
A core-sheath composite cross-sectional fiber characterized in that a core polymer is a thermoplastic polymer, a sheath polymer is a polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component, a boiling water shrinkage ratio is 6.0 to 12.0%, and a stress per unit fineness at 3% elongation in a tensile test of the fiber is 0.60cN/dtex or more. The invention provides a core-sheath composite cross-section fiber which is excellent in moisture absorption performance and wrinkle resistance and can maintain moisture absorption performance even when washed.
Description
Technical Field
The present invention relates to a core-sheath composite cross-sectional fiber having excellent moisture absorption and wrinkle resistance.
Background
Synthetic fibers made of thermoplastic resins such as polyamide and polyester are excellent in strength, chemical resistance, heat resistance, and the like, and thus are widely used for clothing applications, industrial applications, and the like.
In particular, polyamide fibers have excellent moisture absorption and moisture release properties in addition to their unique characteristics such as flexibility, high tensile strength, color development during dyeing, and high heat resistance, and are widely used for underwear, sportswear, and the like. However, polyamide fibers have insufficient moisture absorbing and releasing properties as compared with natural fibers such as cotton, have problems such as stuffiness and sticky feeling, and are inferior to natural fibers in terms of wearing comfort.
Under such circumstances, synthetic fibers which exhibit excellent moisture absorption and release properties for preventing stuffiness and stickiness and have wearing comfort close to that of natural fibers have been strongly demanded mainly for underwear and sportswear.
Patent document 1 discloses a core-sheath composite cross-sectional fiber having a shape in which a core portion is not exposed to the surface of the fiber, the core-sheath composite cross-sectional fiber being composed of a core portion and a sheath portion, the core portion being a polyether block amide copolymer having a hard segment of polycaproamide, the core portion being a polyether block amide copolymer, the polycaproamide being a sheath portion, and the area ratio of the core portion to the sheath portion in the cross section of the fiber being 3/1 to 1/5.
Patent document 2 discloses a core-sheath composite cross-sectional fiber having excellent moisture absorption and moisture release properties, which is characterized in that a thermoplastic polymer is used as a core portion and a fiber-forming polyamide is used as a sheath portion, the main component of the thermoplastic polymer forming the core portion is a polyether ester amide copolymer, and the ratio of the core portion is 5 to 50 wt% of the total weight of the composite fiber.
Patent document 3 discloses a core-sheath composite cross-sectional fiber having excellent antistatic performance, water absorbing performance, and cool contact feeling, which has a polyether block amide copolymer as a core portion, a fiber-forming polymer such as polyamide or polyester as a sheath portion, and an exposure angle of the core portion in the range of 5 ° to 90 °. The core-sheath composite cross-section fibers of patent documents 1 to 3 are used as knitted fabrics for underwear and sports.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2014/10709
Patent document 2: japanese laid-open patent publication No. 6-136618
Patent document 3: international publication No. 2008/123586
Disclosure of Invention
Problems to be solved by the invention
However, the core-sheath composite cross-sectional fibers of patent documents 1 to 3 have excellent moisture absorption and release properties due to the high moisture absorption performance of the core component polymer, but have a problem that the fibers are easily deformed and easily wrinkled in the dyeing step because they are polymers having high shrinkage characteristics and flexibility. In addition, the same phenomenon is likely to occur during washing. Further, the core portion deteriorates due to repeated practical use, and the moisture absorption performance is lowered due to repeated use, which is also a problem.
Means for solving the problems
The present invention has been made to solve the problems of the prior art described above, and an object of the present invention is to provide a core-sheath composite cross-sectional fiber having excellent moisture absorption and moisture release properties and wrinkle resistance. Further, an object of the present invention is to provide a core-sheath composite cross-sectional fiber capable of maintaining moisture absorption performance even when washed.
The present invention includes the following configurations to solve the above problems.
(1) A core-sheath composite cross-sectional fiber characterized in that a core polymer is a thermoplastic polymer, a sheath polymer is a polyamide having a dicarboxylic acid unit comprising a sebacic acid unit as a main component, a boiling water shrinkage ratio is 6.0 to 12.0%, and a stress per unit fineness at 3% elongation in a tensile test of the fiber is 0.60cN/dtex or more.
(2) The core-sheath composite cross-sectional fiber according to (1), wherein the α crystal orientation parameter of the sheath portion is 2.10 to 2.70.
(3) The core-sheath composite cross-sectional fiber according to (1) or (2), characterized in that the stress retention per unit fineness at 3% elongation in a tensile test of the fiber before and after boiling water treatment is 60% or more.
(4) A fabric comprising the core-sheath composite cross-sectional fiber according to any one of (1) to (3) at least in a part of the fabric.
(5) A fiber product comprising the core-sheath composite cross-sectional fiber according to any one of (1) to (3) at least in a part of the fiber product.
Effects of the invention
According to the present invention, it is possible to provide a core-sheath composite cross-sectional fiber which is excellent in moisture absorption performance and wrinkle resistance and can maintain moisture absorption performance even when washed.
Detailed Description
In the core-sheath composite cross-sectional fiber of the present invention, a polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component is used as a sheath polymer, and a thermoplastic polymer having high moisture absorption performance is used as a core polymer.
The polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component in the sheath portion is a polymer formed of a high molecular weight in which a hydrocarbon is linked to a main chain via an amide bond, and specifically includes polypentamethylenesebacamide, polyhexamethylenesebacamide, and copolymers thereof, but from the viewpoints of economy, relatively easy filament production, excellent dyeing properties, excellent mechanical properties, and the like, a polyamide mainly containing polyhexamethylenesebacamide is preferable as such a polyamide.
In the polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component in the sheath portion, various additives such as a delustering agent, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent whitening agent, an antistatic agent, a hygroscopic polymer, carbon, and the like may be copolymerized or mixed as necessary in an amount of 0.001 to 10% by weight of the total additive content.
The thermoplastic polymer having high moisture absorption performance of the core portion means a polymer having a Δ MR of 10% or more as measured in a particle shape, and examples thereof include polyether ester amide copolymers, polyvinyl alcohols, cellulose-based thermoplastic polymers, and the like. Among these, polyether ester amide copolymers are preferable from the viewpoint of good thermal stability, good compatibility with the polyamide of the sheath portion, and excellent peeling resistance.
The Δ MR here is determined by weighing about 1 to 2g of the pellets into a weighing bottle, measuring the weight after drying at 110 ℃ for 2 hours (W0), and then measuring the weight after keeping the pellets at 20 ℃ and 65% relative humidity for 24 hours (W65). Further, the weight of the pellets after they were held at 30 ℃ and 90% relative humidity for 24 hours was measured (W90). Further, the calculation was performed according to the following equation.
MR65(％)＝[(W65-W0)/W0]×100
MR90(％)＝[(W90-W0)/W0]×100
ΔMR(％)＝MR90-MR65。
The polyether ester amide copolymer is a block copolymer having an ether bond, an ester bond and an amide bond in the same molecular chain. More specifically, the block copolymer polymer is obtained by polycondensation reaction of a polyamide component (a) comprising 1 or 2 or more selected from lactams, aminocarboxylic acids, and salts of diamines and dicarboxylic acids, and a polyether ester component (B) comprising a dicarboxylic acid and a poly (oxyalkylene) glycol.
Examples of the polyamide component (A) include lactams such as caprolactam, laurolactam and undecalamide, omega-aminocarboxylic acids such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, and nylon salts of diamine-dicarboxylic acid which is a precursor of polyhexamethylene adipamide, polyhexamethylene sebacamide and polyhexamethylene dodecanoamide, and a preferable polyamide component is caprolactam.
The polyether ester component (B) is a component composed of a dicarboxylic acid having 4-20 carbon atoms and a poly (oxyalkylene) glycol. Examples of the dicarboxylic acid having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and dodecanoic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid, and alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid, and 1 kind or 2 or more kinds of them can be used in combination. Preferred dicarboxylic acids are adipic acid, sebacic acid, dodecanoic acid, terephthalic acid and isophthalic acid. Further, examples of the poly (oxyalkylene) glycol include polyethylene glycol, poly (1, 2-and 1,3-) propylene glycol, poly (1, 4-butanediol, poly (1, 6-hexanediol), etc., and polyethylene glycol having particularly good moisture absorption property is preferable.
The number average molecular weight of the poly (oxyalkylene) glycol is preferably 300 to 10000, more preferably 500 to 5000. The molecular weight of 300 or more is preferable because it is less likely to scatter out of the system during the polycondensation reaction and provides a fiber having stable moisture absorption properties. Further, when 10000 or less, a uniform block copolymer can be obtained, and the yarn formability is stable, which is preferable.
The composition ratio of the polyether ester component (B) is preferably 20 to 80% in terms of a molar ratio. It is preferable that the content is 20% or more because good moisture absorption can be obtained. Further, if it is 80% or less, good dyeing fastness and washing durability can be obtained, so that it is preferable.
Such polyether ester amide copolymers are commercially available as "MH 1657" and "MV 1074" available from アルケマ.
The shrinkage of the core-sheath composite cross-section fiber in boiling water is 6.0-12.0%. When the boiling water shrinkage exceeds 12.0%, the fiber is easily deformed and wrinkled in the dyeing step. When the boiling water shrinkage is less than 6.0%, although the crease resistance is excellent, the workability in the yarn-making step may deteriorate and the quality may deteriorate. When the boiling water shrinkage ratio is in the above range, the crease resistance is excellent. Preferably 6.0 to 10.0%.
The core-sheath composite cross-sectional fiber of the present invention requires that the stress per unit fineness at 3% elongation in the tensile test of the fiber is 0.60cN/dtex or more, the stress at 3% elongation in the tensile test of the fiber is determined by subjecting a sample to the tensile test under the constant-speed elongation conditions shown in JIS L1013 (chemical fiber filament test method, 2010), and determining from the strength at which the sample is elongated by 3% in the tensile strength-elongation curve, and the value obtained by dividing the strength by the fineness of the fiber is the stress per unit fineness at 3% elongation in the tensile test of the fiber.
The stress per unit fineness at 3% elongation in the tensile test of the fiber is a rising part of a tensile strength-elongation curve, and is a parameter indicating the rigidity of the fiber. The larger the value (the steeper the rising gradient of the tensile strength-elongation curve), the stiffer the fiber. That is, by setting the stress per unit fineness at 3% elongation in the tensile test of the fiber to 0.60cN/dtex or more, fiber deformation in the dyeing step is suppressed, and a fiber excellent in crease resistance can be obtained. Preferably 0.70cN/dtex or more.
