WO2005095686A1 - 海島型複合繊維及びその製造方法 - Google Patents
海島型複合繊維及びその製造方法 Download PDFInfo
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- WO2005095686A1 WO2005095686A1 PCT/JP2005/006734 JP2005006734W WO2005095686A1 WO 2005095686 A1 WO2005095686 A1 WO 2005095686A1 JP 2005006734 W JP2005006734 W JP 2005006734W WO 2005095686 A1 WO2005095686 A1 WO 2005095686A1
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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
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester 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
- D01D5/36—Matrix structure; Spinnerette packs therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
- Y10T428/2924—Composite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3065—Including strand which is of specific structural definition
- Y10T442/3089—Cross-sectional configuration of strand material is specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
- Y10T442/425—Including strand which is of specific structural definition
- Y10T442/431—Cross-sectional configuration of strand material is specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
- Y10T442/609—Cross-sectional configuration of strand or fiber material is specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
- Y10T442/64—Islands-in-sea multicomponent strand or fiber material
Definitions
- the present invention relates to a sea-island composite fiber, particularly to a sea-island composite fiber having an extremely large number of island components. Further details
- the sea-island composite fiber which has a very low content of sea components, and from which a fine fiber group with an extremely large number of filament fields can be easily obtained by dissolving and removing this sea component, It relates to a manufacturing method.
- Patent Document 1 when spinning a sea-island composite fiber, a sea-island composite flow is created upstream, and this is aggregated by each of a plurality of primary funnel-shaped portions.
- a method for producing a super-island sea-island composite fiber comprising: assembling together at a secondary funnel disposed downstream thereof, and spinning out the secondary assembling flow from a discharge hole. Proposed ing.
- this method increases the number of islands, but it is complicated and expensive, and difficult to handle in the manufacturing process.In addition, if the number of island components is 200 or more, the fineness of the island components is high.
- the mass ratio of the sea component to the island component is 1: 1 or more and the sea component to be dissolved and discarded.
- the problem is that the amount of polymer is still high.
- Patent Document 2 discloses a method for producing a fiber composed of an aggregate of fine polymer short fibers by removing a composite polymer mixed with a static mixer or the like into a sea-island mixed spun fiber, and then removing the sea component.
- a method for producing a fiber composed of an aggregate of fine polymer short fibers by removing a composite polymer mixed with a static mixer or the like into a sea-island mixed spun fiber, and then removing the sea component.
- the homogeneity is insufficient due to the formation of the island phase by blending, and the strength is low because the aggregate fiber is composed of fine fibers with a finite length in the fiber axis direction. is there
- Patent Document 1 Japanese Patent Publication No. 58-12367
- Patent Document 2 Japanese Patent Publication No. 60-28922 Disclosure of the invention
- An object of the present invention is to provide an islands-in-sea type composite fiber which can easily dissolve and remove a sea component even if the content ratio of the island component is high and can obtain a group of fine fibers having an extremely large number of filaments, and a method for producing the same. It is in.
- the above object can be achieved by the sea-island composite fiber and the method for producing the same according to the present invention.
- the sea-island composite fiber according to the present invention is a sea-island composite fiber having an easily soluble polymer as a sea component and a poorly soluble polymer as an island component, and each of the island components in a cross section of the composite fiber. Is within the range of LOOOnm, the number of island components is above ⁇ , and the distance between adjacent island components is 500nm or less. In the sea-island composite fiber of the present invention, the number of island components is preferably 500 or more.
- the CV% indicating the variation of the diameter in the island component is preferably 0 to 25%.
- the composite mass ratio of sea component to island component (sea: island) force WO: 60 to 5: 95 is preferable.
- the dissolution rate ratio (sea / island) force of the sea component to the island component is preferably 200 or more.
- the easily soluble polymer for the sea component is polylactic acid, ultra-high molecular weight polyalkylene oxide condensed polymer, polyethylene glycol-based compound copolymerized polyester, and polyethylene. It is preferable to include at least one kind of easily soluble polymer in an aqueous solution of an alcohol solution selected from copolymerized polyesters of a dalicol-based compound and 5-hydroxysulfonic acid.
- the copolymerized polyester of the polyethylene glycol-based compound and 5-naphthyl sulfoisophtalic acid contains 6 to 12 mol% of 5-sodium sulfonic acid and 3 to 5 mol%. It is preferably selected from a polyethylene terephthalate copolymer obtained by copolymerizing 10% by weight of polyethylene daricol having a molecular weight of 4000 to 12000.
- the minimum value (Smin) and the fiber diameter (R) of the distance between the island components on the four straight lines and the maximum value (Smax) of the distance between the islands are represented by the following formulas (I) and ( ⁇ )
- the sea-island composite fiber of the present invention in the load-elongation curve measured at room temperature, there is a yield point due to partial breakage of the sea component, and the sea-island composite fiber breaks due to the breakage of the island component.
- the sea component is niobium and is soluble in formic acid.
- the sea-island composite fiber may be an undrawn fiber.
- the sea-island composite fiber may be a drawn fiber.
- the method of the present invention is a method for producing the sea-island composite fiber according to the present invention, comprising: a spinneret for a sea-island composite fiber; a sea component composed of an easily soluble polymer; and a sparingly soluble polymer.
