EP2921576B1 - Fibre conjuguée et procédé de fabrication des fibres ultrafines - Google Patents

Fibre conjuguée et procédé de fabrication des fibres ultrafines Download PDF

Info

Publication number
EP2921576B1
EP2921576B1 EP13855930.7A EP13855930A EP2921576B1 EP 2921576 B1 EP2921576 B1 EP 2921576B1 EP 13855930 A EP13855930 A EP 13855930A EP 2921576 B1 EP2921576 B1 EP 2921576B1
Authority
EP
European Patent Office
Prior art keywords
sea
island
polymer
multicomponent fiber
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13855930.7A
Other languages
German (de)
English (en)
Other versions
EP2921576A1 (fr
EP2921576A4 (fr
Inventor
Masato Masuda
Masaomi MIYASHITA
Joji Funakoshi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of EP2921576A1 publication Critical patent/EP2921576A1/fr
Publication of EP2921576A4 publication Critical patent/EP2921576A4/fr
Application granted granted Critical
Publication of EP2921576B1 publication Critical patent/EP2921576B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00Spinnerette packs; Cleaning thereof
    • D01D4/02Spinnerettes
    • D01D4/025Melt-blowing or solution-blowing dies
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/082Melt spinning methods of mixed yarn
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30Conjugate filaments; Spinnerette packs therefor
    • D01D5/36Matrix structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]