In the core-sheath composite cross-sectional fiber of the present invention, it is preferable that the polyamide of the sheath portion has an α crystal orientation parameter of 2.10 to 2.70, and more preferably 2.20 to 2.60, it is generally known that α crystals are stable crystals and α crystals are formed when high stress is applied, and by setting the α crystal orientation parameter of the polyamide of the sheath portion in such a range, it is possible to preferentially apply drawing from the spinning drawing and drawing between drawing rolls at the time of drawing to the polyamide of the sheath portion, and to sufficiently exist α crystals as stable crystals.
If the α crystal orientation parameter of the polyamide of the sheath portion is 2.10 or more, crystallization of the polyamide of the sheath portion proceeds, tensile stress at 3% elongation as a core-sheath composite cross-sectional fiber becomes good, and crystallization of the thermoplastic polymer having high moisture absorption performance of the core portion does not proceed, and moisture absorption and release performance also becomes good, whereas if the α crystal orientation parameter is 2.70 or less, crystallization of the polyamide of the sheath portion does not proceed, and generation of yarn breakage and fluff in a high-order processing step can be suppressed, and therefore productivity is improved.
In the core-sheath composite cross-sectional fiber of the present invention, the stress retention rate per unit fineness at 3% elongation in a tensile test of the fiber before and after boiling water treatment is preferably 60% or more. By setting the range to such a range, the change in the fiber structure and the change in the degree of crystal orientation in the dyeing step are small, the shrinkage of the fiber is suppressed, and the stiffness of the fiber is easily maintained, and a fiber excellent in wrinkle resistance can be obtained. When the fiber is treated with boiling water, the fiber structure is changed mainly in the amorphous portion, and the hydrogen bonds between the amide bonds in the amorphous portion are broken, so that the mobility of the molecular chain is improved and the degree of orientation is lowered. As a result, the fiber shrinks due to the change in fiber structure and the change in orientation degree of the amorphous portion, and the rigidity of the fiber decreases. Therefore, by suppressing the shrinkage of the fiber as much as possible and maintaining the rigidity of the fiber before and after the boiling water treatment as much as possible, the fiber deformation in the dyeing step is suppressed and the crease resistance is improved. In addition, deformation of the fibers is suppressed even during washing, and crease resistance is improved.
The thermoplastic polymer having high moisture absorption properties constituting the core portion of the core-sheath composite cross-sectional fiber of the present invention is a polymer having low crystallinity and lacking rigidity. Therefore, it is also a polymer which has high shrinkage characteristics by boiling water treatment and is easily increased in flexibility. Therefore, in the core-sheath composite cross-sectional fiber of the present invention, the sheath polymer is selected from the group consisting of polyamides containing polyhexamethylene sebacamide having high rigidity and low shrinkage, whereby the sheath polymer is provided with rigidity, and further, the fiber is formed under specific filament-making conditions (heat-setting temperature, oil-feeding position, etc.) as described later, whereby the shrinkage characteristics are suppressed, the rigidity is improved, and the wrinkle resistance and the moisture absorption performance are improved. More preferably 70% or more.
The tensile strength of the core-sheath composite cross-section fiber of the present invention is preferably 3.0cN/dtex or more, and more preferably 3.5 to 5.0 cN/dtex. By setting the amount to such a range, a product excellent in practical durability can be provided.
The elongation of the core-sheath composite cross-section fiber of the present invention is preferably 35% or more, and more preferably 40 to 65%. By setting the range as described above, the passing property in the high-order step such as weaving, knitting, and false twisting becomes good.
The core-sheath composite cross-section fiber of the present invention is required to have a function of adjusting the humidity in the clothing in order to obtain a good comfort when worn, and Δ MR is used as an index of humidity adjustment, and is represented by the difference between the humidity in the clothing represented by × 90% RH at 30 ℃ in light-to-moderate work or light-to-moderate exercise and the moisture absorption rate under the outside air temperature and humidity condition represented by × 65% RH at 20 ℃.
The Δ MR of the core-sheath composite cross-sectional fiber of the present invention is preferably 5.0% or more. More preferably 7.0% or more, and still more preferably 10.0% or more. By setting the amount to such a range, stuffiness and stickiness at the time of wearing can be suppressed, and a clothing having excellent comfort can be provided.
The core-sheath composite cross-sectional fiber of the present invention has a Δ MR retention ratio after 20 washes of preferably 90% to 100%, more preferably 95% to 100%, and in such a range, it is possible to obtain a clothing that can withstand washing durability in actual use, and therefore, it is possible to provide clothing that maintains excellent comfort, i.e., clothing that has washing durability in actual use, and satisfies △ MR of 5.0% or more and Δ MR retention ratio after 20 washes of 90% or more.
The core-sheath composite cross-section fiber of the present invention may be any of a filament and a staple fiber, and is selected according to the application. The total fineness, the number of single fibers (in the case of long fibers), and the length/crimp number (in the case of short fibers) are not particularly limited, but when the fiber is used as a long fiber material for clothing, the total fineness is preferably 5 to 235dtex, and the number of single fibers is preferably 1 to 144.
The core-sheath composite cross-sectional fiber of the present invention can be obtained by melt spinning or composite spinning, and the following is mentioned as an example. For example, a polyamide (sheath portion) and a thermoplastic polymer (core portion) having high moisture absorption performance are melted and measured and conveyed by a gear pump, directly formed into a composite flow and discharged from a melt spinneret, the filaments are cooled to room temperature by a filament cooling device such as a chimney, fed and collected by an oil feeder, entangled by a 1 st fluid interlacing nozzle device, and stretched at a ratio of peripheral speeds of a drawing roll and a stretching roll. The yarn was heat-set by a drawing roll and wound by a winder (winding device).