- a method including a step of melting and extruding an island component having a lower melt viscosity than the soluble polymer, and a step of drawing out the extruded sea-island composite fiber at a spinning speed of 400 to 6000 mZ min. is there.
- the method for producing a sea-island composite fiber according to the present invention may further comprise a step of subjecting the taken-out composite fiber to oriented crystallization and drawing at a temperature of 60 to 220 ° C.
- the drawn composite fiber is preheated on a preheating roller having a temperature of 60 to: L50 ° C and drawn at a draw ratio of 1.2 to 6.0,
- the method may further include a step of heat setting and winding on a set roller at 120 to 220 ° C.
- the melt viscosity ratio of the polymer for sea component to the polymer for island component in the melt extrusion step is preferably in a range of 1.1 to 2.0.
- the polymer for sea component and the polymer for island component each have a glass transition point of 100 ° C.
- the drawn sea-island composite fibers are immersed in a liquid bath having a temperature of 60 to 100 ° C., and are pre-flowed under the conditions of a draw ratio of 10 to 30 and a draw speed of 300 m / min or less.
- a stretching step may be further included.
- the fine fiber bundle of the present invention is obtained by dissolving and removing a marine component from the sea-island composite fiber of the present invention, and is made of fine fibers having a diameter in the range of 10 to! OOOnm.
- the variation (CV%) of the diameter of the single fiber contained therein is preferably from 0 to 25%.
- the tensile strength of the fine fiber bundle of the present invention is 1.0 to 6.
- OCN / dtex, the elongation at break is 15 to 60%, and the dry heat shrinkage at 150 ° C is 5 to 15%. Is preferred.
- the fiber product of the present invention includes the fine fiber bundle of the present invention.
- the fiber product of the present invention may have a shape of a woven or knitted fabric, a felt, a nonwoven fabric, a braided yarn, or a spun yarn.
- the textile product of the present invention may be selected from clothing products, interior products, industrial material products, living material products, environmental material products, or medical and hygiene products.
- the sea-island type composite fiber of this invention has sufficient mechanical strength which can endure practical use by dissolving and removing a sea component, and the high multifilament 1, which consists of a fine fiber of single fiber, Yarn can be easily obtained, and according to the production method of the present invention, a sea-island composite fiber having a uniform island component diameter can be easily produced even if the proportion of the sea component is reduced.
- FIG. 1 is a cross-sectional explanatory view of a part of an example of a spinneret used for spinning the sea-island composite fiber of the present invention.
- FIG. 2 is a cross-sectional explanatory view of a part of another example of a spinneret used for spinning the sea-island composite fiber of the present invention.
- FIG. 3 is an explanatory cross-sectional view of one embodiment of the sea-island composite fiber of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
- the polymer constituting the sea-island composite fiber of the present invention can be appropriately selected as long as the sea component polymer is a combination having a higher solubility than the island component polymer.
- the dissolution rate ratio (sea / island) force S Preferably it is 200 or more.
- the dissolution rate ratio is less than 200, part of the island component in the surface layer of the fiber cross section is dissolved while the sea component in the center of the fiber cross section is dissolved, so the sea component is completely dissolved and removed.
- the weight of the island component is reduced by a certain percentage, causing unevenness in the thickness of the island component and deterioration in strength due to solvent erosion, resulting in fluff and pilling, which degrades the product quality. May be.
- the sea component polymer is preferably any polymer as long as the dissolution rate ratio with the island component is 200 or more, and in particular, a fiber-forming polyester, polyamide, polystyrene, polyethylene, or the like is preferable.
- a fiber-forming polyester, polyamide, polystyrene, polyethylene, or the like is preferable.
- a fiber-forming polyester, polyamide, polystyrene, polyethylene, or the like is preferable.
- a fiber-forming polyester, polyamide, polystyrene, polyethylene, or the like is preferable.
- Good for example, polylactic acid, an ultra-high molecular weight polyalkylene oxide condensed polymer, a polyethylene glycol-based compound copolymer polyester, a polyethylene glycol-based compound and A copolymer of sodium sulfonate and isophthalic acid is preferred.
- Nylon 6 is soluble in formic acid
- polystyrene / polyethylene copolymer is an organic solvent
- the polymer of the polyester 5-Na DOO polyethylene glyceraldehyde of Li Umusuruhoi Sofutaru acid 6-12 mole 0/0 and molecular weight from 4,000 to 12,000
- Polyethylene terephthalate copolymerized polyester having an intrinsic viscosity of 0.4 to 0.6 obtained by copolymerizing 3 to 10% by weight of coal is preferred.
- 5-sodium sodium isophthalic acid contributes to the improvement of the hydrophilicity and melt viscosity of the obtained copolymer
- polyethylene glycol (PEG) improves the hydrophilicity of the obtained copolymer.
- the island component polymer may be any polymer as long as there is a difference in the dissolution rate between the island component polymer and the sea component.
- fiber-forming polyester, polyamide, polystyrene, Preferred is ethylene.
- polyester is preferably polyethylene terephthalate, polyester terephthalate, polyester terephthalate, etc.
- polyamide is nylon 6 Nylon 66 is preferred.
- polystyrene and polyethylene which are resistant to water, acid, and alkaline, are preferred in terms of durability when used for purification of industrial materials, medical materials, filters, etc. such as fine fiber fabrics.