Definitions

  • the present invention relates to a multicomponent fiber including a sea component and an island component which is obtainable by performing melt spinning by a composite spinning machine using a composite spinneret, and a method for producing the multicomponent fiber.
  • the invention also concerns an ultrafine fiber which is obtainable by removing a sea component from the multicomponent fiber.
  • a sea-island multicomponent fiber, one of multicomponent fibers, is a fiber in which in cross-section observation, two or more polymers having different compositions are phase-separated, some kind of polymer is dispersed in another polymer, and the former polymer looks like islands while the latter polymer looks like sea.
  • the former polymer is referred to as an "island polymer”
  • the latter polymer is referred to as a "sea polymer” in some cases.
  • sea-island multicomponent fibers are produced by performing melt-spinning, a sea polymer as an easily soluble component is removed to leave only an island polymer as a hardly soluble component, so that ultrafine fibers with each single fiber having a thread diameter in a nanometer order can be obtained.
  • those fibers can be applied to artificial leathers and new-touch textiles since soft touch and fineness that cannot be achieved with common fibers are realized. Further, those fibers can be expanded to applications of sports wears required to have windbreaking performance and water repellency as high-density fabrics because they have reduced fiber gaps.
  • those fibers can be applied to high-performance filters in view of increasing the specific surface area to improve dust collecting performance, and to wiping cloths and precise polishing cloths for precision equipment in view of wiping out contaminants with ultrafine fibers entering very small grooves.
  • a method for forming a composite polymer flow in a composite spinneret, and producing a multicomponent fiber therefrom is referred to as a composite spinning method
  • a method for producing a multicomponent fiber by melting and kneading polymers is referred to as a polymer alloy method.
  • the composite spinning method is capable of forming a composite polymer flow composed of two or more polymers in a composite spinneret, and precisely controlling a composite structure. Therefore, the composite spinning method is superior to the polymer alloy method in that a thread cross-section form with high accuracy can be uniformly formed.
  • Composite spinneret techniques related to sea-island multicomponent fibers may be classified broadly into two techniques: a pipe type spinneret technique and a distribution type spinneret technique.
  • FIG. 15 shows a partial enlarged longitudinal sectional view of the composite spinneret disclosed in Patent Document 1.
  • explanations may be omitted when there exists a member with the same reference symbol as that corresponding to a drawing that has already been explained.
  • the pipe type spinneret shown in Fig. 15 includes a distribution device 1 provided with sea polymer introduction channels 21, an island polymer introduction channel 22, pipes 20 and a sea polymer distribution chamber 23; a nozzle plate 2 provided with composite polymer discharge holes 15; and a flow contraction plate 3 provided with a spinneret discharge hole 6.
  • a sea polymer as an easily soluble component is guided from the sea polymer introduction channels 21 to the sea polymer distribution chamber 23, and fills the outer periphery of each of the pipes 20.
  • an island polymer as a hardly soluble component is guided from the island polymer introduction channel 22 to the pipes 20, and is discharged from the pipes 20.
  • the island polymer discharged from the pipes 20 is put in the sea polymer filling the sea polymer distribution chamber 23, so that a composite polymer flow with the island polymer covered with the sea polymer is formed. Thereafter, the composite polymer flow merges with another composite polymer flow by passing through the composite polymer discharge holes 15, and is discharged from the spinneret discharge hole 6 to form a multicomponent fiber having a sea-island cross section.
  • Fig. 17 is a partial enlarged plan view of a nozzle plate employed in each of Patent Documents 2 and 3.
  • the nozzle plate in Fig. 17 has composite polymer discharge holes 15, and is provided with a sea polymer admission channel 11 (which has no discharge hole) in which pipes 20 are not arranged.
  • a sea polymer admission channel 11 which has no discharge hole
  • the sea polymer can be evenly supplied to the whole of a composite polymer discharge hole group. Therefore, even at the central part of the composite polymer discharge hole group, the sea polymer exists between island polymers, so that merging of island polymers can be suppressed. Accordingly, in the spinneret technique in Patent Document 2 or 3, a sea-island multicomponent fiber having a relatively large number of islands can be obtained even in a pipe type spinneret.
  • the distribution type spinneret is an effective technique in view of increasing the number of islands .
  • a typical example thereof is a technique disclosed in Patent Document 4.
  • Fig. 16 is a partial enlarged plan view of a nozzle plate having a shape disclosed in Patent Document 4.
  • discharge holes are arranged in such a manner that at least some of sea discharge holes 12 exist in a region surrounded by two common circumscribing lines 30 of an island discharge hole 13 provided in the nozzle plate and an island discharge hole 13a neighboring the island discharge hole 13 with the shortest center-to-center distance, the island discharge hole 13 being considered as a reference. Therefore, in the nozzle plate in Fig. 16 , the sea polymer is forcibly arranged between island polymers, so that merging of island polymers discharged from the island discharge hole 13 and the island discharge hole 13a can be suppressed.
  • sea-island multicomponent fibers having a large number of islands can be produced by making various modifications.
  • the island polymer by dividing the island polymer into multiple segments according to the number of islands, even nanofibers having a fiber diameter in a nanometer order can be obtained, as described above.
  • the hole packing density is simply increased in the techniques described in Patent Documents 1 to 4
  • the distance between island components existing on the cross section of the sea-island multicomponent fiber decreases. Therefore, in a step of removing with a solvent a sea polymer for production of ultrafine fibers, the sea polymer dissolved in the solvent is not efficiently discharged from between island polymers or ultrafine fibers, and thus the efficiency of sea removal may be reduced.
  • US 2010/0195233 concerns a luminance-enhanced film which includes birefringent islands-in-the-sea yarns.
  • an object of the present invention is to provide a sea-island multicomponent fiber with a sea component that can be soluble with high efficiency, and to provide a composite spinneret suitable for production of the sea-island multicomponent fiber.
  • a first aspect of the present invention provides a sea-island multicomponent fiber, as described in claim 1.
  • the present invention provides:
  • the "distribution hole” means a hole formed by combination of a plurality of distribution plates, the hole serving to distribute a polymer in a polymer spinning passage direction.
  • the “distribution groove” in the present invention means a groove formed by combination of a plurality of distribution plates, the groove serving to distribute a polymer in a direction perpendicular to a polymer spinning passage direction.
  • the distribution groove may be a long and narrow hole, or may be formed by digging a long and narrow groove.
  • the "polymer sinning passage direction" means a main direction in which each polymer passes from a distribution device to a nozzle hole of a spinneret.
  • the "composite polymer discharge hole” means a discharge hole through which a composite polymer is discharged, the composite polymer having an island polymer and a sea polymer merged with each other in a sheath-core form, a side-by-side form, a layered form, a sea-island form or a circumferential form.
  • the "hole packing density” means a value determined by dividing the sum of the number of island discharge holes and the number of composite polymer discharge holes by the sum of cross-section areas of introducting holes. In the present invention, only island discharge holes may exist, or only composite polymer discharge holes may exist.
  • the "center” of a diagram in fiber cross-section observation means the gravity center position.
  • the "sea removal" in the present invention means that a sea polymer of a multicomponent fiber is removed with a solvent.
  • the multicomponent fiber of the present invention even when the number of island components per cross-section area of the multicomponent fiber is large, a sea component can be easily removed with a solvent efficiently, so that an extremely thin ultrafine fiber can be obtained. According to the composite spinneret described herein, the multicomponent fiber can be easily produced.
  • a multicomponent fiber of the present invention includes a sea-island region 42 with an island component 43 arranged in a sea component 41, and a sea component region 44 formed only of the sea component 41 as illustrated in Fig. 13 .
  • the sea component region 44 mentioned in the present invention means a region formed only of a sea polymer as shown in Fig. 13 , the sea component region having a width (H) larger than the maximum value of a distance between island components existing in the sea-island region and neighboring each other.
  • the sea component region is between the sea-island region of the multicomponent fiber, and in cross-section observation, there are one or more sea component regions.
  • one of the purposes of the multicomponent fiber of the present invention is production of an ultrafine fiber, and this structure is intended to ensure that the efficiency of the sea removal treatment is not reduced even if the island packing density is increased.
  • the treatment with a solvent naturally proceeds from the outer layer of the multicomponent fiber gradually.
  • island components are affected by the solvent before the sea removal treatment reaches the inner part of the multicomponent fiber. Therefore, there has been the problem that the resulting ultrafine fiber has significantly poor quality, or sea removal is not completed.
  • the present inventors have conceived an idea that a sea component region composed only of a sea polymer in cross-section observation is provided as in the multicomponent fiber of the present invention. That is, in the multicomponent fiber of the present invention, the sea polymer in the sea component region is removed before the solvent dissolves the sea polymer existing in the sea-island region at the time of removing the sea polymer of the multicomponent fiber. Therefore, the solvent reaches the center of the multicomponent fiber early, so that the elution time of the sea polymer can be reduced.
  • the distance between neighboring island components (inter-island component distance: W) in the sea-island region and the width (H) of the sea component region can be determined in the following manner.
  • the multicomponent fiber is embedded in an embedding medium such as an epoxy resin, and cut along the cross section by a microtome, and the cut surface is then photographed by a scanning electron microscope (SEM) at a magnification that allows the entire cross section to be observed.
  • SEM scanning electron microscope
  • the cross section is stained with a metal compound, a contrast difference between the island component and the sea component can be made clear.
  • the width of the sea component region can be measured using image processing software.
  • the inter-island component distance and width of the sea component region herein mean a distance between island components and width of the sea component region as expressed on an image of a cut surface where the cut surface is a cross section in a vertical direction with respect to the fiber axis from the image.
  • the inter-island component distance refers to the minimum value between an island component and another island component for two island components neighboring each other in the sea-island region.
  • the width of the sea component is calculated in the following manner. A boundary line between the sea component region and the sea-island component region is assumed. Points that form the boundary line are assumed, and the shortest distance between each point and a boundary line between the sea-island component and the sea-island region in the opposite direction is determined.
  • the inter-island component distance and the width of the sea component region are each measured in a unit of ⁇ m to the second decimal place, and rounded off to the first decimal place.
  • the above procedure is carried out for each of 10 or more randomly extracted spots.
  • an average of the measured values is employed for the island component distance.
  • the width (H) of the sea component region and the diameter (D) of the multicomponent fiber satisfy the relationship of 0.001 ⁇ H/D ⁇ 0.2.
  • the multicomponent fiber is physically stimulated by a liquid flow during the sea removal treatment when the treatment is performed in a flow liquid in a jet dyeing machine or the like, so that cracks that are once formed are expanded as the sea removal treatment proceeds. Further, a force is applied to the multicomponent fiber in the compression direction due to the effect of the liquid flow, and the multicomponent fiber is physically divided.
  • H/D is preferably as large as possible, and H/D is preferably 0.01 or more, further preferably 0.03 or more. On the other hand, H/D is less than 0.2 from the viewpoint of homogeneity of cross-section forms (e.g. diameter and shape) of the multicomponent fiber and a plurality of existing island components and ease of quality control by cross-section observation or the like.
  • the cross-section area (As) of the sea component region be in a certain ratio to the cross-section area (Ac) of the multicomponent fiber, and the relationship of 0.05 ⁇ As/Ac is preferably satisfied. Further, the relationship of As/Ac ⁇ 0.35 is preferably satisfied. Sea removal efficiency is improved as the parameter of As/Ac becomes larger.
  • the amount of the sea polymer used for formation of the sea component region is small, and also the sea polymer in an amount sufficient for forming a sea-island cross section can be supplied to the sea-island region, so that the sea-island multicomponent fiber of the present invention can be produced with a high island component ratio.
  • the necessity to unduly increase the difficulty degree of design of a spinneret is eliminated.
  • the sea-island region existing in the multicomponent fiber of the present invention refers to a region with a plurality of island components existing in a sea component as described above.
  • the island components are regularly arranged in the sea-island region.
  • the regular arrangement herein means that in four island components close to one another, straight lines connecting the centers of two neighboring island components (45-(a) (straight line connecting the centers of two island components) and 45-(b) (straight line connecting the centers of other two island components) in Fig. 19 ) are in parallel relationship with each other as illustrated in Fig. 19 .
  • the parallel relationship herein means that the angle formed by the two straight lines is not less than 0° and not more than 5°.
  • angles formed by two straight lines are measured to the first decimal place at 20 randomly selected spots in cross-section images of the multicomponent fiber, and when the value determined by rounding off the average of the measured values to an integer is in the above-mentioned range, it is determined that the island components are in parallel relationship with each other.
  • the ratio (L/D) of the length (L) of the sea component region to the diameter (D) of the multicomponent fiber in the multicomponent fiber of the present invention is preferably 0.25 or more (see, for example, Fig. 13 ).
  • the ratio (L/D) is in the above-mentioned range, cracks are generated in the sea component region in the early stage of the sea removal treatment, and a solvent infiltrates into the cracks to increase the specific surface area of the sea polymer exposed to the solvent, so that the sea component can be efficiently removed. This is because the sea component is progressively removed by a treatment with a solvent.
  • Such crack formation due to embrittlement of the sea component region occurs when the ratio of the diameter of the composite cross section to the width of the sea component region is 0.25 or more, but L/D is preferably 0.50 or more.
  • the ratio (L/D) is in the above-mentioned range, cracks are formed over 1/2 or more of the multicomponent fiber diameter in the early stage of the elution treatment, and transversely propagate across the cross section of the multicomponent fiber as the sea removal treatment proceeds and further the fiber is physically stimulated, and ultimately the multicomponent fiber is divided into two halves.
  • the specific surface area treated with the solvent increases in proportion to the square of the division number of the multicomponent fiber. Therefore, the sea removal efficiency is further improved.
  • the length (L) of the sea component region is preferably as large as possible, the maximum viable value of the above-mentioned ratio is 1, and this value may be particularly preferred.
  • the width (H) of the sea component region is preferably larger than the maximum diameter (d) of the island component. This is because the effect of improving sea removal efficiency by arranging the sea component region intended by the present invention essentially depends on the width (H) of the sea component region, but a width being larger than the maximum diameter (d) of the island component is preferred because infiltration of the solvent and crack formation properly proceed without being hindered by influences of island components.