In order to obtain the core-sheath composite cross-sectional fiber of the present invention, if a polyamide having an appropriate molecular structure is selected and an appropriate drawing speed, oil supply position, and heat-setting temperature after drawing are adopted, it can be appropriately controlled. These are explained in detail below.
As described above, the polyamide used for the core-sheath composite cross-sectional fiber of the present invention is preferably a polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component, or a polymer made of a high molecular weight material in which a hydrocarbon is bonded to a main chain via an amide bond. By selecting a polyamide having high ability to form hydrogen bonds between amide bonds for the sheath portion, the hydrogen bonds between the amide bonds of the amorphous portion are not easily broken even in high-temperature dyeing and drying at temperatures exceeding 100 ℃, and the fiber structure of the sheath portion is less changed, and a core-sheath composite cross-section fiber excellent in crease resistance of the fabric during dyeing can be obtained. The hydrogen bond-forming ability between amide bonds is determined by the degree of freedom of the main chain of the polyamide molecule, that is, the number of methylene groups per 1 amide bond. Therefore, by selecting a polyamide in such a range for the sheath portion, a core-sheath composite cross-sectional fiber excellent in crease resistance of the fabric at the time of dyeing can be obtained.
The polyamide used for the core-sheath composite cross-section fiber of the present invention may be copolymerized or mixed with various additives, such as a delustering agent, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent whitening agent, an antistatic agent, a hygroscopic polymer, carbon, and the like, as needed, in an amount of 0.001 to 10% by weight of the total additive content.
The relative viscosity of sulfuric acid of the polyamide chips (chips) used in the core-sheath composite cross-section fiber of the present invention is preferably 2.30 to 3.30. When the amount is within such a range, the polyamide in the sheath portion can be appropriately stretched. When the relative viscosity of sulfuric acid of the polyamide in the sheath portion is 2.30 or more, a practically usable strong elongation of the fiber can be obtained. On the other hand, if the relative viscosity of sulfuric acid is 3.30 or less, the melt viscosity is suitable for spinning, so that the drawability at the time of melt spinning is improved, and stable production without breakage can be performed. More preferably 2.50 to 3.10.
The ratio of the core portion of the core-sheath composite cross-sectional fiber of the present invention is preferably 20 to 80 parts by weight with respect to 100 parts by weight of the composite fiber. More preferably 30 to 70 parts by weight. When the amount is within such a range, the polyamide in the sheath portion can be appropriately stretched. In addition, good dyeing fastness and moisture absorption properties can be obtained.
In the melting step, the polyamide having dicarboxylic acid units comprising sebacic acid units as the main component used for the sheath portion is preferably 250 to 290 ℃ in the case of polyhexamethylene sebacamide scrap, and the thermoplastic polymer having high moisture absorption performance used for the core portion is preferably 220 to 260 ℃ in the case of "MH 1657" manufactured by アルケマ.
In the drawing step, the drawing speed is preferably 2500 to 3400m/min, and by setting the drawing speed to such a range, the oriented crystallization of the core polymer is appropriately advanced, and the crystallization of the core polymer is appropriately suppressed, so that the stress per unit fineness and the boiling water shrinkage ratio at 3% elongation can be controlled to be in preferable ranges, and the moisture absorption performance and the wrinkle resistance are excellent, and the moisture absorption performance can be maintained even by washing.
In the oil supply step, the oil supply position from the lower surface of the neck ring mold is preferably 800 to 1500 mm. The polymer discharged from the die is solidified by blowing cooling air from a cooling device, stretched by a spinning tension accompanied by a flow between a solidification position and an oil feed position, and then mechanically stretched between a drawing roll and a stretching roll. In the core-sheath composite cross-sectional fiber of the present invention, it is important to increase the mechanical draw ratio in order to promote oriented crystallization of the sheath polymer and improve rigidity, and it is important to reduce the spinning tension in order to suppress oriented crystallization of the core polymer and improve moisture absorption performance. That is, by setting the oil feed position in such a range, the stress per unit fineness at 3% elongation in the tensile test of the fiber can be increased, and a fiber excellent in crease resistance and moisture absorption performance can be obtained. When the oiling position is less than 800mm, the bending between the die and the oiling position becomes large, and the yarn is oiled in a state where the yarn is not sufficiently solidified, so that yarn breakage often occurs, and the workability may be deteriorated. When the oil feed position exceeds 1500mm, the orientation crystallization of the core polymer proceeds due to the high spinning tension, and the hygroscopic property is lowered, and the rigidity of the sheath polymer is lowered due to the low mechanical draw ratio, and hence the fiber is likely to wrinkle. Further preferably 1000 to 1300 mm.
In the stretching step, the heat-setting temperature after stretching is preferably 165 to 180 ℃. The fiber that has been oriented and crystallized by drawing between the rolls is further crystallized by a high-temperature heat setting treatment on the heated rolls, and the fiber structure is stabilized. The boiling water shrinkage rate depends on the shrinkage of the amorphous portion of the fiber, i.e., the proportion of the amorphous portion. The heat-set temperature in the present invention means a set temperature of the heating roller.