- the sea-island type of the present invention comprising the above sea component polymer and island component polymer
- the melt viscosity of the sea component at the time of melt spinning is preferably higher than the melt viscosity of the island component polymer.
- the composite mass ratio of the sea component is as low as less than 40%, the islands are joined to each other, or most of the island components are joined to each other. It does not form different from sea-island composite fibers.
- the preferred melt viscosity ratio (sea-island) is 1 It is more preferably in the range of 1.3 to 1.3. If this ratio is less than 1.1 times, the stability of the process is likely to cause the island components to bond to each other during melt spinning, while if it exceeds 2.0 times, the viscosity difference is too large. In addition, the stability of the spinning process tends to decrease.
- the number of island components is 100 or more, and preferably 500 or more, since smoothness and glossiness can be exhibited. If the number of island components is less than 100, the high multifilament yarn composed of fine single fibers cannot be obtained even if the sea components are dissolved and removed, and the object of the present invention cannot be achieved. . If the number of island components is too large, not only the production cost of the spinneret will increase, but also the processing accuracy of the spinneret will easily decrease.Therefore, the number of island components should be 1000 or less. Is preferred.
- the diameter of the island component needs to be 10 to 1000 nm, preferably 100 to 700 nm. If the diameter of the island component is less than 10 nm, the fiber structure itself becomes unstable, and the physical properties and fiber morphology become unstable, which is not preferable.On the other hand, if the diameter exceeds 100 nm, the softness and texture unique to ultrafine fibers Is not obtained, which is not preferable.
- the uniformity of the diameter of each island component in the cross section of the composite fiber improves the quality and durability of the high multifilament yarn composed of fine fibers obtained by removing the sea component.
- the sea-island composite fiber of the present invention has a sea-island composite mass ratio (sea-island composite mass ratio).
- Island is preferably in the range of 40:60 to 5:95, particularly preferably in the range of 30:70 to 10:90.
- the thickness of the sea component between the island components can be reduced, the sea component can be easily dissolved and removed, and the conversion of the island components into fine fibers becomes easy.
- the proportion of the sea component exceeds 40%, the thickness of the sea component becomes too thick, while when it is less than 5%, the amount of the sea component becomes too small, and mutual bonding occurs between the islands. Easier to do.
- the breaking elongation of the island component is larger than the breaking elongation of the sea component.
- the diameter (r) of the island component and four straight lines passing through the center and having an angular interval of 45 degrees with each other are drawn on the cross section of the fiber.
- the minimum value (Smin) and the fiber diameter (R) of the spacing of the island components on the four straight lines and the maximum value (Smax) of the spacing between the islands satisfy the following equations (I) and ( ⁇ ). In this case, fine fibers having mechanical strength sufficient for practical use can be obtained.
- the central portion of the conjugate fiber is formed of a sea component, the distance between the adjacent island components via the central portion is excluded. From the above, it is more preferable that 0.01 ⁇ SminZr ⁇ 0.7 and Smax / R ⁇ 0.08.
- Smin / r value exceeds 1.0 or the SmaxZR value exceeds 0.15, the high-speed spinnability at the time of producing the conjugate fiber becomes poor, or the draw ratio is reduced. Since it cannot be increased, the drawn yarn physical properties of the obtained sea-island fiber and the mechanical strength of the fine fiber obtained by dissolving and removing the sea component are reduced.
- the distance between adjacent island components is 500 nm or less, preferably in the range of 20 to 200 nm, and the distance between the island components is 500 nm. If it exceeds, the dissolution of the island component proceeds while dissolving and removing the sea component occupying this interval, which not only reduces the homogeneity of the island component but also reduces the fine fibers formed from this island component. When put to practical use, defects during wearing such as fluff and pilling, and spots of dyeing are likely to occur.
- the above-described sea-island composite fiber according to the present invention can be easily produced, for example, by the following method. That is, first, a polymer having a high melt viscosity and being easily soluble and a polymer having a low melt viscosity and being hardly soluble are melt-spun such that the former is a sea component and the latter is an island component.
- the relationship between the melt viscosity of the sea component and the island component is important. If the content ratio of the sea component is low and the spacing between the islands is small, the melting of the sea component is low and if the viscosity is low, the composite fiber melts. In the spinneret, the sea component flows at a high speed in a part of the flow path between the island components, and it is not preferable because mutual connection easily occurs between the islands.
- Some of these unstretched sea-island composite fibers for fine fibers exhibit a yield point corresponding to partial breakage of the sea component in the load-drawing curve at room temperature. This is a phenomenon observed when the sea component solidifies faster than the island component and the degree of orientation of the sea component advances, while the island component has a lower degree of orientation due to the influence of the sea.
- the primary yield point means the partial break point of the sea component (this point is defined as the partial break elongation Ip%), and after the yield point, the island components with low orientation extend.
- both the sea-island component breaks (this point is defined as the total breaking elongation It%).
- the drawing curve at room temperature is not limited to the above, and may be a normal drawing curve.
- any suitable one such as those having a group of hollow pins and a group of micropores for forming an island component can be used.
- an empty pin ⁇ The island component extruded from the micropore and the sea component flow supplied from the flow path designed to fill the gap are merged, and the discharge port is made while gradually narrowing this merged fluid flow
- Any spinneret may be used as long as it can be extruded to form a sea-island composite fiber.