  • the multicomponent fiber of the present invention it is preferable that there exists at least one sea component region where the width (H) of the sea component region is larger than the maximum diameter (d) of the island component, and the length (L1) of the sea component region is equal to or larger than 1/4 of the diameter (D) of the multicomponent fiber.
  • the method for evaluating the island component diameter is as follows.
  • the cross section of the sea-island multicomponent fiber is photographed similarly to the case of the width of the sea component region, and an image is photographed at a magnification that allows 150 or more island components to be observed in multifilaments of the multicomponent fiber.
  • Diameters of 150 island components randomly extracted from the photographed image are measured.
  • the island component diameter herein means a diameter of an imaginary circle circumscribed to a cut surface at three or more points where the cut surface is a cross section in a vertical direction with respect the fiber axis from the image that is two-dimensionally photographed.
  • the value of the island component diameter is measured to the first decimal place in a unit of nm, and rounded off to an integer.
  • the diameters of the 150 photographed island components are measured, and the maximum value thereof is defined as the maximum diameter (d) of the island component in the present invention.
  • the maximum diameter (d) of the island component is preferably smaller than the width (H) of the sea component region, and from the viewpoint of suppressing hindrance to crack formation as described above, H/d is more preferably 2.0 or more.
  • the island component diameter is preferably 100 to 5000 nm. When the island component diameter is in this range, an effect of improving sea removal efficiency in the present invention is obtained, and further, the ultrafine fiber subjected to the sea removal treatment has high quality and excellent characteristics.
  • the effect of the sea component region in the present invention becomes more remarkable without hindering the sea removal treatment, and also ultrafine fibers having extreme thinness unable to be achieved by a single spinning technique can be obtained.
  • Ultrafine fibers generated from the multicomponent fiber of the present invention when having a diameter of 5 ⁇ m or less, have soft touch and fineness that cannot be achieved with common fibers (several tens ⁇ m).
  • the ultrafine fibers can be used, for example, as a material for artificial leathers and high-texture apparels .
  • the ultrafine fibers can be formed into a high-density fabric, and used for sports wears required to have windbreaking performance and water repellency. Extremely thinned fibers enter fine grooves, and the specific surface area increases and contaminants are caught in fine voids between fibers. Therefore, high adsorptivity and dust collecting performance are exhibited.
  • the ultrafine fibers can be used for wiping cloths and precise polishing cloths for precision equipment in applications of industrial materials. Since a high level of wiping performance etc. is required particularly when the ultrafine fibers are to be used for polishing and wiping for IT, the diameter of the ultrafine fiber is preferably as small as possible. A range of 100 to 1000 nm may be a more preferred range. In the multicomponent fiber of the present invention, the island component diameter thereof may be less than 100 nm, but the island component diameter is preferably 100 nm or more from the viewpoint of handling characteristics during the sea removal treatment.
  • the multicomponent fiber of the present invention is suitably used for production of the above-mentioned ultrafine fibers and fiber products composed of the ultrafine fibers. Therefore, improvement of basic characteristics of ultrafine fibers such as mechanical properties, which has been difficult heretofore, can be achieved, and by improving homogeneity of the resulting ultrafine fiber bundles, fiber products composed thereof can be improved in quality.
  • the island polymer is a hardly soluble component and the sea polymer is an easily soluble component.
  • the island polymer may be a polyethylene terephthalate (PET), and the sea polymer may be a copolymerized PET to form an easily soluble component.
  • PET polyethylene terephthalate
  • the copolymerized PET as the sea polymer has a higher solubility with a solvent as compared to the island polymer.
  • the island polymer may be treated with a solvent. Particularly when the island component diameter is small, this effect is very significant.
  • the specific surface area thereof increases, so that the quality may be degraded, for example, mechanical properties of ultrafine fiber bundles are deteriorated, or the island component arranged on the outermost layer and the island component arranged on the inner layer in the multicomponent fiber have different diameters.
  • the sea component region is arranged in accordance with the present invention, and thus the inner part of the multicomponent fiber is affected by the treatment with a solvent in the early stage of the sea removal treatment, so that the degradation in quality which has been the problem with conventional multicomponent fibers is extremely small.
  • ultrafine fibers composed of the island polymer can be produced with a high yield with respect to multicomponent fibers as a raw material by increasing the ratio of the island polymer to the sea polymer.
  • stress in a process for producing fiber spuninning and drawing
  • the fiber structure of the island component can be highly generated. Therefore, mechanical properties of ultrafine fibers can be improved, and also orientation crystallization of the island component proceeds, so that its resistance to a solvent can be improved.
  • the sea component region As described above, owing to existence of the sea component region as a requirement in the present invention, the reduction in sea removal efficiency, which has raised a problem heretofore, can be avoided even if the island packing density is increased. Therefore, fibers can be extremely thinned by increasing the number of islands, and further, by increasing the ratio of the island component, ultrafine fibers having excellent basic characteristics such as mechanical properties can be stably produced with high productivity.
  • the sea component region having the above-mentioned effect exhibits the effects including those illustrated in Figs. 13 , 14 and 20 to 26 when the range defined in the present invention is satisfied. Particularly, it is effective that the sea component region is arranged inward from the surface of the multicomponent fiber.
  • the sea-island component region in the present invention is widely arranged on the cross section of the multicomponent fiber.
  • the sea component region is cruciformly arranged as shown in Fig. 13 .
  • the sea-island multicomponent fiber of the present invention preferably has a strength at break of 0.5 to 10.0 cN/dtex and an elongation of 5 to 700%.
  • the strength herein is a value obtained by determining a load-extension curve of multifilaments under conditions as shown in JIS L 1013 (1999), and dividing the load value at rupture by the initial fineness, and the elongation is a value obtained by dividing the extension at rupture by the initial test length.
  • the initial fineness means a value obtained by calculating the mass per 10000 m from the simple average of a plurality of measurements of the mass of the fiber per unit length.
  • the strength at break of the sea-island multicomponent fiber of the present invention is preferably 0.5 cN/dtex or more in view of passage through the post processing step and endurability of the fiber in actual use.
  • the upper limit of the strength at break of fibers that can be produced is about 10.0 cN/dtex.
  • the elongation is preferably 5% or more in view of passage through the post processing step.
  • An upper limit value of the elongation of fibers that can be produced is generally 700%.
  • the strength at break and elongation can be adjusted by controlling conditions in the production process according to the intended application.
  • ultrafine fibers obtained from the sea-island multicomponent fiber of the present invention are used in applications of general clothes such as inner and outer clothes, it is preferred that the strength at break is 1.0 to 4.0 cN/dtex and the elongation is 20 to 40%. In applications of sports wears etc. in which use conditions are relatively severe, it is preferred that the strength at break is 3.0 to 5.0 cN/dtex and the elongation is 10 to 40%. In applications other than those of clothes, the ultrafine fibers may be used for wiping cloths and polishing cloths. In these applications, a fiber product is rubbed against an object while being pulled under weight.
  • the strength at break is 1.0 cN/dtex or more and the elongation is 10% or more.
  • the sea-island multicomponent fiber of the present invention can be formed into a variety of intermediates such as fiber winding packages and tows, cut fibers, cotton, fiber balls, cords, piles, fabrics and nonwoven fabrics, and subjected to a sea polymer elution treatment to generate ultrafine fibers, from which various fiber products are obtained.
  • the sea-island multicomponent fiber of the present invention can be used in an untreated state, partially freed of a sea polymer, or subjected to a treatment for removal of an island polymer to obtain a fiber product.
  • the fiber products may be used in applications of livingware such as common clothes such as jackets, skirts, pants and underclothes, sports wears, clothing materials, interior products such as carpets, sofas and curtains, vehicle interiors such as car seats, cosmetics, cosmetic masks, wiping cloths and health equipment; applications of environmental/industrial materials such as polishing cloths, filters, harmful substance removal products and separators for batteries; and applications of medical products such as sutures, scaffolds, artificial blood vessels and blood filters.
  • livingware such as common clothes such as jackets, skirts, pants and underclothes, sports wears, clothing materials, interior products such as carpets, sofas and curtains, vehicle interiors such as car seats, cosmetics, cosmetic masks, wiping cloths and health equipment
  • applications of environmental/industrial materials such as polishing cloths, filters, harmful substance removal products and separators for batteries
  • medical products such as sutures, scaffolds, artificial blood vessels and blood filters.
  • Fig. 1 is a schematic sectional view of a composite spinneret as one embodiment of the present invention.
  • Fig. 2 is a schematic sectional view of a composite spinneret 7 of the present invention, a spinning pack 8 that is used along with the composite spinneret 7, a cooler 9, and a periphery thereof.
  • Fig. 4 is a plan view of a nozzle plate that is used as one of embodiments of the present invention
  • Fig. 5 is a partial enlarged plan view of Fig. 4 .
  • Figs. 3 , 7 , 8 , 9 , 11 , 12 , 18 and 27 to 35 are partial enlarged plan views of nozzle plates that are used in various embodiments of the present invention.
  • the composite spinneret 7 that is used in the embodiment of the present invention is mounted in the spinning pack 8, and fixed in a spin block 10 as shown in Fig. 2 .
  • the cooler 9 is provided below the composite spinneret 7.
  • the composite spinneret 7 is formed by stacking a distribution device 1 for distributing polymers, a nozzle plate 2 and a flow contraction plate 3 in order as shown in Fig. 1 . As shown in Fig.
  • the nozzle plate 2 is provided with island discharge holes 13 for discharging an island polymer, or sea discharge holes 12 for discharging a sea polymer, and sea-island discharge hole groups with the island discharge holes 13 and the sea discharge holes 12 forming a group, and sea component region forming hole groups with only the sea discharge holes 12 forming a group form a nozzle hole collection 18.
  • a polymer of each component distributed by a distribution device (not illustrated) is discharged from the island discharge holes 13 or the sea discharge holes 12 shown in Fig. 5 , and a polymer of each component merges with each other to form a composite polymer flow.
  • the composite polymer flow passes through introducting holes 4 and flow contraction holes 5 of the flow contraction plate shown in Fig. 1 , and is discharged from spinneret discharge holes 6.
  • the composite polymer flow is discharged from the spinneret discharge holes 6 shown in Fig. 2 , and then cooled and solidified by an air flow jetted from the cooler 9. Thereafter, an oil is supplied to the composite polymer flow, and then the composite polymer flow is wound as a sea-island multicomponent fiber.
  • a circular cooler 9 that jets an air flow circularly and inward, but a cooler that jets an air flow in one direction may be used.
  • the nozzle plate that is used in the composite spinneret in the embodiment of the present invention has a sea component region forming hole group including a plurality of sea discharge holes 12, and at least one discharge hole group for forming a sea-island region (hereinafter, referred to as a "sea-island discharge hole group"), the discharge hole group including any of the following (i) to (v), and these discharge holes are combined to form one nozzle hole collection.
  • the sea component region forming hole group is continuously arranged with being between the sea-island discharge hole group.
  • an arrangement of the sea-island discharge hole group including the combination (i) is illustrated in Fig.
  • an arrangement of the sea-island discharge hole group including the discharge holes (ii) is illustrated in Fig. 3
  • an arrangement of the sea-island discharge hole group including the combination (iii) is illustrated in Fig. 9
  • an arrangement of the sea-island discharge hole group including the combination (iv) is illustrated in Fig. 11
  • an arrangement of the sea-island discharge hole group including the combination (v) is illustrated in Fig. 18 .
  • the polymers discharged from the sea-island discharge hole group and the sea component region forming hole group of the nozzle plate merge with each other in the introducting hole, and are then discharged from the spinneret discharge hole to form a multicomponent fiber having a sea component region and a sea-island region.
  • the island polymer and the sea polymer are simultaneously discharged to the downstream side from the nozzle plate 2 shown in Fig. 1 .
  • the discharged polymers flow along a polymer spinning passage direction, and are widened in a direction vertical to the polymer spinning passage direction, so that neighboring polymers merge with each other to form a composite polymer flow.
  • the nozzle plate is provided with a sea-island discharge hole group including only the sea discharge holes 12 as shown in Fig. 5 .
  • the discharged polymer moves so as to be widened for filling a channel space, and therefore it is difficult to form the sea component region 44 on the cross section of the multicomponent fiber merely by increasing the distance between sea-island discharge hole groups as shown in Fig. 17 .
  • a nozzle plate as shown in Fig. 17 widening of the polymer is enlarged. Therefore, the cross section of the fiber is destabilized due to deviation of the arrangement of the island polymer, etc., so that island components are not uniformly formed in the multicomponent fiber.
  • sea-island discharge hole group is arranged on the composite spinneret so as to be separated into four parts, and the sea discharge holes 12 are provided in the resulting gap as shown in Fig. 5 .
  • sea discharge holes 12a for the sea component region exist in the gap formed by separation of the sea-island discharge hole group, and thus the widening of the sea-island region can be suppressed to inhibit destabilization of the fiber cross section.
  • two or less island discharge holes 13 are arranged on an imaginary circumference with the sea discharge hole 12a as a center, the radius of which is a center-to-center distance between the sea discharge hole 12a and a discharge hole closest to the sea discharge hole 12a among the sea discharge holes 12 or the island discharge holes 13 close to the sea discharge hole 12a, so that a sea component region forming hole group including a plurality of sea discharge holes 12a is formed.
  • the sea component region forming hole group is continuously arranged with a part of the sea-island discharge hole group held between both sides as shown in Fig. 5 , so that a multicomponent fiber having the sea component region 44 as shown in Fig. 3 is obtained.
  • the sea discharge hole 12 is arranged at each apex of a hexagonal lattice as an arrangement pattern of holes in the sea-island discharge hole group, and the island discharge hole 13 is arranged at the gravity center position of the hexagon that forms the lattice.
  • a tetragonal lattice is shown in Fig. 7
  • a trigonal lattice is shown in Fig. 8 .
  • the distance between neighboring island discharge holes can be reduced, and therefore the hole packing density can be further increased.
  • neighboring island discharge holes 13 can be made closer to each other. Therefore, the hole packing density can be further increased.
  • the hole packing density can be increased in the order of a trigonal lattice, a tetragonal lattice and a hexagonal lattice.
  • spinning conditions such as the island polymer ratio may be restricted, and therefore it is preferred to determine the arrangement pattern of holes in accordance with the cross-section form of an intended multicomponent fiber.
  • Fig. 6 is a partial enlarged longitudinal sectional view of a nozzle plate.
  • the distribution device is formed by stacking one or more thick plates called measuring plate(s) 16 and one or more thin plates called distribution plate (s) 17.
  • the measuring plate 16 and the distribution plate 17 are placed by a positioning pin so as to align with the center position (core) of the composite spinneret 7.
  • the measuring plate 16 and the distribution plate 17 can also be fixed by a screw or a bolt.
  • the plates are metal-bonded (diffusion-bonded) by thermocompression bonding etc. for suppressing leakage of a polymer from a gap between members.