Since the polymer having high moisture absorption performance constituting the core portion of the core-sheath composite cross-sectional fiber of the present invention is highly amorphous and has high shrinkage, it is expected that the boiling water shrinkage is large when the fiber is formed as a homopolymer. Therefore, the core-sheath composite cross-sectional fiber of the present invention is a fiber having a stable fiber structure, in which the boiling water shrinkage ratio can be controlled to 6.0 to 12.0%, and excellent crease resistance can be obtained by using, as a sheath polymer, a polyamide having a dicarboxylic acid unit mainly composed of a sebacic acid unit, which has high rigidity and low shrinkage, among polyamides, thereby imparting rigidity to the sheath and suppressing shrinkage of the core, and by stretching at a temperature in such a range and then heat-setting. When the heat setting temperature is less than 165 ℃, crystallization of the polyamide in the sheath portion may be insufficient, and the fiber structure may be unstable, resulting in a fiber that is likely to wrinkle. In addition, when the heat setting temperature exceeds 180 ℃, although a fiber having excellent crease resistance can be obtained, the fiber may be contaminated with a decomposition product of the spinning oil on the heating roller, and the like, and the fiber may be deteriorated in quality, frequently broken yarn, and workability, and further, the fiber may be deteriorated in the high-order processing step passability. More preferably 170 to 175 ℃.
The core-sheath composite cross-sectional fiber of the present invention is excellent in moisture absorption performance, and therefore, can be preferably used for clothing, and as a fabric form, woven fabric, knitted fabric, nonwoven fabric, and the like can be selected according to the purpose, and as described above, the larger Δ MR, the higher the moisture absorption performance, and the better the wearing comfort, and therefore, a fabric having the core-sheath composite fiber of the present invention at least in a part of the fabric can provide clothing excellent in comfort by adjusting the blending ratio of the composite fiber of the present invention so that △ MR becomes 5.0% or more, and various fiber products such as underwear, sportswear, and the like can be produced as clothing.
Examples
The present invention will be described more specifically with reference to examples. Further, the measurement method of the characteristic value in the examples and the like are as follows.
(1) Relative viscosity of sulfuric acid
A sample of crushed polyamide was dissolved in 1g of 98 wt% sulfuric acid (100 ml) and the flow-down time at 25 ℃ was measured using an Ostwald viscometer (T1). Subsequently, the downflow time was measured for only 98 wt% sulfuric acid (T2). The ratio of T1 to T2, T1/T2, was taken as the relative viscosity of sulfuric acid.
(2) Relative viscosity of o-chlorophenol (OCP relative viscosity)
The sample of the polyether ester amide copolymer crushed material was dissolved in an amount of 1g per 100ml of o-chlorophenol, and the flow-down time at 25 ℃ was measured using an Ostwald viscometer (T1). Subsequently, the flow-down time of the o-chlorophenol alone was measured (T2). The ratio of T1 to T2, namely T1/T2, was taken as the o-chlorophenol relative viscosity.
(3) Fineness of fiber
The fiber sample was set in a 1.125 m/week scale, rotated 200 cycles to prepare an annular skein, dried by a hot air dryer (× 60 minutes at 105. + -. 2 ℃), the weight of the skein was measured by a weighing scale, and the weight was multiplied by a official moisture regain to calculate the metric fineness from the obtained value.
(4) Strength and elongation
The elongation is determined from the elongation at the point showing the maximum strength in the tensile strength-elongation curve, and the value obtained by dividing the maximum strength by the metric fineness is used as the strength, and the average value is used as the strength and the elongation, 10 times.
(5) Stress per fineness at 3% elongation (stress at 3% elongation)
A tensile test of a fiber sample was carried out by the method described in the above item (4), and the strength at the point where the sample showed 3% elongation in the tensile strength-elongation curve was determined as the stress at 3% elongation. The measurement was performed 10 times, and the average value was defined as the stress at 3% elongation.
(6) α crystallographic orientation parameter
Measuring fiber sample by laser Raman spectroscopy at 1120cm-1The ratio of the intensity ratio under parallel polarized light (I1120) parallel to the intensity ratio under perpendicular polarized light (I1120) of the Raman band derived from the crystal of nylon α observed in the vicinity thereof to be perpendicular to the intensity ratio under perpendicular polarized light was used as a parameter for evaluating the degree of orientation-1Nearby) as a reference, the scattering intensity under each polarization condition (parallel/perpendicular) was normalized.
α crystal orientation parameter (I1120/I1440) parallel/(I1120/I1440) perpendicular
The fiber sample for orientation measurement was cut into sections with a microtome after resin embedding (bisphenol epoxy resin, cured for 24 hours). The slice thickness was 2.0. mu.m. The sliced sample was cut off with a slight inclination from the fiber axis so that the cross section thereof was an ellipse, and the measurement was performed by selecting a position where the thickness of the minor axis of the ellipse was constant. The measurement was carried out in a microscopic mode, and the spot diameter of the laser light at the sample position was 1 μm. The orientation of the central portions of the core and sheath was analyzed, and the orientation was measured under polarized light conditions. The degree of orientation was evaluated from the ratio of the raman band intensities obtained under the parallel condition that the polarization direction was aligned with the fiber axis and under the perpendicular condition that the polarization direction was perpendicular to the fiber axis. In addition, 3 measurements were performed for each measurement point, and the average value thereof was used. The detailed conditions are shown below.