- An example of a spinneret that is preferably used is shown in FIGS. 1 and 2, but the spinneret that can be used in the method of the present invention is not necessarily limited to these.
- the polymer (melt) for the island component in the polymer reservoir 2 for the island component before distribution is introduced into the polymer for the island component formed by a plurality of hollow pins.
- the sea component polymer (melt) is introduced into the sea component polymer reservoir 5 through the sea component polymer introduction passage 4 before being distributed.
- the hollow pins forming the polymer introduction path 3 for the island component respectively penetrate the polymer reservoir 5 for the sea component, and the center of each of the plurality of core-sheath composite flow paths 6 formed thereunder. It is open downward at the part. From the lower end of the island component polymer introduction channel 3, the island component polymer flow is introduced into the central portion of the core-sheath composite flow channel 6, and the sea component polymer flow in the sea component polymer reservoir 5 is a core-sheath type.
- the island component polymer stream is introduced so as to enclose the island component polymer stream into the multi-junction passage 6, and a core-sheath composite stream is formed with the island component polymer stream as the core and the sea component polymer stream as the sheath.
- the composite flow is introduced into the funnel-shaped merging passage 7, and in this merging passage 7, a plurality of core-sheath composite flows are joined together at their respective sheaths, forming a sea-island composite flow. It is formed. While flowing down the funnel-shaped merging passage 7, the sea-island composite flow gradually reduces its horizontal cross-sectional area, and is discharged from the outlet 8 at the lower end of the merging passage 7.
- the island component polymer reservoir 2 and the sea component polymer reservoir 5 are connected by an island component polymer introduction passage 13 composed of a plurality of through holes.
- the island component polymer (melt) in the component polymer reservoir 2 is distributed into the plurality of island component polymer introduction passages 13, and is introduced into the sea component polymer reservoir 5 through the island polymer.
- the polymer flow passes through the sea component polymer (melt) contained in the sea component polymer reservoir 5, flows into the core-sheath type composite flow passage 6, and flows down the central portion thereof.
- the marine polymer in the marine polymer reservoir 5 flows down in the core-sheath composite flow passage 6 so as to surround the island polymer flow flowing down the center thereof.
- a plurality of core-in-sheath composite flows are formed in the plurality of core-in-sheath composite flow passages 6 and flow down into the funnel-shaped merge passage 7 in the same manner as the spinneret of FIG. It forms a sea-island complex flow, flows down while reducing its horizontal cross-sectional area, and is discharged through the discharge port 8.
- the discharged sea-island cross-section composite fiber is solidified by cooling air, preferably wound up at a speed of 400 to 6000 m / min, more preferably 1000 to 3500 m / min. If the spinning speed is less than 400 m / min, the productivity will be insufficient, and if the spinning speed is more than 6000 m / min, the spinning stability will be poor.
- the obtained unstretched fiber is subjected to a separate stretching step to give a stretched conjugate fiber having a desired tensile strength, a breaking elongation and a heat shrinkage property, or at a constant speed without winding.
- Any of the following methods may be used: a method in which the film is taken up by a roller, subsequently passed through a stretching process, and then wound up. Specifically, it is preheated on a preheating roller at 60 to 190 ° C, preferably 75 to 180 ° C, and stretched at a stretching ratio of 1.2 to 6.0 times, preferably 2.0 to 5.0 times.
- the preheating temperature is insufficient, Magnification stretching cannot be achieved. If the setting temperature is too low, the resulting drawn fiber has too high a shrinkage ratio, which is not preferable. On the other hand, if the setting temperature is too high, the physical properties of the obtained drawn fiber are remarkably reduced, which is not preferable.
- the fiber in order to produce a sea-island type composite fiber having a particularly fine island component diameter with high efficiency, the fiber is preceded by neck stretching (oriented crystallization stretching) accompanied by ordinary so-called oriented crystallization. It is preferable to employ a fluid drawing step in which only the fiber diameter is reduced without changing the structure.
- neck stretching oriented crystallization stretching
- both the sea component polymer and the island component polymer are polymers having a glass transition temperature of 100 ° C or less, and especially PET, PBT, polylactic acid, and polymethylene terephthalate.
- polyester such as Specifically, the drawn conjugate fiber is immersed in a hot water path in the range of 60 to 100 ° C, preferably 60 to 80 ° C, and is uniformly heated while being stretched at a draw ratio of 10 to 30 times. It is preferable to carry out pre-flow stretching at a speed of 1 to 10 m / min and a winding speed of 300 m / min or less, especially within a range of 10 to 300 m / min. If the preheating temperature is insufficient and the stretching speed is too high, the intended high-magnification stretching cannot be achieved.
- the pre-drawn fiber pre-drawn in the fluidized state is oriented and crystallized at a temperature of 60 to 150 ° C. in order to improve mechanical properties such as high elongation. If the drawing conditions are outside the above range, the physical properties of the obtained fiber will be insufficient.
- the stretching ratio can be set according to melt spinning conditions, flow stretching conditions, oriented crystallization stretching conditions, and the like. Generally, however, it is preferable to set the maximum draw ratio of 0.6 to 0.95 times that can be stretched under the oriented crystallization stretching conditions.