  • the measuring plate 16 in Fig. 6 is processed to have a channel groove and a channel hole for distributing the island polymer and the sea polymer and supplying the polymers to the distribution plate 17.
  • the channel hole applies a constant channel pressure loss to the polymer, so that the polymer can be uniformly supplied to an inflow channel of the distribution plate 17 positioned on the top part.
  • the distribution plate 17 is provided with a distribution groove 51 and/or a distribution hole 52 for distributing the island polymer and the sea polymer.
  • the distribution groove 51 serves to guide the polymer in a direction vertical to the polymer spinning passage direction (leftward arrows and rightward arrows in Fig. 6 ), and the distribution hole 52 serves to guide the polymer in the polymer spinning passage direction (downward arrows in Fig. 6 ).
  • the distribution plate 17 having the distribution hole 52 and the distribution plate 17 having the distribution groove 51 are alternately stacked, one distribution groove 51 communicating with one distribution hole 52 at a position on the downstream side in the polymer spinning passage direction is formed. Therefore, a tournament type channel that forms a plurality of distribution holes 52 each communicating with the end of the distribution groove 51 is formed, so that the polymer of each component distributed by the measuring plate 16 can be evenly divided into smaller quantity polymers.
  • Fig. 3 is a partial enlarged plan view of the nozzle plate and Fig. 10 that is a schematic longitudinal sectional view of the composite spinneret.
  • the nozzle plate shown in Fig. 3 shows that the sea-island discharge hole group includes composite polymer discharge holes.
  • the nozzle plate shown in Fig. 3 is generally called a pipe type spinneret, with the sea-island discharge hole group including composite polymer discharge holes 15. As shown in Fig.
  • a distribution device 64 is provided with pipes 62 for supplying the island polymer, sea polymer introduction channels 61 for supplying the sea polymer, and a sea polymer distribution chamber 63 communicating with the sea polymer introduction channels 61.
  • the pipes 62 of the distribution device 64 are formed so as to communicate with composite polymer discharge holes 66 of the sea-island discharge hole group on a one-to-one basis.
  • the sea polymer distribution chamber 63 is formed so as to communicate with composite polymer discharge holes 66 and a sea discharge hole 65 of the sea component region forming hole group.
  • the resulting composite polymer flow has a sheath-core structure in which the island polymer forms a core and the sea polymer forms a sheath.
  • the sea polymer is supplied from the sea polymer distribution chamber 63 to the sea discharge hole 65 of the sea component region forming hole group.
  • the composite polymer discharged from the sea-island discharge hole group and the sea polymer discharged from the sea component region forming hole group merge with each other on the lower surface of a nozzle plate 67. Since the sea polymer discharged from the sea component region forming hole group exists between composite polymer flows, a multicomponent fiber with a sea component region formed on the cross section according to the present invention can be produced.
  • the sea-island discharge hole group includes composite polymer discharge holes 15 and sea discharge holes 12.
  • Each polymer supplied from a distribution device (not illustrated) is distributed, and supplied to each hole of the nozzle plate.
  • the composite polymer discharge hole 15 of the sea-island discharge hole group shown in Fig. 9 the sea polymer and the island polymer merge with each other to form a composite polymer flow, and the composite polymer flow is discharged.
  • the sea discharge hole 12 only the sea polymer is discharged.
  • the polymers are discharged from the composite polymer discharge holes 15 and the sea discharge holes 12 of the sea-island discharge hole group, and the polymers merge with each other to form a composite polymer flow having a sea-island form.
  • the feature of the form shown in Fig. 9 is that the sea-island discharge hole group is provided with the sea discharge holes 12 in addition to the composite polymer discharge holes 15. Therefore, the sea polymer is arranged on the periphery of the composite polymer flow in a sheath-core form (core: island polymer and sheath: sea polymer), which is formed by the composite polymer discharge holes 15. Accordingly, in the case of the multicomponent fiber shown in Fig. 13 , the distance between the island components 43 can be increased.
  • island polymers may merge with each other as the ratio of the island component is increased, but this form is preferred from the viewpoint of suppressing merging of island polymers because the sea polymer exists in a large amount between island polymers.
  • Fig. 11 is a partial enlarged plan view of a nozzle plate.
  • the sea-island discharge hole group includes composite polymer discharge holes 15 and island discharge holes 13.
  • Each polymer supplied from a distribution device (not illustrated) is distributed, and supplied to each hole of the nozzle plate.
  • the composite polymer discharge hole 15 of the sea-island discharge hole group the sea polymer and the island polymer merge with each other, and the resulting composite polymer flow is discharged.
  • the island discharge hole 13 only the island polymer is discharged.
  • the island discharge hole group is provided with the island discharge holes 13 in addition to the composite polymer discharge holes 15. Therefore, a composite polymer flow with the island polymer existing on the periphery of a polymer flow in a sheath-core form (core: island polymer and sheath: sea polymer) can be formed. As a result, as compared to the arrangement (ii) shown in Fig. 3 , the hole packing density can be increased, so that a larger number of island components can be arranged on the cross section of the multicomponent fiber.
  • Fig. 18 is a partial enlarged plan view of a nozzle plate.
  • the sea-island discharge hole group includes composite polymer discharge holes 15, sea discharge holes 12 and island discharge holes 13.
  • Each polymer supplied from a distribution device (not illustrated) is distributed, and supplied to each hole of the nozzle plate.
  • the composite polymer discharge hole 15 of the sea-island discharge hole group the sea polymer and the island polymer merge with each other, and the resulting composite polymer flow is discharged.
  • the island discharge hole 13 In the island discharge hole 13, only the island polymer is discharged, and in the sea discharge hole 12, only the sea polymer is discharged.
  • the feature of the nozzle plate shown in Fig. 18 is that the island discharge hole group is provided with the island discharge holes 12 and the sea discharge holes 13 in addition to the composite polymer discharge holes 15. Therefore, a composite polymer flow with a sea polymer surrounding a sheath-core (core: island polymer and sheath: sea polymer) polymer and an island polymer can be formed. Accordingly, the number of island components in the multicomponent fiber is larger as compared to the arrangement (iv) shown in Fig. 11 , and smaller as compared to the arrangement (iii) shown in Fig. 9 .
  • the distance between island components is larger as compared to the arrangement (iii) shown in Fig. 9 , and smaller as compared to the arrangement (iv) shown in Fig. 11 . Therefore, the effect of increasing the number of islands and improving the sea removal efficiency of the sea polymer is not lower as compared to the arrangement (iii) and not higher as compared to the arrangement (iv).
  • Figs. 9 , 11 and 18 in which a pipe type spinneret is used show an example in which a composite polymer flow formed by the composite polymer discharge holes 15 has a sheath-core structure of an island polymer and a sea polymer, but the present invention is not limited to the example.
  • the composite polymer flow may be a side-by-side form, a multi-layered form or a sea-island form, and can be formed diversely according to the state of distribution or merging of the polymers in the distribution device.
  • the sea component region forming hole group in the present invention is continuously arranged from the outer circumference of a circumscribed circle of the nozzle hole collection 18 to a region with a radius of 0.5R or less where R is the radius of the circumscribed circle of the nozzle hole collection 18, with a part of the sea-island discharge hole group surrounding both sides of the sea component region forming hole group as shown in Fig. 12 , the purpose of the present invention can be achieved.
  • An removing discharge hole group is not necessarily cruciformly arranged, and may be arranged in a radial form, a latticed form, or in the form of three parallel lines, and the important point here is that the sea component region forming hole group is arranged with a part of the sea-island discharge hole group being in contact with both sides.
  • the shape of the composite spinneret 7 shown in Fig. 1 when seen from above, is not limited to a circular shape, and may be a tetragonal shape or a polygonal shape.
  • the arrangement of the spinneret discharge holes 6 in the composite spinneret 7 shown in Fig. 1 or the nozzle hole collection 18 shown in Fig. 4 may be changed in accordance with the number of sea-island multicomponent fibers, the number of yarn threads and a cooler.
  • the cooler 9 shown in Fig. 2 is a circular cooler, it is preferred to circularly arrange the spinneret discharge holes or the nozzle hole collection over one line or a plurality of lines.
  • the cooler 9 shown in Fig. 2 is a unidirectional cooler, it is preferred to arrange the spinneret discharge holes or the nozzle hole collection in zigzags.
  • Each channel hole for discharging the polymer of each component may have any shape such as a circular shape, a polygonal shape or a star shape. Depending on the embodiment, each channel hole may be made variable such that, for example, the cross section is changed along the polymer spinning passage direction.
  • the introducting hole 4 shown in Fig. 1 is provided with a definite approach zone extending from the lower surface of the nozzle plate 2 in the polymer spinning passage direction, and thus serves to stabilize the composite polymer flow by reducing the flow rate difference immediately after the island polymer and the sea polymer merge with each other. It is preferred that the hole diameter of the introducting hole 4 is larger than the diameter of a circumscribed circle of the nozzle hole collection provided on the nozzle plate 2, and that the ratio of the cross-section area of the circumscribed circle of the nozzle hole collection to the cross-section area of the introducting hole 4 is as small as possible.
  • the introducting hole 4 is formed as described above, widening of each polymer discharged from the nozzle plate 2 is suppressed, so that the composite polymer flow can be stabilized.
  • the composite spinneret 7 can be downsized, and an instable phenomenon such as draw resonance of the composite polymer flow can be suppressed to stably supply the composite polymer flow.
  • the method for producing a multicomponent fiber according to the present invention can be carried out using a known composite spinning machine, and it is preferred to use the composite spinneret 7 shown in Fig. 1 from the viewpoint of controlling the composite cross section unique to the present invention.
  • a purpose of the present invention is to produce a sea-island multicomponent fiber for generating ultrafine fibers
  • the island polymer and sea polymer include melt-moldable polymers such as polyethylene terephthalate or copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyolefins, polycarbonate, polyacrylate, polyamide, polylactic acid and thermoplastic polyurethane.
  • melt-moldable polymers such as polyethylene terephthalate or copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyolefins, polycarbonate, polyacrylate, polyamide, polylactic acid and thermoplastic polyurethane.
  • polycondensation-based polymers represented by polyester and polyamide are preferred because they have a high melting point.
  • the melting point of the polymer is preferably 165°C
  • the polymer may contain various kinds of additives such as an inorganic material such as titanium oxide, silica or barium oxide, a colorant such as carbon black, a dye or a pigment, a flame retardant, a fluorescent brightening agent, an antioxidant and an ultraviolet absorber.
  • an inorganic material such as titanium oxide, silica or barium oxide
  • a colorant such as carbon black, a dye or a pigment, a flame retardant, a fluorescent brightening agent, an antioxidant and an ultraviolet absorber.
  • the polymer can be selected from melt-moldable polymers which are more easily soluble than other components, such as polyester and copolymers thereof, polylactic acid, polyamide, polystyrene and copolymers thereof, polyethylene and polyvinyl alcohol.
  • the easily soluble component is preferably copolymerized polyester, polylactic acid, polyvinyl alcohol or the like which is easily soluble in an aqueous solvent or hot water, and in particular, polyester and polylactic acid copolymerized with polyethylene glycol and/or sodium sulfoisophthalic acid alone or in combination are preferable from the viewpoint of spinnability and solubility in low-concentration aqueous solvents. Polyester copolymerized with sodium sulfoisophthalic acid alone is particularly preferable from the viewpoint of the ease of sea removal and fiber openability of the resulting ultrafine fibers.
  • a difference in speed of dissolution between the hardly soluble component and the easily soluble component in a solvent used for sea removal is preferably large from the viewpoint of stability of the cross-sectional shape and retention of mechanical properties of ultrafine fibers, and a combination should be selected from the above-mentioned polymers based on a dissolution speed ratio ranging from 10 to 3000.
  • preferred combinations of polymers for obtaining ultrafine fibers from the sea-island multicomponent fiber of the present invention include, for example, combinations of polyethylene terephthalate copolymerized with 1 to 10 mol% of 5-sodium sulfoisophthalic acid as a sea polymer and polyethylene terephthalate or polyethylene naphthalate as an island polymer; and combinations of polylactic acid as a sea polymer and nylon 6, polytrimethylene terephthalate or polybutylene terephthalate as an island polymer.
  • the spinning temperature in spinning of the sea-island multicomponent fiber for use in the present invention is equal to or higher than a temperature at which one of two or more polymers that has the highest melting point or viscosity is flowable.
  • the temperature at which the polymer is flowable although it depends on the molecular weight, is indicated by the melting point of the polymer, and may be set in the range up to 60°C above the melting point. Such a temperature is preferable because thermal decomposition of polymers in a spinning head or a spinning pack is prevented to suppress a decrease in molecular weight.
  • the through-put rate of the polymer in the production method of the present invention may be 0.1 g/min/hole to 20.0 g/min/hole per nozzle hole as a range that allows the polymer to be stably discharged. It is preferable that at this time the pressure loss in the nozzle hole, which can ensure discharge stability, is taken into consideration. It is preferred that, with the pressure loss herein considered to be 0.1 MPa to 40 MPa, the through-put rate is selected from the above-mentioned range in relation to the melt viscosity of the polymer, the nozzle hole diameter and the nozzle hole length.
  • the ratio of the island component (hardly soluble component) to the sea component (easily soluble component) can be selected from the range of 10/90 to 95/5 in terms of the ratio of sea component /island component on the basis of the mass of each polymer through-put rate. It is preferred that the ratio of the island component is increased in the ratio of sea component/island component from the viewpoint of productivity of ultrafine fibers.
  • the ratio of sea component/island component is more preferably in the range of 20/80 to 50/50 for producing multicomponent fibers and ultrafine fibers efficiently while maintaining stability by the production method of the present invention from the viewpoint of long-term stability of the cross section of the sea-island multicomponent fiber.
  • the sea-island composite polymer flow thus discharged from the composite spinneret is cooled and solidified, supplied with a spinning oil, and taken up by a roller, the circumferential speed of which is controlled, to form a sea-island multicomponent fiber.
  • the spinning velocity may be determined from the through-put rate and the intended fiber diameter, the spinning velocity is preferably in the range of 100 to 7000 m/min in the production method of the present invention.
  • the fiber can be made to have not only a circular shape, but also a shape other than a circular shape, such as a trigonal shape or a flat shape, or hollowed by changing the shape of the spinneret discharge hole 6.
  • the multicomponent fiber may have one yarn thread as a monofilament, or two or more yarn threads as a multifilament.
  • the spun multicomponent fiber may be wound up and then drawn from the viewpoint of improving mechanical properties by enhancing orientation, or may be subsequently drawn without being wound up.
  • a fiber composed of a thermoplastic polymer that is generally capable of being melt-spun is well drawn out in a fiber axis direction in response to the circumferential speed ratio of a first roller set at a temperature that is not lower than the glass transition temperature and not higher than the melting point to a second roller set at a temperature equivalent to the crystallization temperature, and the fiber is subjected to heat-setting and wound up, so that the multicomponent fiber having a sea-island multicomponent fiber cross section as shown in Fig. 7 can be obtained.