Laser Raman spectroscopy
The device comprises the following steps: t-64000(Jobin Yvon/love staline)
Conditions are as follows: a measurement mode; micro-Raman
× 100 Objective lens
Beam diameter: 1 μm
Light source: ar + laser/514.5 nm
Laser power: 50mW
Diffraction grating: single 600gr/mm
Slit: 100 μm
Detector CCD/Jobin Yvon 1024 × 256.
(7) Shrinkage in boiling water
Measured according to JIS L1013: 20108.18.1 (method B).
(8) Manufacture of fabrics
The core-sheath composite cross-sectional fiber of the present invention was used for warp and weft, and the warp density was set to 188 threads/2.54 cm and the weft density was set to 155 threads/2.54 cm, and the fiber was woven in a plain weave by a water jet loom.
The obtained gray fabric was scoured with a solution containing 2g of caustic soda (NaOH) per 1 liter by an open width soaper, dried at 120 ℃ by a drum dryer, and then pre-set at 170 ℃ according to a conventional method. Then, the temperature was raised to 120 ℃ at a rate of 2.0 ℃/min by a pressure-resistant drum type dyeing machine, and dyeing was performed at a set temperature of 120 ℃ for 60 minutes. After dyeing, the fabric was washed with running water for 20 minutes, dehydrated and dried to obtain a fabric having a warp density of 200 pieces/2.54 cm and a weft density of 160 pieces/2.54 cm.
(9) Evaluation of crease resistance
The fabric obtained in (8) above was judged to have excellent crease resistance in the range of 5 (the most smooth appearance) to 1 (the most wrinkled appearance) by the method described in item 9 of JIS L1059-2 (method for crease resistance test of fiber products, section 2: evaluation of appearance after wrinkling (Winkle method, 2009).
(10)ΔMR
The fabric obtained in (8) above was weighed into a weighing bottle at about 1-2 g, dried by holding at 110 ℃ for 2 hours, and then the weight was measured (W0), and the target substance was held at 20 ℃ and a relative humidity of 65% for 24 hours, and then the weight was measured (W65). Further, the sample was held at 30 ℃ and 90% relative humidity for 24 hours, and then the weight of the sample was measured (W90). Further, the calculation is performed according to the following equation.
MR65＝[(W65-W0)/W0]×100％ (1)
MR90＝[(W90-W0)/W0]×100％ (2)
ΔMR＝MR90-MR65 (3)。
(11) After washing Δ MR
The fabric obtained in (8) above was washed 20 times by repeating the method described in JIS L0217 (1995) with reference to No. 103 in table 1, and then △ MR described in (10) above was measured and calculated.
When Δ MR was 5.0% or more, it was judged that good comfort was obtained when the garment was worn.
(12) Delta MR retention after washing
As an index of change in Δ MR before and after washing, the Δ MR retention after washing was calculated by the following formula.
(Δ MR after washing treatment- Δ MR before washing treatment)/Δ MR × 100 before washing treatment
When the Δ MR retention rate was 90% or more, it was judged that the cleaning durability was exhibited.
(13) High-order machining process passability
Using the core-sheath composite cross-sectional fiber of the present invention, 10-piece (1000 m/piece) plain woven fabric was woven by a water jet loom under conditions of a loom rotation speed of 750rpm and a weft length of 1620mm, and the number of stops due to yarn breakage of the loom at that time was evaluated, and when the yarn breakage was 2 or less, it was judged to be good process passability.
(example 1)
A polyether ester amide copolymer having a relative viscosity of o-chlorophenol of 1.69 (MH 1657 (scrap Δ MR: 18.9, product of アルケマ)) was used as a core portion, and nylon 610 having a relative viscosity of sulfuric acid of 2.72 was used as a sheath portion, and the respective portions were melted at 270 ℃.
At this time, the number of revolutions of the gear pump was selected so that the total fineness of the core-sheath composite yarn obtained became 56dtex, and the discharge amount was 22 g/min. Further, the filaments were cooled and solidified by a filament cooling device, an oil-free water-containing oil agent was fed at an oil feed position 1000mm from the lower surface of the die by an oil feeder, and then interlacing was carried out by a 1 st fluid interlacing nozzle device so that the peripheral speed of a drawing roll as the 1 st roll was 2800m/min, the draw ratio between the drawing roll and the drawing roll was 1.50 times, the set temperature of the drawing roll was 170 ℃ to carry out heat setting, and the winding speed was 4000m/min to carry out winding, thereby obtaining a 56dtex/24F core-sheath composite cross-section fiber.
The fineness, strength, elongation, stress per fineness at 3% elongation, boiling water shrinkage, retention of stress per fineness at 3% elongation before and after boiling water treatment, and α crystal orientation parameter were measured for the obtained core-sheath composite cross-section fiber, and crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 2)
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that the heat-setting temperature of the heated rolls was set to 180 ℃.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 3)
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that the heat-setting temperature of the heated rolls was 165 ℃.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section filaments, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabrics, and the results are shown in table 1.
(example 4)
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that the oil feed position was 1500mm from the lower surface of the die and winding was carried out at a winding speed of 3900 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 5)
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that the oil feed position was set to 800mm from the lower surface of the die.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 6)
A56 dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the oil feed position was set to 1500mm from the lower surface of the die, the draw ratio between the take-off roll and the draw roll was set to 1.45 times, and the winding speed was set to 3900 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 7)
A56 dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the oil feed position was set at 800mm from the lower surface of the die, the draw ratio between the take-off roll and the drawing roll was set at 1.55 times, and the winding speed was set at 4100 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 8)
A56 dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the peripheral speed of the take-up roll as the 1 st roll was 2500m/min, the draw ratio between the take-up roll and the take-up roll was 1.65 times, and the take-up speed was 3900 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
(example 9)
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that winding was performed at a peripheral speed of the take-up roll as the 1 st roll of 3400m/min, a draw ratio between the take-up roll and the take-up roll of 1.20 times, and a winding speed of 3900 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 1.