- the diameter obtained from the sea-island type composite fiber of the present invention by dissolving and removing the sea component is 10 or more;
- the CV% value representing the variation in the fineness of the fine single fiber of LOOOnm is preferably 0 to 25%. More preferably, it is 0 to 20%, and still more preferably 0 to: L5%.
- a lower CV value means less variation in fineness.
- the sea component is obtained by dissolving and removing the sea component from the sea-island composite fiber of the present invention, and the tensile strength of the fine fiber bundle composed of the fine fiber having a diameter of 10 to: LOOO nm is 1.0 to 6.0 cNZ dt ex.
- the elongation at break is preferably 15 to 60%, and the dry heat shrinkage at 150 ° C is preferably 5 to 15%. It is important that the physical properties, especially the tensile strength, of the fine fiber bundle is not less than 1. OcNZ dt ex. If the tensile strength is lower than this, the application is limited.
- the fine fiber bundle of the present invention has a large specific surface area. For this reason, it has excellent adsorption and absorption characteristics. Taking advantage of this effect, for example, new applications can be developed by absorbing functional drugs.
- Functional drugs include, for example, drugs for promoting health and beauty such as proteins and vitamins, as well as pharmaceuticals such as anti-inflammatory agents and disinfectants.
- it has excellent release / release characteristics as well as absorption / adsorption characteristics. Taking advantage of this effect, It can be deployed in a variety of pharmaceutical and hygiene applications, including drug delivery systems, including the release of functional drugs that have been released.
- the fiber product of the present invention having at least a part of the fine fiber bundle is a yarn, a braided yarn, a spun yarn made of short fibers, an intermediate product such as a woven fabric, a knitted fabric, a felt, a nonwoven fabric, and an artificial leather.
- These include jackets, scarts, pants, underwear and other clothing, sports clothing, clothing materials, carpets, sofas, curtains and other interior products, car seats and other vehicle interior products, cosmetics, cosmetic masks, Used for daily use such as wiping cloth and health goods, and for environment such as abrasive cloths, filters, harmful substance removal products, battery separators, industrial materials, and medical uses such as sutures, scaffolds, artificial blood vessels, and blood filters.
- FIG. 3 is an explanatory cross-sectional view of one embodiment 21 of the sea-island composite fiber according to the present invention, in which a sea component 22 forming a matrix and a sea component 22 therein are arranged apart from each other. And a number of island components23.
- a method for measuring the interval between island components in the sea-island composite fiber shown in FIG. 3 will be described.
- four straight lines 25, 1-1, 25—2, 25-3, and 25—4 are drawn on the cross-section 21 through the center 24 and at an angular interval of 45 degrees from each other. measures the spacing of the island component in this 4 straight line, defined maximum spacing Sma X, the minimum interval Sm in from them, and calculates the average value Save of the island component spacing.
- the island components on the four straight lines are mainly described, and other island components are omitted.
- the test polymer is dried, set in an orifice set to the melting temperature of a melt spinning extruder, kept in a molten state for 5 minutes, and extruded under a predetermined level of load. And the melt viscosity were plotted. The above operation was repeated under multiple levels of load. Based on the above data, a shear rate-melt viscosity relationship curve was created. Estimate the melt viscosity when the shear rate is 1000 seconds- 1 on this curve.
- Each of the polymer for both sea and island components is extruded through a spinneret for the production of sea-island composite fibers having 24 holes 0.3 mm in diameter and a discharge hole with a land length of 0.6 mm, and 1000 to 2000 m / min.
- the fiber was wound at a speed and the fiber was drawn.
- a multifilament with 75 dtex / 24 f was manufactured. This multifilament was dissolved in a solvent at a predetermined temperature at a bath ratio of 50, and the rate of weight loss was calculated from the dissolution time and the amount dissolved at this time.
- the dissolution and separation performance of the sea-island composite fiber is evaluated and displayed as 2 (good). If less than this, it was rated as 1 (bad). In the above-mentioned melt spinning step, the case where continuous operation was possible for 7 hours or more was evaluated and indicated as good, and the other cases were evaluated as poor.
- a cross-sectional photograph of the test islands-in-sea composite fiber was taken at a magnification of 30,000 using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the diameter R of the conjugate fiber and the diameter r of the island component are measured, and in the cross-sectional photograph, they pass through the center point of the conjugate fiber and have an angle of 45 degrees with each other.
- four straight lines intersecting with each other were drawn, the maximum interval Smin and the maximum interval Smax between the island components on the straight line were measured, and the average interval Save between the island components was calculated.
- the sea component is removed from the test sea-island composite fiber using a solvent, and the obtained fine fiber bundle made of the island component polymer is observed at a magnification of 30,000 times using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the fineness of the fine single fiber was measured, the standard deviation ( ⁇ ) of the fineness and the average fine fiber diameter (r) were calculated, and the variation (CV%) was calculated by the following equation.
- the average fine single fiber diameter (r) is an average value of the major axis and the minor axis of the fine single fibers measured by observing the cross section of the fine fiber bundle at a magnification of 30,000 using a TEM.
- the test islands-in-sea conjugate fiber is treated with a solvent for sea components, and when a decrease in mass corresponding to the sea component content ratio is observed, the dissolution treatment is stopped, and the cross section of the obtained fine fiber bundle is subjected to TEM. From a closer observation, the uniformity of the island component was evaluated and displayed as 1 (uniform) or 2 (non-uniform) based on the uniformity of the cross section of the fine single fiber.