  • the dynamic elasticity (tan ⁇ ) of the multicomponent fiber is measured, and a temperature equal to or higher than the peak temperature on the high-temperature side of the obtained tan ⁇ may be selected as a preheating temperature. It is also preferred to perform the drawing step in multiple stages from the viewpoint of increasing the stretch ratio to improve mechanical properties.
  • the multicomponent fiber is immersed in a solvent etc. in which an easily soluble component can be removed, so that the easily soluble component is removed, i.e. a sea removal step is performed, and thus ultrafine fibers composed of a hardly soluble component can be obtained.
  • a solvent etc. in which an easily soluble component can be removed, so that the easily soluble component is removed, i.e. a sea removal step is performed, and thus ultrafine fibers composed of a hardly soluble component can be obtained.
  • the easily soluble component is copolymerized PET, polylactic acid (PLA) or the like copolymerized with 5-sodium sulfoisophthalic acid etc.
  • an aqueous alkali solution such as an aqueous sodium hydroxide solution can be used.
  • the multicomponent fiber or a fiber structure formed thereof may be immersed in an aqueous alkali solution.
  • heating of the aqueous alkali solution to 50°C or more is preferable because the hydrolysis can be accelerated.
  • the use of a fluid dyeing machine etc. for the treatment is preferable from an industrial point of view because a large batch can be processed at a time to achieve high productivity.
  • the method for producing the ultrafine fiber according to the present invention is described above on the basis of a common melt spinning technique, but needless to say, meltblowing and spunbonding can be used for its production, and further, a wet or a dry-wet solution spinning technique can also serve for its production.
  • the ultrafine fiber according to the present invention will be described in detail below by way of examples. For examples and comparative examples, evaluations were performed as described below.
  • the measurement was performed at 25°C using ortho-chlorophenol as a solvent.
  • Chips of a polymer were dried in a vacuum dryer down to a moisture content of 200 ppm or less, and subjected to melt viscosity measurement in Capilograph 1B manufactured by Toyo Seiki Seisaku-sho, Ltd. in which the strain speed was changed in stages.
  • the measuring temperature was set to about the spinning temperature, and the melt viscosity at 1,216 s -1 was shown in examples and comparative examples. The measurement was started 5 minutes after feeding a sample into a heating furnace and performed in a nitrogen atmosphere.
  • the mass per 100 m was measured and multiplied by 100 to calculate the fineness.
  • the mass per 10 m was measured and multiplied by 1000 to calculate the fineness. Weighing of these samples was performed in an atmosphere at a temperature of 25°C and a humidity of 55% RH.
  • a tensile tester "Tensilon" (registered trademark) Model UCT-100 manufactured by Orientec Co., Ltd. was used to obtain a stress-strain curve of each of the multicomponent fiber and the ultrafine fiber under the conditions of a sample length of 20 cm and a tension speed of 100%/min.
  • the load at rupture was measured, and the load was divided by the initial fineness to calculate the strength.
  • the strain at rupture was measured, and divided by the sample length to calculate the elongation. Evaluations were performed with a unit of cN/dtex for the strength and a unit of % for the elongation.
  • the obtained sea-island multicomponent fiber was embedded in an epoxy resin, the embedded sample was frozen by Cryosectioning System Model FC ⁇ 4E manufactured by Reichert, and cut by Reichert-Nissei Ultracut N equipped with a diamond knife, and the cross section of the multicomponent fiber was then photographed using a scanning electron microscope (SEM) Model VE-7800 manufactured by KEYENCE CORPORATION.
  • SEM scanning electron microscope
  • the multicomponent fiber diameter D, the island component maximum diameter d, the inter-island component distance W, the sea component region width H, the sea component region length L and neighboring island component parallelization degree ⁇ ) were evaluated from randomly selected images using image processing software (WINROOF).
  • island component maximum diameter d an image was photographed at a magnification allowing 150 or more island components to be observed, and island component diameters of 150 island components randomly extracted from the photographed image were measured.
  • the value of the island component diameter is measured to the first decimal place in a unit of nm, and rounded off to an integer.
  • the diameters of the 150 photographed island components were measured, and the maximum value thereof was defined as the island component maximum diameter d.
  • the multicomponent fiber diameter D, the inter-island component distance W, the sea component region width H and the sea component region length L were each measured to the second decimal place in a unit of ⁇ m from the cross-section image for randomly selected 10 or more multicomponent fibers in multifilaments, and the measured value was rounded off to the first decimal place.
  • the above procedure was carried out for 10 or more spots, and the simple number average thereof was determined. From the thus obtained multicomponent fiber diameter D, sea component region width H and sea component region length L, the multicomponent fiber cross-section area Ac and the sea component region total cross-section area As per multicomponent fiber were determined.
  • the neighboring island component parallelization degree is an index showing the regularity of arrangement of island components.
  • An angle ⁇ formed by straight lines connecting the centers of two neighboring island components (45- (a) (straight line 1 connecting the centers of two island components) and 45-(b) (straight line 2 connecting the centers of other two island components) in Fig. 19 ) in four island components close to one another as illustrated in Fig. 19 was defined as the neighboring island component parallelization degree. Measurement was performed for 10 or more spots for each of randomly selected 10 or more multicomponent fibers in multifilaments, and the simple number average thereof was determined.
  • This item is intended for evaluating an effect of existence of a sea component region.
  • the multicomponent fiber obtained under each of the spinning conditions was woven, and the obtained woven fabric was immersed for 15 minutes in a sea removal bath filled with a 3 wt% aqueous sodium hydroxide solution of 80°C (bath ratio: 1 : 100 (woven fabric : solvent)), so that a sea polymer was removed.
  • the bath ratio herein means the mass ratio of the sample to the solvent
  • the bath ratio of 1 : 100 means that the removal treatment is performed using a solvent with a mass that is 100 times as large as the mass of a sample.
  • the multicomponent fiber obtained under each of the spinning conditions was woven, 10 g of the obtained knitted fabric was prepared, and 99% or more of the sea polymer was removed in a removal bath filled with a 3 wt% aqueous sodium hydroxide solution of 80°C (bath ratio: 1 : 100).
  • the bath ratio herein means the mass ratio of the sample to the solvent, and the bath ratio of 1 : 100 means that the sea removal treatment is performed using a solvent with a mass that is 100 times as large as the mass of a sample. Removal of the sea component is evaluated based on the weight reduction rate of the sample on the premise that the removal rate of the sea component and the weight reduction rate of the sample (equation described below) are the same value.
  • Weight reduction rate % 1 ⁇ weight of sample after elution treatment / weight of sample before elution treatment ⁇ 100
  • a 100 ml portion was sampled from the solution used for the sea removal treatment, and this solution was passed through glass fiber filter paper with a retained particle diameter of 0.5 ⁇ m. Based on the difference in dry mass of the filter as measured in an atmosphere at a temperature of 25°C and a humidity of 55% RH between before and after the treatment, the degree of coming-off of the ultrafine fiber was evaluated in four ranks as described below.
  • Example 1 Polyethylene terephthalate (PET, melt viscosity: 120 Pa ⁇ s) with an intrinsic viscosity (IV) of 0.63 dl/g as an island polymer, and PET (hereinafter referred to as "copolymer PET 1," melt viscosity: 140 Pa ⁇ s) with an IV of 0.58 dl/g, which was copolymerized with 5.0 mol% of 5-sodium sulfoisophthalic acid, as a sea polymer were separately melted at 290°C, then weighed, and fed into a spinning pack containing a composite spinneret 7 of the embodiment as shown in Fig. 2 , so that a sea-island composite polymer flow was melt-discharged.
  • PET polyethylene terephthalate
  • IV intrinsic viscosity
  • the sea-island component ratio based on the mass of the fed polymer per unit time was 50/50.
  • the discharged composite polymer flow was cooled and solidified, then supplied with an oil, and wound up at a spinning velocity of 1500 m/min to obtain an as-spun fiber of a 150 dtex-15 filament (single hole through-put rate: 2.25 g/min).
  • the wound-up as-spun fiber was drawn at a ratio of 3.0 between rollers heated to 90°C and 130°C, respectively, to form a multicomponent fiber of a 50 dtex-15 filament.
  • a distribution type spinneret as shown in Fig. 6 was used.
  • a nozzle plate 2 holes corresponding to the condition (i) were arranged to form a hexagonal lattice as illustrated in Fig. 28 , so that the hole packing density was 1.5 (holes/mm 2 ).
  • the radius of a circumscribed circle of a nozzle hole collection was defined as "radius R". (The "radius R" has the same meaning hereinafter.)
  • sea component region forming hole groups were arranged from the outer periphery of the circumscribed circle of the nozzle hole collection to the circumference with a radius of 0.7R in such a manner that four sea component region forming hole groups were between sea-island discharge hole groups.
  • Example 2 The same procedure as in Example 1 was carried out except that a composite spinneret was used which included a nozzle plate in which as illustrated in Fig. 29 , island discharge holes 13 and sea discharge holes 12 were arranged to form a tetragonal lattice, the hole packing density was 2.0 (holes/mm 2 ), and similarly to Example 1, some of sea-island discharge hole groups between four sea component region forming hole groups.
  • Example 2 sea component regions were formed on the composite cross section similarly to Example 1, and thus sea component solubility was satisfactory (sea component solubility: Good), so that the degree of coming-off of the ultrafine fiber during sea removal was low (evaluation of coming-off: Good). Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 1.
  • Example 3 Except that a composite spinneret was used which included a nozzle plate as illustrated in Fig. 30 in which island discharge holes 13 were arranged to form a trigonal lattice, sea discharge holes 12 were arranged, the hole packing density was 3.0 (holes/mm 2 ), and similarly to Example 1, four sea component region forming hole groups were arranged so as to surround some of sea-island discharge hole groups on both sides, the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • the cross section of the multicomponent fiber of Example 3 had four sea component regions as illustrated in Fig. 14 . In cross-section observation, these sea component regions extended toward the center from the upper side, the right side, the lower side and the left side on the surface of the fiber, but did not reach the center. The shape thereof was almost rectangular.
  • the cross-sectional parameter of the multicomponent fiber was as shown in Table 1, and satisfied the requirement of the multicomponent fiber of the present invention.
  • Example 3 satisfactory sea component solubility comparable to sea component solubility in Examples 1 and 2 (sea component solubility: Good) was achieved although the island packing density was further increased, and further, the degree of coming-off of the ultrafine fiber during sea removal was also low (evaluation of coming-off: Good) although the diameter of the ultrafine fiber was reduced. Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 1.
  • Example 4 Except that a composite spinneret used in Example 4 was a pipe type spinneret as shown in Fig. 10 , and included a nozzle plate as shown in Fig. 31 , and the hole packing density was 1.2 (holes/mm 2 ), the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • the multicomponent fiber of Example 4 had four sea component regions formed on the cross section as illustrated in Fig. 14 .
  • the cross-sectional parameter of the multicomponent fiber was as shown in Table 1, and satisfied the requirement of the multicomponent fiber of the present invention.
  • the fiber had satisfactory sea component solubility (sea polymer solubility: Good), but island components in the sea-island region were arranged in closest packing, and thus it took a little longer time to complete sea removal as compared to Example 1. Therefore, the degree of coming-off of the ultrafine fiber during sea removal tended to slightly increase, but remained at an acceptable level (evaluation of coming-off: Fair).
  • Example 5 Except that a composite spinneret was used which included a nozzle plate in which as shown in Fig. 12 , sea component region forming hole groups were arranged so as to reach the circumference with a radius of 0.5R, and the hole packing density was 1.4 (holes/mm 2 ), the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • the multicomponent fiber of Example 5 had four sea component regions on the cross section as illustrated in Fig. 14 .
  • the cross-sectional parameter of the multicomponent fiber was as shown in Table 1, and satisfied the requirement of the multicomponent fiber of the present invention.
  • sea component region forming hole groups were arranged so as to reach the circumference with a radius of 0.5R, and therefore as compared to Example 1, the sea component region extended to the inner part of the multicomponent fiber, so that sea component solubility was extremely excellent (sea component solubility: Very Good) although the ratio (H/D) of the multicomponent fiber diameter D to the sea component region width H was 0.03, a value comparable to that in Example 1.
  • Example 5 The sample of Example 5 was treated for 5 minutes under the same sea removal treatment conditions as in the evaluation of sea polymer solubility, an ultrafine fiber bundle of the treated sample was observed, and the result of the observation showed that the multicomponent fiber was divided into a plurality of parts due to formation of cracks in the multicomponent fiber. This effect is ascribable to improvement of sea component solubility. Since the treatment time required for completing sea removal was shortened, coming-off of the ultrafine fiber hardly occurred (evaluation of coming-off: Very Good), and the ultrafine fiber had excellent strength characteristics (strength: 2.6 cN/dtex and elongation: 57%). Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 1.
  • the multicomponent fiber of Example 6 had four sea component regions on the cross section as illustrated in Fig. 14 .
  • the cross-sectional parameter of the multicomponent fiber was as shown in Table 1, and satisfied the requirement of the multicomponent fiber of the present invention.
  • the mechanical properties of the multicomponent fiber were significantly improved (strength: 3.3 cN/dtex and elongation: 31%) as compared to Example 1 by increasing the island polymer ratio.
  • fiber breakage etc. did not occur during a Spinning step such as spinning and drawing, and a step of processing the fiber into a fabric, and thus excellent quality was achieved.
  • sea polymer solubility was satisfactory (sea polymer solubility: Good) owing to the effect of the sea component region as a feature of the present invention.
  • the fiber structure of the island component was highly formed in the Spinning step, so that coming-off of the ultrafine fiber during sea removal did not occur (evaluation of coming-off: Very Good), and the ultrafine fiber had excellent mechanical properties (strength: 3.1 cN/dtex and elongation: 40%). Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 1.
  • the multicomponent fiber of Example 7 had four sea component regions on the cross section as illustrated in Fig. 14 .
  • the cross-sectional parameter of the multicomponent fiber was as shown in Table 1, and satisfied the requirement of the multicomponent fiber of the present invention.
  • the island polymer ratio was reduced, and thus the ratio (H/D) of the multicomponent fiber diameter D to the sea component region width H increased to 0.25, so that sea component solubility was extremely excellent (sea component solubility: Very Good) .
  • Example 5 the sample was treated for 5 minutes under the same elution treatment conditions as in the evaluation of sea component solubility, an ultrafine fiber bundle of the treated sample was observed, and the result of the observation showed that the multicomponent fiber was already divided into a plurality of parts, and ultrafine fibers were already generated at many parts.
  • the degree of coming-off of the ultrafine fiber slightly increased as compared to Example 1, but remained at a practically acceptable level (evaluation of coming-off: Fair). Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 1.
  • Example 2 Except that a composite spinneret was used which included a nozzle plate in which island discharge holes and sea discharge holes were arranged to form a hexagonal lattice similarly to Example 1, and a sea component region forming hole group was not arranged, the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • the cross section thereof was not provided with a sea component region as a feature of the present invention because a sea component region forming hole group was not arranged, and thus the same sea-island multicomponent fiber as conventional one as illustrated in Fig. 27 was obtained.
  • Comparative Example 1 mechanical properties were almost comparable to those in Example 1 (strength: 2.3 cN/dtex and elongation: 32%), but since elution of the sea polymer gradually proceeded from the outermost layer of the multicomponent fiber, sea component solubility was considerably reduced (sea component solubility: Poor).