Comparative example 1
A56 dtex/24F core-sheath composite cross-sectional yarn was obtained in the same manner as in example 1 except that the heat-setting temperature of the heated rolls was set to 190 ℃.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At such a level that the heat-setting temperature of the heating roller is high, the moisture absorption performance and the wrinkle resistance are excellent, and the moisture absorption performance can be maintained even when washing is performed, but contamination of the heating roller, a decomposition product of the spinning oil, and the like is promoted, and yarn breakage frequently occurs in a high-order processing step, resulting in poor process passability.
Comparative example 2
A56 dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the set temperature of the drawing rolls was set to 150 ℃.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At this level where the heat-setting temperature of the heating roller is low, the balance between the shrinkage characteristics of the sheath nylon 610 and the core polyetheresteramide copolymer is broken, and the boiling water shrinkage ratio is as high as 15.0%, resulting in a fabric having wrinkles.
Comparative example 3
A56 dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the oil feed position was 1800mm away from the lower surface of the die, the draw ratio between the take-off roll and the draw roll was 1.30 times, and the winding speed was 3500 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At such a level that the distance from the lower surface of the die to the oil feed position is long, the rigidity of the sheath nylon 610 is lowered, the balance between the shrinkage characteristics of the core polyetheresteramide copolymer is lost, and the stress per unit fineness at 3% elongation is as low as 0.58cN/dtex, resulting in a wrinkled fabric.
Comparative example 4
A 56dtex/24F core-sheath composite cross-section fiber was obtained in the same manner as in example 1, except that the peripheral speed of the take-up roll as the 1 st roll was 2200m/min, the draw ratio between the take-up roll and the take-up roll was 1.80 times, and the take-up speed was 3800 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At this level of low pulling rate, the stiffness of the sheath nylon 610 decreased, the balance between the shrinkage characteristics of the core polyetheresteramide copolymer collapsed, and the boiling water shrinkage became 12.3%, resulting in a wrinkled fabric.
Comparative example 5
A 56dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1, except that the peripheral speed of the take-up roll as the 1 st roll was 3700m/min, the draw ratio between the take-up roll and the take-up roll was 1.05 times, and the take-up speed was 3700 m/min.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At such a level that the drawing speed is high, the rigidity of the sheath nylon 610 is lowered, the balance between the shrinkage characteristics of the core polyetheresteramide copolymer is lost, the stress per unit fineness at 3% elongation is as low as 0.54cN/dtex, and a fabric having wrinkles is formed, and the yarn breakage frequently occurs in the high-order processing step, resulting in poor process passability.
Comparative example 6
A56 dtex/24F core-sheath composite cross-sectional fiber was obtained in the same manner as in example 1 except that nylon 6 having a sulfuric acid relative viscosity of 2.40 was used as the sheath portion and the heat-setting temperature of the heated rolls was set to 150 ℃.
The fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention of stress at 3% elongation before and after boiling water treatment, and α crystal orientation parameters were measured for the obtained core-sheath composite cross-section fiber, and the crease resistance, △ MR, △ MR after washing, and △ MR retention after washing were evaluated for the obtained fabric, and the results are shown in table 2.
At such a level that the sheath polyamide is nylon 6, the rigidity of the sheath nylon 6 is low, the balance between the shrinkage characteristics of the core polyetheresteramide copolymer is lost, and the stress per unit fineness at 3% elongation is as low as 0.53cN/dtex, resulting in a wrinkled fabric.
TABLE 1
TABLE 2
Claims (5)
1. A core-sheath composite cross-section fiber is characterized in that:
the core polymer is polyether ester amide copolymer,
the sheath polymer is a polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component,
the boiling water shrinkage is 6.0 to 12.0%,
the fiber has a stress per unit fineness of 0.60cN/dtex or more at 3% elongation in a tensile test,
the boiling water shrinkage is measured according to method B of JIS L1013: 20108.18.1,
the stress per unit fineness at 3% elongation in the tensile test of the fiber was determined from the strength at the point where the sample was elongated by 3% in the tensile strength-elongation curve by subjecting the sample to a tensile test under the constant-speed elongation condition shown in JIS L1013, i.e., the chemical fiber filament test method: 2010.
2. The core-sheath composite cross-sectional fiber according to claim 1, wherein the α crystal orientation parameter of the sheath portion is 2.10 to 2.70,
the α crystallographic orientation parameter is calculated by the following formula:
α crystal orientation parameter (I1120/I1440) parallel/(I1120/I1440) perpendicular
Wherein the fiber sample is measured at 1120cm by laser Raman spectroscopy-1Intensity ratio in parallel polarized light of Raman band derived from nylon α crystal observed nearby, namely(I1120) The intensity ratio of parallel polarized light to vertical polarized light, i.e. (I1120) is vertical, and the anisotropy with respect to the orientation is small, i.e. 1440cm-1The parallel/perpendicular scattering intensity of each polarization condition was normalized with the nearby raman band intensity as a reference.