- Fineness of fine fiber bundle D X (1 -Ra)
- a tubular knitted fabric having a mass of 1 g or more was prepared from the sea-island composite fiber yarn, and the knitted fabric was subjected to a solvent treatment. Sea components were removed.
- the test fine fiber bundle was wound 10 times around a skein frame having a circumference of 12.5 cm to prepare a skein, and the length L Q under a load of 1/30 cN / dtex was measured. Remove the load from the skein and put it in a thermostatic dryer in a free state, 150. (: Heat treatment was performed for 30 minutes. A load of 1/30 cNZ dtex was applied to the dried skein and the length L of the skein after the dry heat treatment was measured. The drying shrinkage rate of the fine fiber bundle DHS was calculated from the following equation.
- Table 1 shows the polymer for island component and the polymer for sea component used.
- the polymer for sea and island components is heated and melted and supplied to a spinneret for spinning sea-island composite fiber, and is extruded at a spinning temperature of 280 ° C. At 06734 degrees, it was wound on a winding roller. The obtained undrawn fiber bundle is displayed
- Roll stretching was performed at the stretching temperature and stretching ratio described in 2 (however, in this case, in Example 10, the film was stretched 22 times in a hot water path at a temperature of 80 ° C, and then stretched at a temperature of 90 ° C. The roller was stretched three times).
- the stretched fiber bundle was subjected to a heat treatment at a temperature of 150 ° C. and wound up. At this time, in Examples 1 to 10, the spinning discharge flow rate and the draw ratio were adjusted so that the yarn count of the obtained fiber bundle subjected to the drawing heat treatment was 22 dtex / 10 f.
- Tables 1 and 2 show the results of performance measurement and evaluation of the obtained sea-island composite fibers.
- Example 1 Modified PET1 PET1 500 60/40 1500 Good 2 250 0.48 0.05
- Example 2 Modified PET1 PET1 500 60/40 1000 Good 2 250 0.48 0.05
- Example 3 Modified PET1 PET1 500 80/20 1500 good 2 180 0.30 0.011
- Example 4 Modified PET1 PET1 500 95/5 1500 Good 2 75 0.12 0. 009
- Example 5 Modified PET5 PET1 900 70/30 3500 Good 2 60 0.14 0.03 Comparative Example 1 Modified PET1 PET1 100 50/50 1500 Good 2 520 0.49 0.1 Comparative Example 2 Modified PET1 PET1 25 70/30 1500 Good 2 1200 0.48 0.03 Comparative Example 3 Modified PET2 PET1 100 80/20 1500 Good 2 One
- Example 4 Modified PET3 PET1 500 80/20 1000 Good 1 180 0.3 0.35
- Example 6 Ny-6 PET2 500 70/30 1500 Good 2 200 0.32 0.03
- Example 7 Modified PETl Ny- 6 500 70/30 1500 Good 2 190 0.34 0.03
- Example 8 Polyacid PET3 500 80/20 1500 Good 2 180 0.31 0.011
- Example 9 Modified PBT PET3 500 80/20 1500 Good 2 180 0.29 0.01
- Example 10 Polystyrene PET3 500 90/10 1500 Good 2 110 0.1.8 0.00.09
- Example 11 Modified PET4 PETl 1000 70/30 1500 Good 2 90 0.14 0.02
- Example 12 Modified PET5 PETl 1000 70/30 1500 Good 2 20 0.24 0.02
- PET1 Polyethylene terephthalate with a melt viscosity of 120 Pa.s at 280 ° C.
- PET3 Polyethylene terephthalate with a melt viscosity at 270 ° C of 60 Pa.s.
- NY-6 Nylon 6-modified PET with a melt viscosity at 280 ° C of 40 Pa.s poise 1: 5-mol sodium phthalic acid with a melt viscosity at 280 ° C of 175 Pa, s poise 6 mol 0 / o and polyethylene terephthalate copolymerized with 6% by weight of polyethylene glycol having a number average molecular weight of 4000.
- Modified PET2 Polyethylene terephthalate copolymerized with 2 mol% of 5-sodium sulfonic acid isophthalic acid having a melt viscosity at 280 ° C of 75 Pa.s and 10% by weight of polyethylene glycol having a number average molecular weight of 4000.
- Modified PET3 Polyethylene terephthalate having a melt viscosity at 280 ° C of 200 Pa.s and a copolymer of 3% by weight of polyethylene glycol having a number average molecular weight of 4000.
- Modified PET4 Polyethylene copolymer having a melt viscosity at 280 ° C of 155 Pa.s, copolymerized with 8 mol% of 5-hydroxysulfonic acid and 30% by weight of polyethylene glycol having a number average molecular weight of 400,000. Lifter rate.
- Modified PET5 Polyester having a melt viscosity at 280 ° C of 135 Pa.s, copolymerized with 9 mol% of 5-hydroxysulfonic acid and 3 wt% of polyethylene glycol having a number average molecular weight of 4000 Polyethylene terephthalate.
- Polylactic acid Polylactic acid having a melt viscosity at 270 ° C of 175 Pa ⁇ s poise and a D-form purity of 99%.