  • the sample of Comparative Example 1 was treated for 5 minutes under the same elution treatment conditions as in the evaluation of sea component solubility, an ultrafine fiber bundle of the treated sample was observed, and the result of the observation showed that only the sea component on the surface layer of the multicomponent fiber was removed, and sea removal hardly proceeded.
  • Example 2 Except that a composite spinneret was used which included a nozzle plate in which island discharge holes and sea discharge holes were arranged to form a hexagonal lattice similarly to Example 1, a sea component region forming hole group was not arranged, and the hole packing density was 3.0 (holes/mm 2 ), and the island polymer ratio was 80%, the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • the cross section thereof was not provided with a sea component region as a feature of the present invention because a sea component region forming hole group was not arranged, and the number of islands increased by a factor of 2 as compared to Comparative Example 1, so that the multicomponent fiber had a cross-section structure in which the whole cross section thereof was closely packed with the island component.
  • the multicomponent fiber had relatively satisfactory mechanical properties (strength: 3.3 cN/dtex and elongation: 33%), but the fiber had a structure in which the island component was densely arranged, so that elution of the sea polymer was extremely hard to proceed, leading to extremely low sea component solubility (sea component solubility: Poor).
  • the sample of Comparative Example 2 was treated for 5 minutes under the same elution treatment conditions as in the evaluation of sea component solubility, a fiber bundle of the sample was observed, and the result of the observation showed that elution of the sea polymer hardly proceeded, and the state of the multicomponent fiber was almost unchanged from the state before the treatment. Since ultrafine fibers were in part generated in Comparative Example 1, the sea component solubility of the sample of Comparative Example 2 was further reduced as compared to Comparative Example 1.
  • the multicomponent fiber of Comparative Example 3 was not provided with a sea component region as a feature of the present invention similarly to Comparative Example 1, had the island component arranged concentrically from the center of the multicomponent fiber as compared to Example 1, and had a neighboring island component parallelization degree ⁇ of 25°.
  • the multicomponent fiber of Comparative Example 3 had no particular problem in the spinning step, but suffered frequent thread breakage in the drawing step.
  • the mechanical properties of the multicomponent fiber although varied, were satisfactory (strength: 2.5 cN/dtex and elongation: 38%), and due to a large inter-island component distance, sea component solubility was acceptable (sea component solubility: Good).
  • the quality of the multicomponent fiber was not satisfactory, and also the arrangement of the island component was not a regular arrangement as intended by the present invention, there was a limit on enhancement of the fiber structure of the island component, and coming-off of the ultrafine fiber frequently occurred at the time when sea removal was completed (evaluation of coming-off: Bad).
  • the ultrafine fiber had much lower mechanical properties (strength: 1.5 cN/dtex and elongation: 13%) as compared to Example 1, and was poor in quality. Spinning conditions and results of evaluation of the multicomponent fiber and the ultrafine fiber are shown in Table 2.
  • Comparative Example 4 Except that the same pipe type spinneret as that in Comparative Example 3, which included a nozzle plate in which a sea component region forming hole group was not arranged, was used, and the island polymer ratio was 70%, the same procedure as in Example 1 was carried out to obtain a multicomponent fiber. In Comparative Example 4, spinning was performed with the island polymer ratio set to 80%, but island components were fused together to collapse the composite cross section, and therefore spinning was performed with the island polymer ratio reduced to 70%.
  • the multicomponent fiber of Comparative Example 4 was not provided with a sea component region as a feature of the present invention similarly to Comparative Example 3, and had the island component densely arranged on the cross section of the multicomponent fiber because the island polymer ratio was increased as compared to Comparative Example 3.
  • the neighboring island component parallelization degree ⁇ was 17°.
  • a composite spinneret was used which included a nozzle plate 11 in which island component pipe groups were arranged to form an equilateral-triangular lattice, and as illustrated in Fig. 17 , composite polymer discharge holes 15 existed, and sea polymer admission channels (having no discharge holes) were provided, the composite spinneret being the same pipe type spinneret as that in Comparative Example 3 in which a sea component region forming hole group was not arranged. Further, the island polymer ratio was 80%. This condition was based on the method disclosed in Patent Document 2. Except that the above-described condition was employed, the same procedure as in Example 1 was carried out to obtain a multicomponent fiber.
  • Example 8 A composite spinneret was used which included a nozzle plate in which the number of holes in the sea component region forming hole group in the nozzle plate illustrated in Fig. 28 and used in Example 6 was increased by a factor of 3 (Example 8), by a factor of 10 (Example 9) and by a factor of 40 (Example 10) in the shaded regions in Fig. 28 for changing the sea component region width H. Further, the island polymer ratio was changed as shown in Table 3 for adjusting the inter-island component distance. Except that the above-described changes were made, the same procedure as in Example 6 was carried out to obtain a multicomponent fiber.
  • the multicomponent fiber had excellent mechanical properties with the strength being 3.2 cN/dtex or more and the elongation being 29% or more.
  • the fabric had excellent quality.
  • sea component solubility tended to be improved as the size of the sea component region increased, and particularly in Examples 9 and 10, the multicomponent fiber had extremely excellent performance, and similarly to Example 5, ultrafine fibers were already generated in a sample obtained through the treatment performed for 5 minutes.
  • Example 11 A composite spinneret was used which included, in place of the nozzle plate used in Example 5, a nozzle plate provided with eight sea component region forming hole groups which extended inward from the outer layer and which were absent at the center.
  • the island polymer ratio was 70%. Except that the above-described changes were made, the same procedure as in Example 5 was carried out to obtain a multicomponent fiber (Example 11).
  • Example 12 spinning was carried out at a stretch ratio of 1.7 under the same spinning conditions as in Example 11 except that the spinning velocity was changed to 3000 m/min.
  • Example 11 eight sea component regions were formed as illustrated in Fig. 20 . From comparison with the cross section in Example 5, it was confirmed that a composite cross section was formed in which the number of sea component regions was increased from 4 to 8 while the size of the sea component region was comparable (L/D: 0.25 and H/D: 0.03) . In each of Examples 11 and 12, there was no problem in the Spinning step, and particularly in Example 12, thread breakage was not noticeable although the spinning velocity was increased by a factor of 2 to 3000 m/min.
  • sea component solubility was satisfactory (sea component solubility: Good) due to an increase in the number of sea component regions, and ultrafine fibers generated from the multicomponent fibers had excellent mechanical properties.
  • the results are shown in Table 3.
  • Example 13 a composite spinneret was used which included a nozzle plate in which sea component region forming hole groups were arranged so as to extend across the nozzle hole collection while orthogonally crossing each other as shown in Fig. 5 . Except that the above-described change was made, the same procedure as in Example 11 was carried out to obtain a multicomponent fiber (Example 13). In Example 14, spinning was carried out at a stretch ratio of 1.7 under the same spinning conditions as in Example 13 except that the spinning velocity was changed to 3000 m/min.
  • sea component regions were formed so as to extend across the cross section of the multicomponent fiber and orthogonally cross each other at the center of the multicomponent fiber as shown in Fig. 13 (L/D: 1.00).
  • the area ratio of the sea component region increased at the multicomponent fiber cross section with the ratio As/Ac being 0.153 while the sea component region width (H/D: 0.03) was comparable to that in Example 11, and sea component solubility of the multicomponent fiber was further improved as compared to Example 11 (sea component solubility: Very Good).
  • the multicomponent fiber was observed to be divided into a plurality of parts for samples treated with an aqueous sodium hydroxide solution for 5 minutes similarly to Example 5.
  • the multicomponent fiber was divided into a plurality of parts in the initial stage of sea removal in the sea removal treatment. Owing to this effect, the treatment time for completing sea removal was reduced although the multicomponent fiber had a relatively high island polymer ratio of 70% in the multicomponent fibers of Examples 13 and 14. Accordingly, coming-off of the ultrafine fiber was hardly observed (evaluation of coming-off: Very Good). The results are shown in Table 3.
  • Example 13 In place of the nozzle plate used in Example 13, a nozzle plate was provided in which sea component region forming hole groups continuously arranged so as to extend across the nozzle hole collection 18 were added and evenly arranged as shown in Fig. 32 . Except that a composite spinneret was used which included a nozzle plate as illustrated in Fig. 32 , the same procedure as in Example 13 was carried out to spin a multicomponent fiber. In Example 15, four sea component regions were arranged at intervals of 45° so as to extend across the cross section of the multicomponent fiber as shown in Fig. 21 (H/D: 0.03 and L/D: 1.00).
  • Example 15 sea component regions extended through the cross section of the fiber to further divide the sea-island region, so that in the initial stage of sea removal, the multicomponent fiber was easily divided into a plurality of parts, leading to an increase in apparent surface area exposed to an aqueous sodium hydroxide solution, and thus the multicomponent fiber had more satisfactory sea component solubility as compared to Example 13 (sea component solubility: Very Good) .
  • the time required for completing sea removal was reduced as compared to comparative examples, and coming-off of the ultrafine fiber hardly occurred (evaluation of coming-off: Very Good).
  • the results are shown in Table 3.
  • a nozzle plate was provided in which as shown in Fig. 33 , island discharge holes 13 and sea discharge holes 12 were arranged to form a tetragonal lattice, and the sea component region forming hole group was arranged over a range of 0.5R from the center of the nozzle hole collection 18 toward the outer layer (hole packing density: 1.5 holes/mm 2 ).
  • Example 17 a multicomponent fiber (Example 17) .
  • Example 17 Except that a nozzle plate 2 was used in which the hole packing density of the spinneret used in Example 17 was changed to 0.3 holes/mm 2 , the same procedure as in Example 11 was carried out to perform spinning in Example 18. In each of Examples 17 and 18, sea component regions were formed so as to extend in eight directions from the center of the multicomponent fiber as shown in Fig. 22 . Since the hole packing density was changed, the ratios H/D and As/Ac of the multicomponent fiber were changed as shown in Table 4 while the ratio L/D was 0.50.
  • the multicomponent fiber of each of Examples 17 and 18 had cracks formed on the cross section thereof through the removal treatment performed for 5 minutes in the same manner as in Example 5, so that an aqueous sodium hydroxide solution infiltrated into the inner part of the multicomponent fiber in the initial stage of the sea removal treatment although the sea component region did not reach the outermost layer of the multicomponent fiber. Therefore, the multicomponent fiber of Example 18 had excellent sea component solubility (sea component solubility: Very Good) because the sea component region was widely formed, and the multicomponent fiber of Example 17 also had satisfactory sea component solubility (sea component solubility: Good) owing to the effect of crack formation as described above. The results are shown in Table 4.
  • a nozzle plate was used in which removing sea discharge hole groups were arranged in such a manner that sea component regions were formed in a trapezoidal shape at the center of the multicomponent fiber as shown in Fig. 34 , and the hole packing density was 0.3 holes/mm 2 .
  • the removing sea discharge hole groups were continuously arranged over a range of 0.4R from the center of the nozzle hole collection 18, with the sea component regions formed horizontally symmetrically in the multicomponent fiber. Except that a composite spinneret was used which included a nozzle plate as illustrated in Fig. 34 , the same procedure as in Example 17 was carried out to obtain a multicomponent fiber.
  • Example 19 In the multicomponent fiber of Example 19, trapezoidal sea component regions continuously extending in the circumferential direction (120°) as shown in Fig. 23 were formed on the cross section of the fiber depending on the arrangement of sea component region forming hole groups. In Example 19, the sea component region did not reach the outermost layer of the multicomponent fiber similarly to Example 18, but from observation of a sample similar to that of Example 5, which was subjected to a short-time sea removal treatment (5 minutes), it was found that cracks were formed on the cross section of the multicomponent fiber in the initial stage of sea removal.
  • Example 21 spinning was carried out at a stretch ratio of 1.5 under the same spinning conditions as in Example 20 except that the spinning velocity was changed to 3000 m/min.
  • Example 20 due to expansion of the range over which the removing sea discharge hole group was arranged, the sea component region formed in the multicomponent fiber was expanded in comparison with Example 19 as illustrated in Fig. 24 .
  • Example 20 due to expansion of the sea component region formed in the multicomponent fiber, crack formation and infiltration of an aqueous sodium hydroxide solution in the initial stage of sea removal were facilitated as compared to Example 19, so that the multicomponent fiber had excellent sea component solubility (sea component solubility: Very Good), and the treatment time required for completing sea removal was reduced, so that coming-off of the ultrafine fiber was not observed (evaluation of coming-off: Very Good).
  • the ultrafine fiber after sea removal had excellent mechanical properties, and the resulting ultrafine fiber bundle was free from fibrillation etc., and thus had excellent quality.
  • thread breakage did not occur in the spinning step and the drawing step although the spinning velocity was increased, and thus the multicomponent fiber had satisfactory Spinning performance.
  • cracks were formed in the multicomponent fiber in the initial stage of the sea removal treatment similarly to Example 19, and thus the multicomponent fiber was confirmed to have satisfactory sea component solubility (sea component solubility: Good).
  • Example 11 Except that a composite spinneret was used which included a nozzle plate in which removing sea discharge hole groups were arranged in such a manner that sea component regions orthogonally crossed one another at equal intervals on the cross section of the multicomponent fiber as illustrated in Fig. 35 , the same procedure as in Example 11 was carried out to obtain a multicomponent fiber.
  • sea component regions were formed at equal intervals while being between a sea-island region as illustrated in Fig. 26 .
  • Example 22 a plurality of cracks were apparently formed on the composite cross section in a short-time-treated sample similar to that of Example 5, and the sea-island region was divided into a plurality of parts. Owing to the effect of dividing the multicomponent fiber into a plurality of parts in the initial stage of the sea removal treatment, the specific surface area of the sea polymer exposed to an aqueous sodium hydroxide solution increased, so that the multicomponent fiber had extremely excellent sea component solubility (sea component solubility: Very Good) .
  • Example 19 Except that a composite spinneret was used which included a nozzle plate in which removing sea discharge hole groups were arranged in such a manner that sea component regions were formed in a trigonal shape at the center of the multicomponent fiber as illustrated in Fig. 36 , and the hole packing density was 0.3 holes/mm 2 , the same procedure as in Example 19 was carried out to obtain a multicomponent fiber.
  • Example 23 trigonal sea component regions as shown in Fig. 25 were formed on the cross section of the fiber depending on the arrangement of sea component region forming hole groups.
  • the sea component region did not reach the outermost layer of the multicomponent fiber similarly to Example 19, but from observation of a sample similar to that of Example 5, which was subjected to a short-time sea removal treatment (5 minutes), it was found that cracks were formed on the cross section of the multicomponent fiber in the initial stage of sea removal. Therefore, sea component solubility of the sample was satisfactory (sea component solubility: Very Good), and the sea removal time was reduced, so that coming-off of the ultrafine fiber at the time when sea removal was completed was suppressed (evaluation of coming-off: Very Good). The results are shown in Table 4.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Multicomponent Fibers (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (9)