3. The core-sheath composite cross-sectional fiber according to claim 1 or 2, wherein a stress retention rate per unit fineness at 3% elongation in a tensile test of the fiber before and after boiling water treatment is 60% or more.
4. A fabric comprising the core-sheath composite cross-sectional fiber according to any one of claims 1 to 3 at least in a part of the fabric.
5. A fibrous article having the core-sheath composite cross-sectional fiber of any one of claims 1 to 3 at least in a part of the fibrous article.
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| JP2015-220438 | 2015-11-10 | ||
| JP2015220438 | 2015-11-10 | ||
| PCT/JP2016/082368 WO2017082110A1 (en) | 2015-11-10 | 2016-11-01 | Core-sheath composite cross-section fiber having excellent moisture absorbency and wrinkle prevention |
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| CN108138378B true CN108138378B (en) | 2020-07-28 |
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| US (1) | US20190024264A1 (en) |
| EP (1) | EP3375918B1 (en) |
| JP (1) | JP6213693B2 (en) |
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| CN (1) | CN108138378B (en) |
| AU (1) | AU2016351997B2 (en) |
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| CN115989344A (en) * | 2020-09-24 | 2023-04-18 | 东丽株式会社 | Polyamide core-sheath composite fiber and fabric |
| TWI781555B (en) * | 2021-03-16 | 2022-10-21 | 立綺實業有限公司 | Waterproof and breathable wire, fabric and manufacturing method thereof |
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| JPS5145687B2 (en) * | 1973-09-04 | 1976-12-04 | ||
| JP3144092B2 (en) | 1992-10-26 | 2001-03-07 | 東レ株式会社 | Core-sheath type composite fiber with excellent hygroscopicity |
| JP3297492B2 (en) * | 1993-04-23 | 2002-07-02 | 旭化成株式会社 | Sheath-core type composite fiber |
| JPH0941221A (en) * | 1995-07-28 | 1997-02-10 | Toray Ind Inc | Synthetic fiber excellent in comfortableness |
| JP2001159030A (en) * | 1999-11-29 | 2001-06-12 | Toray Ind Inc | Conjugate polyamide fiber |
| JP2002088577A (en) * | 2000-09-13 | 2002-03-27 | Toray Ind Inc | Polyamide fiber and method of producing the same and use thereof |
| JP2004518828A (en) * | 2000-09-29 | 2004-06-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Extensible polymer fibers and articles produced therefrom |
| EP1939336B1 (en) * | 2005-10-19 | 2012-06-13 | Toray Industries, Inc. | Crimped yarn, method for manufacture thereof, and fiber structure |
| CN101313091A (en) * | 2005-10-19 | 2008-11-26 | 东丽株式会社 | Crimped yarn, method for manufacture thereof, and fiber structure |
| JP4872339B2 (en) | 2005-12-26 | 2012-02-08 | 東レ株式会社 | Core-sheath type composite fiber, crimped yarn, and fiber structure using them |
| TW200741049A (en) * | 2005-12-27 | 2007-11-01 | Shell Int Research | Polyester yarn and process for producing |
| JP2007321295A (en) * | 2006-06-01 | 2007-12-13 | Teijin Ltd | Crimped conjugated fiber |
| DE602007008568D1 (en) | 2006-07-03 | 2010-09-30 | Kuraray Co | CONDUCTIVE COVER CORE CONJUGATE FIBER AND METHOD OF MANUFACTURING THEREOF |
| US7892640B2 (en) * | 2007-04-04 | 2011-02-22 | Kb Seiren, Ltd. | Conjugate fibers excellent in antistatic property, water absorption and cool feeling by contact |
| JP2011200352A (en) * | 2010-03-25 | 2011-10-13 | Toray Monofilament Co Ltd | Tapered bristle and brush |
| JP5807456B2 (en) * | 2011-08-31 | 2015-11-10 | 東レ株式会社 | Polyamide 410 fiber and fiber structure comprising the same |
| TWI595127B (en) * | 2012-02-29 | 2017-08-11 | 東麗股份有限公司 | Polyamide fiber and method for producing the same |
| JP6068470B2 (en) | 2012-07-12 | 2017-01-25 | Ｋｂセーレン株式会社 | Core-sheath composite fiber |
| WO2015129735A1 (en) * | 2014-02-26 | 2015-09-03 | 東レ株式会社 | Crimped polyamide yarn, and woven or knit fabric employing same |
| JP2016204784A (en) * | 2015-04-23 | 2016-12-08 | 東レ株式会社 | Polyamide core-sheath composite fiber excellent in hygroscopicity and contact cool feeling and fabric using the same |
| JP6600969B2 (en) * | 2015-04-02 | 2019-11-06 | 東レ株式会社 | Core-sheath composite cross-section fiber with excellent moisture absorption / release performance |
| WO2016190102A1 (en) * | 2015-05-22 | 2016-12-01 | 東レ株式会社 | Hygroscopic core-sheath conjugate yarn and production method therefor |
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| EP3375918A4 (en) | 2019-06-26 |
| AU2016351997A1 (en) | 2018-05-17 |
| EP3375918B1 (en) | 2022-05-11 |
| CN108138378A (en) | 2018-06-08 |
| TW201734273A (en) | 2017-10-01 |
| WO2017082110A1 (en) | 2017-05-18 |
| JP6213693B2 (en) | 2017-10-18 |
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| JPWO2017082110A1 (en) | 2017-11-16 |
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| KR20180079288A (en) | 2018-07-10 |
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