- Polystyrene Polystyrene whose melt viscosity at 270 ° C is less than 100 Pa.s.
- Example 1 PET1 and modified PET1 were used as an island component and a sea component, respectively, at a ratio of 60:40.
- the resulting islands-in-sea composite fiber had a thin island-to-island thickness and uniform island diameter, and had formed a sea-island cross-section. In the elongation curve at room temperature, no yield point corresponding to the partial breakage of the sea component did not appear.
- TEM observation of the cross section of the yarn revealed that the relationship between the island diameter (r), the minimum spacing between island components (Sinin), the fiber diameter (R), and the maximum spacing between islands (Smax) was determined.
- r 0.48
- Smax, R 0.05.
- the cross-section of the obtained fine fiber bundle was reduced by 40% at 95 ° C with a 4% aqueous NaOH solution, and the cross section of the obtained fine fiber bundle was observed. As a result, a group of fine fibers having a uniform fine single fiber diameter was formed.
- the tensile strength of the fine fiber bundle after sea loss was 2.5 cN / dtex, and the elongation at break was 75%.
- Example 2 the same sea-island fibers as in Example 1 were subjected to roller stretching at the stretching temperature and the stretching ratio shown in Table 2.
- a tubular knit was formed using the drawn yarn, and the cross section of the fiber whose weight was reduced by 40% at 95 ° C with a 4% aqueous NaOH solution was observed.
- a group of fine fibers having a uniform fine single fiber diameter was formed.
- the tensile strength of the fine fiber bundle after sea loss is 5.9 cN / dtex, and the elongation at break is 4 0%.
- the sea-island cross-section was formed with a thin island-to-island sea thickness and uniform sea-island diameter.
- a tubular knit was made using the drawn yarn obtained by roller drawing at the drawing temperature and draw ratio shown in Table 2, and the resulting fine fiber bundle was reduced by 20% at 95 ° C with a 4% aqueous NaOH solution.
- a group of fine fibers having a uniform fine single fiber diameter was formed.
- the tensile strength of the fine fiber bundle after removing the sea component was 3.0 cN / dtex, and the elongation at break was 70%.
- a tubular knit was made using the drawn yarn obtained by roller drawing at the drawing temperature and draw ratio shown in Table 2, and the cross-section of the fiber bundle obtained by reducing the weight by 5% at 95 ° C with a 4% aqueous NaOH solution As a result, it was found that a fine fiber bundle having a uniform fine single fiber diameter was formed.
- the tensile strength of the fine fiber bundle after sea component removal was 4.0 cN / dtex, and the elongation at break was 55%.
- the elongation at break of the island component was higher than that of the sea component, and the sea / island alkali weight loss rate ratio was 2000 times.
- a yield point corresponding to the partial fracture of the sea component appeared.
- the difference between the elongation at break and the elongation at break at the intermediate yield point was 120%.
- the cross section of the raw yarn was observed by TEM, the sea-island cross-section formation was good.
- a tubular knit was prepared, and the weight was reduced by 30% at 95 ° C with a 4% aqueous NaOH solution.
- a group of fine fibers having a uniform diameter was formed.
- the tensile strength of the fine fiber bundle after removing the sea component was 3.8 cNZ dt ex, and the elongation at break was 55%.
- Comparative Example 3 uses PET1 and modified PET2 for the island and sea components, respectively, at a ratio of 80:20. Because the melt viscosity of the sea component polymer is lower than that of the island component, 90% or more of the island components are bonded to each other, and the bonded island components 2005/006734 had a cross-sectional shape that surrounded the sea component. Therefore, it was not possible to form a fine fiber bundle by removing sea components by weight loss.
- Comparative Example 4 uses PET1 and modified PET3 for the island and sea components, respectively, at a ratio of 80:20. Although sea-island formation was good, the rate of weight loss of the sea component was insufficient compared to that of the island component, so a considerable amount of islands on the fiber surface was reduced, and the sea equivalent was reduced. Despite the removal, most of the sea components distributed in the center of the composite fiber remained without being reduced in weight, and the softness unique to the fine fiber bundle was not obtained.
- Example 6 spinning was performed using PET2 and nylon 6 for the island-to-sea ratio at an island-to-sea ratio of 70:30, but the melt viscosity of the islands was high, and the sea-island formability was good. .
- a yield point corresponding to partial breakage of the sea component did not appear, and it was a normal elongation curve.
- TEM observation of the cross section of the raw yarn showed that the sea-island cross-section formation was good.
- Example 7 spin-drawing was performed in the same manner as in Example 5, except that the nylon 6 used in the sea of Example 5 was used as the island component polymer, and the modified PET 1 used in Example 1 was used as the sea component polymer. went. The sea-island section formation was good. In the load elongation curve, no yield point corresponding to partial breakage of the sea component was found. Dissolve and remove sea components with 4% NaOH aqueous solution at 90 ° C As a result, a fine fiber bundle could be manufactured.
- Example 8 spin drawing was performed using PET3 and polylactic acid as island / sea components at an island: sea mass ratio of 80:20.
- Polylactic acid aqueous solution The rate of weight loss was very fast, a fine fiber bundle could be formed in a short time, and the uniformity of the fine single fiber diameter was good.