  1. Fibre multicomposant comprenant un composant de mer et un composant d'îlot, dans laquelle
    dans l'observation en section transversale de la fibre multicomposant, la fibre multicomposant comprend :
    une région mer-îlot avec la pluralité de composants d'îlot agencés de façon régulière dans le composant de mer ; et
    une ou plusieurs régions de composant de mer formées uniquement du composant de mer entre la région mer-îlot, et dans laquelle
    la largeur (H) de la région de composant de mer est plus élevée que la valeur maximale de la distance (W) entre les composants d'îlot existant dans la région mer-îlot et voisins les uns des autres, et la largeur (H) de la région de composant de mer et le diamètre (D) de la fibre multicomposant satisfont à la formule suivante : 0,001 < H / D < 0,2.
    Figure imgb0016
  2. Fibre multicomposant selon la revendication 1, dans laquelle la région de composant de mer s'étend vers l'intérieur depuis une couche de surface de la fibre multicomposant.
  3. Fibre multicomposant selon la revendication 1 ou 2, dans laquelle, dans l'observation en section transversale de la fibre multicomposant mer-îlot, la largeur (H) de la région de composant de mer est supérieure au diamètre maximal (d) du composant d'îlot.
  4. Fibre multicomposant selon l'une quelconque des revendications 1 à 3, dans laquelle, dans l'observation en section transversale, l'aire de section transversale (Ac) de la fibre multicomposant et la somme des aires (As) des régions de composant de mer satisfont à la formule suivante : As / Ac 0,35.
    Figure imgb0017
  5. Fibre multicomposant selon l'une quelconque des revendications 1 à 4, dans laquelle, dans l'observation en section transversale, l'aire de section transversale (Ac) de la fibre multicomposant et la somme des aires (As) des régions de composant de mer satisfont à la formule suivante : 0,05 As / Ac .
    Figure imgb0018
  6. Fibre multicomposant selon l'une quelconque des revendications 1 à 5, dans laquelle, dans l'observation en section transversale, la région de composant de mer est cruciforme.
  7. Procédé de production d'une fibre ultrafine, comprenant l'étape de : retrait d'un composant de mer de la fibre multicomposant selon l'une quelconque des revendications 1 à 6.
  8. Produit de fibre comprenant la fibre selon l'une quelconque des revendications 1 à 6.
  9. Produit de fibre comprenant une fibre ultrafine obtenue par le procédé selon la revendication 7.
EP13855930.7A 2012-11-19 2013-11-15 Fibre conjuguée et procédé de fabrication des fibres ultrafines Active EP2921576B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012253208 2012-11-19
PCT/JP2013/080891 WO2014077359A1 (fr) 2012-11-19 2013-11-15 Filière composite, fibre conjuguée et procédé de fabrication de la fibre conjuguée