- Example 9 when the same island component polymer as in Example 7 was used and melt-spinning was performed using the modified PBT as the sea component polymer, the sea-island sectional formability was good. In addition, since the alkaline content of the sea component was also very fast, a fine fiber bundle having excellent uniformity and a soft feel and having no spots could be obtained as in Example 7.
- Example 10 spinning was carried out using the same island component polymer as in Example 8 and using polystyrene as the sea component polymer at an island: sea component mass ratio of 90:10. .
- the obtained drawn yarn was subjected to a treatment for dissolving and removing sea components at 60 ° C using toluene as a solvent, the quality of the obtained fine fiber bundle was good.
- Example 11 the same polymer as in Example 1 was used as the island component, and the modified PET4 was used as the sea component, and stretching was performed at 1000 islands and an island: sea mass ratio of 70:30.
- the alkali polymer reduction rate of the marine polymer was faster due to the increase in the PEG content, and despite the number of islands of 1,000, a good fine fiber bundle could be produced.
- Melt spinning was performed at a take-up speed.
- the obtained undrawn yarn is bundled to form a tow of 2.2 million dtex and fed into a hot water path at 80 ° C at a supply speed of 5 m / min, and the immersion length in the path is 2 m
- the neck was stretched at a draw ratio of 2.3 times, heat-treated with a heat set roller at 150 ° C, and wound up at 250 m / min.
- the work efficiency of the weight reduction process for this conjugate fiber in a 4% NaOH aqueous solution was good, and a fine fiber bundle with extremely fine single fiber fineness was obtained.
- Example 13 a plain woven fabric was produced using the sea-island fiber prepared in Example 10.
- the plain fabric was scoured, subjected to a weight reduction step (30% weight reduction) in a 4% aqueous NaOH solution, dyed, and subjected to a final set.
- the obtained plain woven fabric composed of a bundle of fine fibers having a single fiber diameter of 640 nm was an interesting woven fabric having no dyeing spots and a hand-like feeling.
- this fabric was subjected to force rendering, a sheet with a film-like appearance that could not be considered as a fabric was obtained.
- the sea-island composite fiber of the present invention can easily dissolve and remove the sea component, a high multifilament yarn composed of a fine fiber bundle having excellent uniformity of single fiber fineness can be produced with high productivity and low cost. It can be provided at Therefore, it can be suitably used in various application fields that require lower cost or further miniaturization.
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- Multicomponent Fibers (AREA)
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- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Braiding, Manufacturing Of Bobbin-Net Or Lace, And Manufacturing Of Nets By Knotting (AREA)
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Abstract
Description
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Priority Applications (8)
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KR1020067017666A KR101250683B1 (ko) | 2004-03-30 | 2005-03-30 | 해도형 복합섬유 및 그 제조방법 |
EP20050728636 EP1731634B1 (en) | 2004-03-30 | 2005-03-30 | Composite fiber and composite fabric of island-in-sea type and process for producing the same |
DE200560023136 DE602005023136D1 (de) | 2004-03-30 | 2005-03-30 | Verbundfaser und flächige verbundware vom typ inseln im meer und verfahren zu ihrer herstellung |
JP2006511882A JP4473867B2 (ja) | 2004-03-30 | 2005-03-30 | 海島型複合繊維束およびその製造方法 |
CN2005800106857A CN1938461B (zh) | 2004-03-30 | 2005-03-30 | 海岛型复合纤维及其制造方法 |
AT05728636T ATE478986T1 (de) | 2004-03-30 | 2005-03-30 | Verbundfaser und flächige verbundware vom typ inseln im meer und verfahren zu ihrer herstellung |
US10/592,667 US7622188B2 (en) | 2004-03-30 | 2005-03-30 | Islands-in-sea type composite fiber and process for producing the same |
US12/576,593 US7910207B2 (en) | 2004-03-30 | 2009-10-09 | Islands-in-sea type composite fiber and process for producing same |
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US10/592,667 A-371-Of-International US7622188B2 (en) | 2004-03-30 | 2005-03-30 | Islands-in-sea type composite fiber and process for producing the same |
US12/576,593 Division US7910207B2 (en) | 2004-03-30 | 2009-10-09 | Islands-in-sea type composite fiber and process for producing same |
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CN (2) | CN1938461B (ja) |
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US20070196649A1 (en) | 2007-08-23 |
US7622188B2 (en) | 2009-11-24 |
EP1731634A4 (en) | 2008-11-05 |
EP1731634B1 (en) | 2010-08-25 |
CN1938461A (zh) | 2007-03-28 |
JP4473867B2 (ja) | 2010-06-02 |
JPWO2005095686A1 (ja) | 2008-02-21 |
KR101250683B1 (ko) | 2013-04-03 |
TWI341339B (en) | 2011-05-01 |
CN1938461B (zh) | 2011-04-27 |
DE602005023136D1 (de) | 2010-10-07 |
ATE478986T1 (de) | 2010-09-15 |
US20100029158A1 (en) | 2010-02-04 |
CN101880921A (zh) | 2010-11-10 |
CN101880921B (zh) | 2013-03-27 |
EP1731634A1 (en) | 2006-12-13 |
KR20060130193A (ko) | 2006-12-18 |
TW200536971A (en) | 2005-11-16 |
US7910207B2 (en) | 2011-03-22 |
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