Publications (3)

Publication Number Publication Date
EP2921576A1 EP2921576A1 (fr) 2015-09-23
EP2921576A4 EP2921576A4 (fr) 2016-06-29
EP2921576B1 true EP2921576B1 (fr) 2019-06-05

Family

ID=50731268

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13855930.7A Active EP2921576B1 (fr) 2012-11-19 2013-11-15 Fibre conjuguée et procédé de fabrication des fibres ultrafines

Country Status (7)

Country Link
US (2) US20150329991A1 (fr)
EP (1) EP2921576B1 (fr)
JP (1) JP6344235B2 (fr)
KR (1) KR102061153B1 (fr)
CN (1) CN104797748B (fr)
TW (1) TWI633216B (fr)
WO (1) WO2014077359A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11566349B2 (en) 2015-03-27 2023-01-31 The United States Of America As Represented By The Secretary Of The Army High strength 3D-printed polymer structures and methods of formation
US10773405B2 (en) * 2016-06-30 2020-09-15 The Gillette Company Llc Shaving aid for razor cartridges comprising a nano-filament comprising a core and sheath
WO2018083047A1 (fr) * 2016-11-03 2018-05-11 ETH Zürich Échafaudage fibrillaire poreux aligné pour ingénierie tissulaire et application chirurgicale
JP7260362B2 (ja) * 2019-03-29 2023-04-18 帝人フロンティア株式会社 海島型複合繊維およびそれからなる多孔中空繊維
US11945154B2 (en) * 2019-11-18 2024-04-02 Pablo Gabriel de León Printer and printing method for space and pressure suits using additive manufacturing
CN111101238B (zh) * 2019-12-24 2023-02-28 江苏恒力化纤股份有限公司 一种并列型自卷曲弹性纤维及其制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531368A (en) * 1966-01-07 1970-09-29 Toray Industries Synthetic filaments and the like
JPS463816Y1 (fr) * 1966-04-11 1971-02-09
JPS6052202B2 (ja) * 1982-09-20 1985-11-18 東レ株式会社 多成分系繊維用紡糸装置
JPH063816A (ja) * 1992-06-19 1994-01-14 Fuji Photo Film Co Ltd 印刷版用ポジ型感光性組成物
JP3288469B2 (ja) * 1993-03-24 2002-06-04 日本バイリーン株式会社 多孔質繊維の製造方法
JP3506790B2 (ja) * 1994-12-27 2004-03-15 日本バイリーン株式会社 複合繊維及びこれを用いた繊維シート
DE19748733A1 (de) * 1997-11-05 1999-05-06 Pedex & Co Gmbh Monofil zur Herstellung von Borsten und Verfahren zur Herstellung von Borsten aus solchen Monofilen
JP4220640B2 (ja) 2000-01-07 2009-02-04 帝人ファイバー株式会社 海島型複合繊維の紡糸口金及びそれを用いた紡糸方法
US20050095935A1 (en) * 2003-11-03 2005-05-05 Mark Levine Durable highly conductive synthetic fabric construction
CN1938461B (zh) * 2004-03-30 2011-04-27 帝人纤维株式会社 海岛型复合纤维及其制造方法
JP2008038275A (ja) * 2006-08-03 2008-02-21 Teijin Fibers Ltd 分割型複合繊維の複合紡糸口金
JP5145004B2 (ja) * 2007-10-05 2013-02-13 帝人ファイバー株式会社 海島型複合繊維用紡糸口金
KR100975351B1 (ko) * 2009-01-30 2010-08-11 웅진케미칼 주식회사 휘도강화필름
KR100953437B1 (ko) * 2009-02-13 2010-04-20 웅진케미칼 주식회사 해도사 제조용 방사구금
JP2011032611A (ja) * 2009-08-04 2011-02-17 Teijin Fibers Ltd 海島型複合繊維用紡糸口金
JP5703785B2 (ja) * 2010-01-29 2015-04-22 東レ株式会社 複合口金
US8969224B2 (en) * 2010-01-29 2015-03-03 Toray Industries, Inc. Sea-island composite fiber, ultrafine fiber, and composite spinneret
JP5505030B2 (ja) 2010-03-30 2014-05-28 東レ株式会社 複合口金および複合繊維の製造方法
WO2012090538A1 (fr) * 2010-12-27 2012-07-05 東レ株式会社 Filière composite et procédé de fabrication de fibres composites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2921576A1 (fr) 2015-09-23
CN104797748A (zh) 2015-07-22
TW201425666A (zh) 2014-07-01
WO2014077359A1 (fr) 2014-05-22
TWI633216B (zh) 2018-08-21
JPWO2014077359A1 (ja) 2017-01-05
EP2921576A4 (fr) 2016-06-29
JP6344235B2 (ja) 2018-06-20
CN104797748B (zh) 2018-04-03
KR102061153B1 (ko) 2019-12-31
US20180320290A1 (en) 2018-11-08
US20150329991A1 (en) 2015-11-19
KR20150086235A (ko) 2015-07-27

Similar Documents

Publication Publication Date Title
US20180320290A1 (en) Composite spinneret that produces multicomponent fibers
US10604866B2 (en) Sea-island composite fiber, composite ultra-fine fiber, and fiber product
KR101250683B1 (ko) 해도형 복합섬유 및 그 제조방법
TWI551738B (zh) 海島型複合纖維、極細纖維及複合紡嘴
US9663876B2 (en) Sea-island composite fiber, mixed yarn and fiber product
TWI541399B (zh) 複合纖維
TWI579423B (zh) 海島纖維
JP5821714B2 (ja) 複合口金および複合繊維の製造方法
US11142847B2 (en) Spinning nozzle, process for producing fibrous mass, fibrous mass, and paper
JP2013014872A (ja) 複合口金および複合繊維の製造方法
JP4705451B2 (ja) 海島型複合繊維の製造方法
KR102584803B1 (ko) 고강력 세섬도 폴리에스테르 멀티필라멘트
WO2023171363A1 (fr) Procédé de fabrication d&#39;une fibre bicomposée, et filière bicomposante
TW202223184A (zh) 海島型複合纖維及含有海島型複合纖維之纖維製品
KR950000722B1 (ko) 추출형 복합섬유

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150507

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20160531

RIC1 Information provided on ipc code assigned before grant

Ipc: D01D 5/36 20060101ALI20160524BHEP

Ipc: D01F 8/00 20060101AFI20160524BHEP

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20181218

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MASUDA, MASATO

Inventor name: MIYASHITA, MASAOMI

Inventor name: FUNAKOSHI, JOJI

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1140062

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013056332

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190905

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190906

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1140062

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191007

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191005

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013056332

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

26N No opposition filed

Effective date: 20200306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191130

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191115

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131115

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20210930

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20211014

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20211018

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190605

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220621

Year of fee payment: 10

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230515

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20221201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20221115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20231010

Year of fee payment: 11